CN112221536B - Titanium-silicon molecular sieve encapsulated nano copper catalyst and preparation method and application thereof - Google Patents

Titanium-silicon molecular sieve encapsulated nano copper catalyst and preparation method and application thereof Download PDF

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CN112221536B
CN112221536B CN202011105750.7A CN202011105750A CN112221536B CN 112221536 B CN112221536 B CN 112221536B CN 202011105750 A CN202011105750 A CN 202011105750A CN 112221536 B CN112221536 B CN 112221536B
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furfural
titanium
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谢林峰
罗文豪
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Kunshan Puruikai Nano Technology Co ltd
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C07D307/44—Furfuryl alcohol
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention provides a titanium-silicon molecular sieve crystal internal packaging copper metal nanoparticle catalyst and application thereof in furfuryl alcohol preparation reaction by furfural selective hydrogenation, which can realize that under mild conditions, the furfural conversion rate is up to more than 99%, and the furfuryl alcohol selectivity is up to more than 98%. The catalyst consists of a titanium-silicon molecular sieve carrier, an active component and a catalytic auxiliary agent, wherein the active component and the catalytic auxiliary agent are loaded on the carrier, the active component is copper nano-particles, and the catalytic auxiliary agent is sodium. The metal is uniformly dispersed on the carrier, and the valence state of copper is 72 percent by taking monovalent copper as the main component; the auxiliary sodium optimally adjusts the proportion of monovalent copper and the acid quantity, and adjusts and improves the selectivity of the furfuryl alcohol product. The reaction system is simple, the reaction condition is mild, and the catalyst and the solvent are easy to separate and recycle. The copper nanoparticle-loaded titanium-silicon molecular sieve catalyst provided by the invention has a novel structure, is applied to furfuryl alcohol preparation reaction by selective hydrogenation of furfural, has higher reaction activity and selectivity, and has wide application in the furfuryl alcohol preparation application field by selective hydrogenation of furfural.

Description

Titanium-silicon molecular sieve encapsulated nano copper catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a molecular sieve catalyst containing copper nano particles, a preparation method thereof and application thereof in furfuryl alcohol preparation reaction by selective hydrogenation of furfural.
Background
With the increasing exhaustion of non-renewable fossil energy sources and the continuous worsening of environmental problems, development of bio-based chemicals that use renewable biomass resources to produce high added values has been the focus of research in recent years. The furfural is an inexpensive chemical raw material prepared from cheap and easily available wood or agricultural and sideline products with wide sources through the processes of hydrolysis, dehydration, distillation, refining and the like, is taken as an important biomass platform molecule, and is an important intermediate for synthesizing various chemical products. Furfuryl alcohol is an important product prepared by catalytic hydrogenation of furfural, and is widely applied to synthesis of industrial products such as resin, rubber, fiber, pesticide and the like.
Since the molecular structure of furfural is special, furan ring functional groups and aldehyde functional groups exist in the molecular structure of furfural at the same time, so that the chemical property of the furfural is very active, and the hydrogenation reaction of the furfural is a complex product (ChemSusChem, 2012,5 (1): 150-66). Therefore, how to avoid excessive hydrogenation of furan ring, ensure preferential hydrogenation of aldehyde group is the first problem to be solved in the process of synthesizing furfuryl alcohol by selective hydrogenation of furfural, and developing a proper catalyst plays a key role in solving the problem.
