CN112221536A - Titanium-silicon molecular sieve packaged nano-copper catalyst and preparation method and application thereof - Google Patents

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

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CN112221536A
CN112221536A CN202011105750.7A CN202011105750A CN112221536A CN 112221536 A CN112221536 A CN 112221536A CN 202011105750 A CN202011105750 A CN 202011105750A CN 112221536 A CN112221536 A CN 112221536A
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copper
molecular sieve
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furfural
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CN112221536B (en
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谢林峰
罗文豪
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Kunshan Puruikai Nano Technology Co ltd
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • B01J35/393—
    • B01J35/399—
    • 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
    • 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)
    • 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
    • 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
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention provides a titanium silicalite molecular sieve crystal encapsulated copper metal nanoparticle catalyst and application thereof in a reaction for preparing furfuryl alcohol through selective hydrogenation of furfural, which can realize that the conversion rate of furfural is up to more than 99% and the selectivity of furfuryl alcohol is up to more than 98% under mild conditions. The catalyst consists of a titanium silicalite molecular sieve carrier, and an active component and a catalytic assistant which are loaded on the carrier, wherein the active component is copper nanoparticles, and the catalytic assistant is sodium. The metal is uniformly dispersed on the carrier, and the valence state of copper is mainly monovalent copper and accounts for 72 percent; the auxiliary agent sodium optimizes and adjusts the proportion of monovalent copper and the acid amount, and adjusts and improves the selectivity of the product furfuryl alcohol. 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 silicalite molecular sieve catalyst provided by the invention is novel in structure, has higher reaction activity and selectivity when being applied to the reaction of preparing furfuryl alcohol by selective hydrogenation of furfural, and has wide application in the field of furfuryl alcohol preparation by selective hydrogenation of furfural.