The industrial production of furfuryl alcohol by gas phase hydrogenation of furfural using copper-chromium catalyst has problems of severe hydrogenation conditions, high cost, and easy heavy metal pollution (Chemical Reviews,2007, 107:2411-2502). The liquid-phase hydrogenation of furfural can be carried out under milder conditions, and the catalyst generally does not contain heavy metals. Active metals used in the furfural liquid-phase hydrogenation catalyst include common noble metal catalysts such as palladium, platinum and ruthenium (Fuel, 2018,226:607-617;Applied Catalysis B:Environmental,2016,180:580-585) and non-noble metal catalysts such as nickel, copper and cobalt (Journal of Catalysis,2011,277 (1): 1-13;Journal of Catalysis,2016,336:107-115; fuel,2010,89 (10): 2697-2702). Noble metal catalysts, although having high hydrogenation activity, suffer from the disadvantages of high cost, difficult selectivity control, and the like. In order to solve the above problems, research and development of non-noble metal catalysts in the reaction are receiving increasing attention from researchers, especially the precise preparation of catalysts at the nanometer level. Therefore, it is necessary to develop a catalyst with low cost, high activity and high selectivity and a corresponding preparation process thereof.
Disclosure of Invention
The invention aims to provide a copper nanoparticle catalyst, a preparation method thereof and application thereof in furfuryl alcohol preparation reaction by furfural selective hydrogenation, and solves the problem that the existing copper-based catalyst taking copper as an active component has lower activity in furfuryl alcohol preparation by furfural hydrogenation. According to the invention, the titanium-silicon molecular sieve crystal structure is utilized to encapsulate the copper nano particles in situ, and the aggregation and growth of copper can be inhibited due to the limited domain effect of the molecular sieve framework and the pore canal structure, so that copper clusters with smaller size are obtained, and the activity of the copper clusters on the hydrogenation reaction of furfural is improved. Meanwhile, the addition of sodium can effectively modulate the electronic structure of copper, inhibit side reactions in the reaction process, such as aldol condensation reaction and the like, improve the selectivity of the copper to furfuryl alcohol, and have important research value and application potential.
The invention adopts the following technical means:
a titanium-silicon molecular sieve encapsulated nano copper catalyst comprises a molecular sieve carrier, an active component and a catalytic auxiliary agent, wherein the active component and the catalytic auxiliary agent are loaded on the molecular sieve carrier; the molecular sieve carrier is TS-1; the active component is metallic copper; the catalyst promoter is sodium.
Further, the mass percentage of the active component metallic copper is 0.5-3wt%, wherein the monovalent copper accounts for 60-80%, and the zero-valent copper accounts for 20-40%.
Further, the mass percent of the catalyst promoter sodium is 0.05 to 0.25 percent.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
(1) Uniformly mixing tetraethoxysilane and tetrapropylammonium hydroxide to obtain silica sol; uniformly mixing butyl titanate and isopropanol, adding the mixture into the silica sol, stirring, adding deionized water, and stirring to generate titanium-silica sol; stirring and aging the titanium-silicon sol at the temperature of between 30 and 90 ℃ to obtain titanium-silicon gel;
(2) Dissolving copper nitrate trihydrate in deionized water, adding tetravinyl pentamine, and uniformly mixing to obtain a copper complex solution; adding a copper complex solution into the titanium-silicon gel to obtain a copper-containing titanium-silicon gel precursor;
(3) Filling the obtained copper-containing titanium-silicon gel precursor into a reaction kettle, crystallizing at 160-200 ℃ for 24-72 hours, and cooling to room temperature after crystallization; centrifuging the cooled product, drying for 2-12 hours at 60-100 ℃, and roasting for 6-12 hours at 550-600 ℃ to obtain the target molecular sieve;
(4) Adding the target molecular sieve obtained in the step (3) into 0.5-1.5 mol/L sodium nitrate solution, heating to 80-90 ℃ for ion exchange, keeping for 2-4 hours, centrifuging, and drying the molecular sieve obtained by centrifugation at 60-100 ℃ for 2-12 hours; and (3) placing the dried molecular sieve in a hydrogen/nitrogen mixed gas with the hydrogen volume fraction of 5%, and reducing for 1-4 hours at the temperature of 250-450 ℃ to obtain the target catalyst.
Further, in the step (1), the molar ratio of tetrapropylammonium hydroxide to tetraethoxysilane is 0.1-2; the mol ratio of the isopropanol to the butyl titanate is 10-100.
Further, in the step (2), the molar ratio of the tetravinyl pentamine to the copper nitrate trihydrate is 0.1-3.
The invention also provides application of the catalyst in furfuryl alcohol preparation reaction by selective hydrogenation of furfural.
Further, the furfuryl alcohol is prepared by selectively hydrogenating the furfural in a closed high-pressure reaction kettle with stirring, the reactant is furfural, the solvent is ethanol or isopropanol, and the concentration of the reaction solution is 0.05-0.5 mol/liter.
Further, the reaction temperature of furfuryl alcohol preparation reaction by selective hydrogenation of furfural is 100-140 ℃; the reaction time is 0.5-4 hours.
Further, the hydrogen pressure in the reaction kettle for preparing furfuryl alcohol by selectively hydrogenating furfural is 0.5-2 megapascals.
Compared with the prior art, the invention has the following advantages:
(1) The complexing mode of the organic amine and the copper ions can effectively promote the copper precursor to be uniformly dispersed in the initial gel synthesized by the molecular sieve, and ensure that the copper precursor is encapsulated in the molecular sieve crystal in the crystallization process. Due to the limited domain function of the molecular sieve pore canal, the sintering resistance of the copper nano particles can be improved, so that the copper nano particles are highly dispersed in the molecular sieve crystal, and the particle size is obviously smaller than that of the copper-loaded titanium silicon molecular sieve obtained by the impregnation method.
(2) The introduction of sodium changes the valence state of copper, reduces the proportion of monovalent copper, reduces the acidity of the catalyst, and is beneficial to improving the selectivity of furfural.
(3) The catalyst provided by the invention has excellent catalytic activity when used for catalyzing furfuryl alcohol preparation reaction by selective hydrogenation of furfural, the conversion rate can reach more than 99%, and the furfuryl alcohol selectivity can reach more than 98%.
(4) When the catalyst is used for catalyzing furfuryl alcohol preparation reaction by selective hydrogenation of furfural, the reaction system is simple (comprising furfural, isopropanol and catalyst), the reaction condition is mild, and the catalyst and the reaction liquid are easy to separate and recycle.
Drawings
Fig. 1: (a) is a scanning transmission electron micrograph of Na-Cu@TS-1 prepared in example 1, (b) is a scanning transmission electron micrograph of Cu@TS-1 prepared in comparative example 1, and (c) is a scanning transmission electron micrograph of Na-Cu/TS-1 prepared in comparative example 2;
fig. 2: cu LMM Auger electron energy spectra of catalyst samples, wherein Na-Cu@TS-1, cu@TS-1 and Na-Cu/TS-1 correspond to the catalyst samples obtained in example 1, comparative example 1 and comparative example 2, respectively.
Detailed Description
Example 1 preparation of Na-Cu@TS-1 catalyst
Weighing 20 g of ethyl orthosilicate, adding the ethyl orthosilicate into 11.4 g of tetrapropylammonium hydroxide (the concentration is 25%), stirring for 30 minutes to obtain a silica sol, adding 1.08 g of butyl titanate into 13.1 g of isopropanol, stirring for 5 minutes, adding the butyl titanate into the silica sol, stirring for 60 minutes, adding 37.68 g of deionized water, and stirring for 30 minutes to obtain titanium-silica sol; placing the obtained titanium-silicon gel in a water bath at 60 ℃ for heating and stirring for 150 minutes to remove alcohol, so as to obtain titanium-silicon gel; adding 0.43 g of copper nitrate trihydrate into 13.1 g of deionized water, stirring until the copper nitrate trihydrate is dissolved, adding 0.37 g of tetraethylenepentamine, stirring for 5 minutes, adding the copper nitrate trihydrate into titanium-silicon gel, and stirring for 1 hour; putting the titanium-silicon gel into a reaction kettle, crystallizing for 48 hours at 170 ℃, cooling to room temperature after crystallization, centrifuging the obtained product, drying for 6 hours at 100 ℃, and roasting for 6 hours at 550 ℃; adding the obtained product into 1 mol/L sodium nitrate solution, heating to 90 ℃ for ion exchange for 2 hours, centrifuging the obtained product, and drying at 100 ℃ for 6 hours; and (3) placing the obtained product in a reducing atmosphere (hydrogen and nitrogen mixed gas with the hydrogen volume fraction of 5 percent), and reducing at 400 ℃ for 1 hour to obtain the Na-Cu@TS-1 molecular sieve catalyst.
The scanning transmission electron microscope of the obtained Na-Cu@TS-1 catalyst is shown in FIG. 1a, and it can be seen from the figure that the copper nanoparticles with average particle diameters of 1-2 nanometers are obtained in example 1 and are highly dispersed in the TS-1 molecular sieve.
The Cu LMM Auger electron spectrum of the obtained Na-Cu@TS-1 catalyst is shown in FIG. 2, and the content of monovalent copper in the copper nanoparticles obtained in example 1 is 72%.
The Lewis acid site characterization result of the obtained Na-Cu@TS-1 catalyst is shown in Table 1, NH 3 The total acid content of example 1 was determined to be 0.054mmol/g by TPD characterization, the weak acid content of example 1 was determined to be 0.034mmol/g by pyridine IR characterization at a desorption temperature of 200 degrees Celsius, and the strong acid content was determined to be 0.019mmol/g at a desorption temperature of 350 degrees Celsius.
Preparation of comparative example 1 Cu@TS-1 catalyst
Weighing 20 g of ethyl orthosilicate, adding the ethyl orthosilicate into 11.4 g of tetrapropylammonium hydroxide (the concentration is 25%), stirring for 30 minutes to obtain a silica sol, adding 1.08 g of butyl titanate into 13.1 g of isopropanol, stirring for 5 minutes, adding the butyl titanate into the silica sol, stirring for 60 minutes, adding 37.68 g of deionized water, and stirring for 30 minutes to obtain a titanium silica sol; placing the obtained titanium silicagel in a water bath at 60 ℃ for heating and stirring for 150 minutes to remove alcohol, thus obtaining titanium silicagel; adding 0.43 g of copper nitrate trihydrate into 13.1 g of deionized water, stirring until the copper nitrate trihydrate is dissolved, adding 0.37 g of tetraethylenepentamine, stirring for 5 minutes, adding the copper nitrate trihydrate into titanium silicagel, and stirring for 1 hour; putting the titanium silicagel into a reaction kettle, crystallizing for 48 hours at 170 ℃, cooling to room temperature after crystallization, centrifuging the obtained product, drying for 6 hours at 100 ℃, and roasting for 6 hours at 550 ℃; and (3) placing the obtained product in a reducing atmosphere (hydrogen and nitrogen mixed gas with the hydrogen volume fraction of 5 percent), and reducing at 400 ℃ for 1 hour to obtain the Cu@TS-1 molecular sieve catalyst.
The scanning transmission electron microscope of the obtained Cu@TS-1 catalyst is shown in FIG. 1b, and as can be seen from the figure, the comparative example 1 obtains copper nanoparticles of 1-2 nanometers, and the copper nanoparticles are highly dispersed in a TS-1 molecular sieve.
The Cu LMM Auger electron spectrum of the obtained Cu@TS-1 catalyst is shown in FIG. 2, and the content of monovalent copper in the obtained copper nanoparticles of comparative example 1 is 83%, which is obviously higher than the monovalent copper proportion (72%) in example 1.
The characterization result of the acid site of the obtained Cu@TS-1 catalyst is shown in table 1, NH 3 TPD characterization measures a total acid amount of 0.060mmol/g for comparative example 1, which is significantly higher than the total acid amount (0.054 mmol/g) in example 1. This comparative example illustrates that the introduction of Na ions reduces the number of acid sites of the catalyst.
Preparation of comparative example 2 Na-Cu/TS-1 catalyst
Weighing 20 g of ethyl orthosilicate, adding the ethyl orthosilicate into 11.4 g of tetrapropylammonium hydroxide (the concentration is 25%), stirring for 30 minutes to obtain a silica sol, adding 1.08 g of butyl titanate into 13.1 g of isopropanol, stirring for 5 minutes, adding the butyl titanate into the silica sol, stirring for 60 minutes, adding 37.68 g of deionized water, and stirring for 30 minutes to obtain a titanium silica sol; placing the obtained titanium silicagel in a water bath at 60 ℃ for heating and stirring for 150 minutes to remove alcohol, thus obtaining titanium silicagel; putting the titanium silicagel into a reaction kettle, crystallizing for 48 hours at 170 ℃, cooling to room temperature after crystallization, centrifuging the obtained product, drying for 6 hours at 100 ℃, and roasting for 6 hours at 550 ℃ to obtain a TS-1 molecular sieve; weighing 0.076 g of copper nitrate nonahydrate solid, adding 1.32 ml of water for dissolution according to the water absorption capacity of 1 g of TS-1 molecular sieve, weighing 1 g of TS-1 molecular sieve, mixing the solution and the molecular sieve by adopting an isovolumetric impregnation method, uniformly stirring and standing overnight, drying at 80 ℃ for 5 hours, and roasting at 400 ℃ for 4 hours; adding the obtained product into 1 mol/L sodium nitrate solution, heating to 90 ℃ for ion exchange for 2 hours, centrifuging the obtained product, and drying at 100 ℃ for 6 hours; and (3) placing the obtained product in a reducing atmosphere (hydrogen and nitrogen mixed gas with the volume fraction of 5 percent of hydrogen), and reducing at 400 ℃ for 1 hour to obtain the Na-Cu/TS-1 molecular sieve catalyst.
The scanning transmission electron microscope of the obtained Na-Cu/TS-1 catalyst is shown in FIG. 1c, and as can be seen from the figure, the comparative example 2 obtained copper nanoparticles of 5.0 nanometers, and the aggregation phenomenon can be clearly observed.
The Cu LMM Auger electron spectrum of the obtained Na-Cu/TS-1 catalyst is shown in figure 2, and the content of monovalent copper in the copper nano-particles obtained in comparative example 2 is 49%.
The characterization result of the acid site of the obtained Na-Cu/TS-1 catalyst is shown in Table 1, NH 3 TPD characterization measured a total acid amount of 0.036mmol/g for comparative example 2. This comparative example demonstrates that the catalyst Cu particles without a coating structure become larger in size and that the introduction of Na ions greatly reduces the monovalent copper content and acid sites.
Table 1 characterization of the acid sites of different catalysts
Figure BDA0002726901180000061
Example 2 reaction of furfurol preparation by Selective hydrogenation of Furfural catalyzed by Na-Cu@TS-1 catalyst
The furfuryl alcohol is prepared by selectively hydrogenating furfural in a high pressure reactor with heating jacket. Firstly, 0.3 g of furfural, 0.3 g of Na-Cu@TS-1 catalyst and 23.56 g of isopropanol are added into a 100 ml high-pressure reaction kettle at room temperature, nitrogen is introduced for three times, hydrogen is introduced for three times, the hydrogen pressure is set to 1 megaPa, stirring is carried out at the speed of 200 revolutions per minute, the temperature is increased to 110 ℃, the rotating speed is adjusted to 1000 revolutions per minute at the moment, and the reaction is carried out for 1 hour. After the reaction is finished, stopping stirring and cooling to below 20 ℃, taking a proper amount of reaction liquid for centrifugal separation, and carrying out gas chromatography analysis. The reaction results are shown in Table 2.
Example 3 reaction of furfurol preparation by Selective hydrogenation of Furfural catalyzed by Na-Cu@TS-1 catalyst
The furfuryl alcohol is prepared by selectively hydrogenating furfural in a high pressure reactor with heating jacket. Firstly, 0.3 g of furfural, 0.3 g of Na-Cu@TS-1 catalyst and 23.56 g of isopropanol are added into a 100 ml high-pressure reaction kettle at room temperature, nitrogen is introduced for three times, hydrogen is introduced for three times, the hydrogen pressure is set to 1 megaPa, stirring is carried out at the speed of 200 revolutions per minute, the temperature is increased to 110 ℃, the rotating speed is adjusted to 1000 revolutions per minute at the moment, and the reaction is carried out for 2 hours. After the reaction is finished, stopping stirring and cooling to below 20 ℃, taking a proper amount of reaction liquid for centrifugal separation, and carrying out gas chromatography analysis. The reaction results are shown in Table 2.
Example 4 reaction of furfurol preparation by Selective hydrogenation of Furfural catalyzed by Na-Cu@TS-1 catalyst
The furfuryl alcohol is prepared by selectively hydrogenating furfural in a high pressure reactor with heating jacket. Firstly, 0.3 g of furfural, 0.3 g of Na-Cu@TS-1 catalyst and 23.56 g of isopropanol are added into a 100 ml high-pressure reaction kettle at room temperature, nitrogen is introduced for three times, hydrogen is introduced for three times, the hydrogen pressure is set to 1 megaPa, stirring is carried out at the speed of 200 revolutions per minute, the temperature is increased to 110 ℃, the rotating speed is adjusted to 1000 revolutions per minute at the moment, and the reaction is carried out for 3 hours. After the reaction is finished, stopping stirring and cooling to below 20 ℃, taking a proper amount of reaction liquid for centrifugal separation, and carrying out gas chromatography analysis. The reaction results are shown in Table 2.
Example 5 Na-Cu@TS-1 catalyst catalyzes the reaction of preparing furfuryl alcohol by selectively hydrogenating furfuraldehyde
The furfuryl alcohol is prepared by selectively hydrogenating furfural in a high pressure reactor with heating jacket. Firstly, 0.3 g of furfural, 0.3 g of Na-Cu@TS-1 catalyst and 23.56 g of isopropanol are added into a 100 ml high-pressure reaction kettle at room temperature, nitrogen is introduced for three times, hydrogen is introduced for three times, the hydrogen pressure is set to 1 megaPa, stirring is carried out at the speed of 200 revolutions per minute, the temperature is increased to 110 ℃, the rotating speed is adjusted to 1000 revolutions per minute at the moment, and the reaction is carried out for 4 hours. After the reaction is finished, stopping stirring and cooling to below 20 ℃, taking a proper amount of reaction liquid for centrifugal separation, and carrying out gas chromatography analysis. The reaction results are shown in Table 2.
Example 6 Na-Cu@TS-1 catalyst catalyzes the reaction of preparing furfuryl alcohol by selectively hydrogenating furfuraldehyde
The furfuryl alcohol is prepared by selectively hydrogenating furfural in a high pressure reactor with heating jacket. Firstly, 0.3 g of furfural, 0.3 g of Na-Cu@TS-1 catalyst and 23.56 g of isopropanol are added into a 100 ml high-pressure reaction kettle at room temperature, nitrogen is introduced for three times, hydrogen is introduced for three times, the hydrogen pressure is set to 1 megaPa, stirring is carried out at the speed of 200 revolutions per minute, the temperature is increased to 120 ℃, the rotating speed is adjusted to 1000 revolutions per minute at the moment, and the reaction is carried out for 1 hour. After the reaction is finished, stopping stirring and cooling to below 20 ℃, taking a proper amount of reaction liquid for centrifugal separation, and carrying out gas chromatography analysis. The reaction results are shown in Table 2.
Example 7 Na-Cu@TS-1 catalyst catalyzes the reaction of preparing furfuryl alcohol by selectively hydrogenating furfuraldehyde
The furfuryl alcohol is prepared by selectively hydrogenating furfural in a high pressure reactor with heating jacket. Firstly, 0.3 g of furfural, 0.3 g of Na-Cu@TS-1 catalyst and 23.56 g of isopropanol are added into a 100 ml high-pressure reaction kettle at room temperature, nitrogen is introduced for three times, hydrogen is introduced for three times, the hydrogen pressure is set to 1 megaPa, stirring is carried out at the speed of 200 revolutions per minute, the temperature is increased to 130 ℃, the rotating speed is adjusted to 1000 revolutions per minute at the moment, and the reaction is carried out for 1 hour. After the reaction is finished, stopping stirring and cooling to below 20 ℃, taking a proper amount of reaction liquid for centrifugal separation, and carrying out gas chromatography analysis. The reaction results are shown in Table 2.
Example 8 reaction of furfurol preparation by Selective hydrogenation of Furfural catalyzed by Na-Cu@TS-1 catalyst
The furfuryl alcohol is prepared by selectively hydrogenating furfural in a high pressure reactor with heating jacket. Firstly, 0.3 g of furfural, 0.3 g of Na-Cu@TS-1 catalyst and 23.56 g of isopropanol are added into a 100 ml high-pressure reaction kettle at room temperature, nitrogen is introduced for three times, hydrogen is introduced for three times, the hydrogen pressure is set to 1 megaPa, stirring is carried out at the speed of 200 revolutions per minute, the temperature is increased to 140 ℃, the rotating speed is adjusted to 1000 revolutions per minute at the moment, and the reaction is carried out for 1 hour. After the reaction is finished, stopping stirring and cooling to below 20 ℃, taking a proper amount of reaction liquid for centrifugal separation, and carrying out gas chromatography analysis. The reaction results are shown in Table 2.
TABLE 2 catalytic reaction results
Figure BDA0002726901180000081
Example 9 comparison of catalytic reactivity of catalysts
The reaction conditions are the same as in example 2 and the reaction results are shown in Table 3, wherein the reaction performance of the Na-Cu@TS-1, cu@TS-1 and Na-Cu/TS-1 catalysts for catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol are compared.
TABLE 3 comparison of catalytic Properties of different catalysts
Figure BDA0002726901180000082
As can be seen from Table 3, the Na-Cu@TS-1 catalyst had the highest reactivity and selectivity to furfuryl alcohol.

Claims (7)

1. A titanium-silicon molecular sieve encapsulated nano-copper catalyst for preparing furfuryl alcohol by selective hydrogenation of furfural comprises a molecular sieve carrier, an active component and a catalytic auxiliary agent, wherein the active component and the catalytic auxiliary agent are loaded on the molecular sieve carrier, and the molecular sieve carrier is TS-1; the active component is metallic copper; the catalyst auxiliary agent is sodium;
the mass percentage of the active component metallic copper is 0.5-3wt%, wherein monovalent copper accounts for 60-80%, and zero-valent copper accounts for 20-40%;
the mass percentage of the catalyst promoter sodium is 0.05 to 0.25 percent;
the preparation method of the catalyst comprises the following steps:
(1) Uniformly mixing tetraethoxysilane and tetrapropylammonium hydroxide to obtain silica sol; uniformly mixing butyl titanate and isopropanol, adding the mixture into the silica sol, stirring, adding deionized water, and stirring to generate titanium-silica sol; stirring and aging the titanium-silicon sol at the temperature of between 30 and 90 ℃ to obtain titanium-silicon gel;
(2) Dissolving copper nitrate trihydrate in deionized water, adding tetravinyl pentamine, and uniformly mixing to obtain a copper complex solution; adding a copper complex solution into the titanium-silicon gel to obtain a copper-containing titanium-silicon gel precursor;
(3) Filling the obtained copper-containing titanium-silicon gel precursor into a reaction kettle, crystallizing at 160-200 ℃ for 24-72 hours, and cooling to room temperature after crystallization; centrifuging the cooled product, drying for 2-12 hours at 60-100 ℃, and roasting for 6-12 hours at 550-600 ℃ to obtain the target molecular sieve;
(4) Adding the target molecular sieve obtained in the step (3) into 0.5-1.5 mol/L sodium nitrate solution, heating to 80-90 ℃ for ion exchange, keeping for 2-4 hours, centrifuging, and drying the molecular sieve obtained by centrifugation at 60-100 ℃ for 2-12 hours; and (3) placing the dried molecular sieve in a hydrogen/nitrogen mixed gas with the hydrogen volume fraction of 5%, and reducing for 1-4 hours at the temperature of 250-450 ℃ to obtain the target catalyst.
2. The catalyst of claim 1, wherein in step (1), the molar ratio of tetrapropylammonium hydroxide to tetraethyl orthosilicate is 0.1-2; the mol ratio of the isopropanol to the butyl titanate is 10-100.
3. The catalyst of claim 1, wherein in step (2), the molar ratio of tetravinyl pentamine to copper nitrate trihydrate is 0.1 to 3.
4. Use of the catalyst of claim 1 in a process for preparing furfuryl alcohol by selective hydrogenation of furfural.
5. The method according to claim 4, wherein the furfuryl alcohol is prepared by selectively hydrogenating furfural in a closed high-pressure reactor with stirring, the reactant is furfural, the solvent is ethanol or isopropanol, and the concentration of the reaction solution is 0.05-0.5 mol/liter.
6. The use according to claim 4, wherein the reaction temperature of the furfuryl alcohol preparation reaction by selective hydrogenation of furfural is 100-140 ℃; the reaction time is 0.5-4 hours.
7. The use according to claim 4, wherein the hydrogen pressure of the furfuryl alcohol prepared by selective hydrogenation of furfural is 0.5 to 2 mpa.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009016141A1 (en) * 2007-07-31 2009-02-05 Shell Internationale Research Maatschappij B.V. Catalyst composition, its preparation and use
CN109126792A (en) * 2018-08-31 2019-01-04 中触媒新材料股份有限公司 A kind of synthesis and application of Cu-Silicate-1 catalyst
CN109833897A (en) * 2017-11-28 2019-06-04 中国科学院大连化学物理研究所 A method of for produce furfuryl alcohol catalyst and its preparation and production furfuryl alcohol
CN110152663A (en) * 2018-02-11 2019-08-23 中国科学院大连化学物理研究所 It is a kind of for the catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol and its preparation and application
CN110368982A (en) * 2019-07-25 2019-10-25 大连理工大学 Non-noble metal nano cluster catalyst and preparation method and application are stablized in Silicalite-1 molecular sieve pore passage confinement
CN111574483A (en) * 2020-05-19 2020-08-25 中山大学 Preparation method of 2, 5-furandimethanol

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009016141A1 (en) * 2007-07-31 2009-02-05 Shell Internationale Research Maatschappij B.V. Catalyst composition, its preparation and use
CN109833897A (en) * 2017-11-28 2019-06-04 中国科学院大连化学物理研究所 A method of for produce furfuryl alcohol catalyst and its preparation and production furfuryl alcohol
CN110152663A (en) * 2018-02-11 2019-08-23 中国科学院大连化学物理研究所 It is a kind of for the catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol and its preparation and application
CN109126792A (en) * 2018-08-31 2019-01-04 中触媒新材料股份有限公司 A kind of synthesis and application of Cu-Silicate-1 catalyst
CN110368982A (en) * 2019-07-25 2019-10-25 大连理工大学 Non-noble metal nano cluster catalyst and preparation method and application are stablized in Silicalite-1 molecular sieve pore passage confinement
CN111574483A (en) * 2020-05-19 2020-08-25 中山大学 Preparation method of 2, 5-furandimethanol

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Selectivity Modulation of Encapsulated Palladium Nanoparticles by Zeolite Microenvironment for Biomass Catalytic Upgrading";Yuchao Chai et al.;《ACS Catal.》;20180806;第8卷;8578-8589 *

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