Description

Titanium-silicon molecular sieve packaged 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 nanoparticles, a preparation method of the molecular sieve catalyst and application of the molecular sieve catalyst in the reaction of preparing furfuryl alcohol through selective hydrogenation of furfural.
Background
With the increasing depletion of non-renewable fossil energy and the increasing worsening of environmental issues, the development of high-value-added bio-based chemicals produced using renewable biomass resources has become the focus of research in recent years. The furfural is a cheap chemical raw material prepared by hydrolyzing, dehydrating, distilling, refining and the like wood or agricultural and sideline products which are cheap and easily available and have wide sources, is used as an important biomass platform molecule, and is an important intermediate for synthesizing various chemical products. Wherein, furfuryl alcohol is an important product prepared by catalytic hydrogenation of furfural, and is widely applied to the synthesis of industrial products such as resin, rubber, fiber, pesticide and the like.
Due to the special molecular structure of furfural, furan ring functional groups and aldehyde functional groups exist in the molecular structure of furfural, so that the furfural has very active chemical properties, and the product of hydrogenation reaction is complex (ChemSusChem,2012,5(1): 150-66). Therefore, how to avoid the over-hydrogenation of furan ring and ensure the preferential hydrogenation of aldehyde group is the problem to be solved firstly in the process of synthesizing furfuryl alcohol by selective hydrogenation of furfural, and the development of a proper catalyst plays a key role in solving the problem.
The gas phase hydrogenation of furfural to produce furfuryl alcohol is generally carried out by using a copper-chromium catalyst in the industry, but the method has the problems of harsh hydrogenation conditions, high cost, easy heavy metal pollution and the like (Chemical Reviews,2007,107: 2411-2502). The furfural liquid phase hydrogenation can be carried out under mild conditions, and the catalyst does not contain heavy metals. The active metals used in the furfural liquid phase hydrogenation catalyst include common noble metal catalysts such as palladium, platinum, ruthenium (Fuel,2018,226: 607-617; Applied Catalysis B: Environmental,2016,180:580-585) and non-noble metal catalysts such as nickel, copper, cobalt (Journal of Catalysis,2011,277(1): 1-13; Journal of Catalysis,2016,336: 107-115; Fuel,2010,89(10): 2697-2702). Although the noble metal catalyst has high hydrogenation activity, the noble metal catalyst also has the defects of high cost, difficult control of selectivity and the like. In order to solve the above problems, the research and development of non-noble metal catalysts in the reaction are receiving more and more attention from researchers, especially the precise preparation of the catalysts at nanometer level. Therefore, it is necessary to develop a catalyst with low cost, high activity and high selectivity and a corresponding preparation process.
Disclosure of Invention
The invention aims to provide a copper nanoparticle catalyst, a preparation method thereof and application of the copper nanoparticle catalyst in the reaction of preparing furfuryl alcohol by selective hydrogenation of furfural, and solves the problem that the activity of the existing copper-based catalyst taking copper as an active component is low when furfuryl alcohol is prepared by hydrogenation of furfural. The method utilizes the crystal structure of the titanium-silicon molecular sieve to package the copper nanoparticles in situ, and can inhibit the aggregation and growth of copper due to the limited domain effect of the framework and the pore structure of the molecular sieve, so as to obtain copper clusters with smaller sizes, thereby being beneficial to improving the activity of the copper clusters on the furfural hydrogenation reaction. 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 furfuryl alcohol, and have important research value and application potential.
The technical means adopted by the invention are as follows:
a titanium-silicon molecular sieve packaged nano-copper catalyst comprises a molecular sieve carrier, an active component and a catalytic assistant, wherein the active component and the catalytic assistant are loaded on the molecular sieve carrier; the molecular sieve carrier is TS-1; the active component is metallic copper; the catalytic promoter is sodium.
Furthermore, the mass percentage of the active component metallic copper is 0.5 wt% -3 wt%, wherein the monovalent copper accounts for 60% -80%, and the zero-valent copper accounts for 20% -40%.
Furthermore, the mass percent of the catalytic promoter sodium is 0.05 wt% -0.25 wt%.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
(1) uniformly mixing ethyl orthosilicate 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-silica sol at 30-90 ℃ to obtain titanium-silica gel;
(2) dissolving copper nitrate trihydrate into deionized water, adding tetraethylenepentamine, 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) putting 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 is finished; centrifuging the cooled product, drying at 60-100 ℃ for 2-12 hours, and roasting at 550-600 ℃ for 6-12 hours 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, then performing centrifugal operation, and drying the molecular sieve obtained by centrifugation at 60-100 ℃ for 2-12 hours; and (3) placing the dried molecular sieve in hydrogen/nitrogen mixed gas with the hydrogen volume fraction of 5%, and reducing for 1-4 hours at 250-450 ℃ to obtain the target catalyst.
Further, in the step (1), the molar ratio of tetrapropylammonium hydroxide to ethyl orthosilicate is 0.1-2; the molar 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 an application of the catalyst in the reaction of preparing furfuryl alcohol by selective hydrogenation of furfural.
Further, the reaction for preparing furfuryl alcohol by selective hydrogenation of furfural is carried out in a closed high-pressure reaction kettle by stirring, the reactant is furfural, the solvent is ethanol or isopropanol, and the concentration of the reaction solution is 0.05-0.5 mol/L.
Further, the reaction temperature of the reaction for preparing furfuryl alcohol by selective hydrogenation of furfural is 100-140 ℃; the reaction time is 0.5 to 4 hours.
Further, the hydrogen pressure in a reaction kettle for preparing furfuryl alcohol by selective hydrogenation of furfural is 0.5-2 MPa.
Compared with the prior art, the invention has the following advantages:
(1) the organic amine and copper ion complexing mode can effectively promote the copper precursor to be uniformly dispersed in the initial gel synthesized by the molecular sieve, and the copper precursor is ensured to be encapsulated in the molecular sieve crystal in the crystallization process. Due to the limited domain effect of the molecular sieve pore canal, the anti-sintering performance of the copper nanoparticles can be improved, so that the copper nanoparticles are highly dispersed in the molecular sieve crystal, and the particle size of the copper-loaded titanium silicalite molecular sieve obtained by the impregnation method is obviously smaller than that of the copper-loaded titanium silicalite molecular sieve obtained by the impregnation method.
(2) The introduction of sodium changes the valence state of copper, reduces the proportion of monovalent copper, simultaneously reduces the acidity of the catalyst, and is beneficial to improving the selectivity of furfural.
(3) The catalyst of the invention shows excellent catalytic activity when used for catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol, 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 selective hydrogenation of furfural to prepare furfuryl alcohol, a reaction system (comprising furfural, isopropanol and the catalyst) is simple, the reaction condition is mild, and the catalyst and a 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 spectrum of the catalyst sample, 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 silica sol, adding 1.08 g of butyl titanate into 13.1 g of isopropanol, stirring for 5 minutes, adding the mixture into the silica sol, stirring for 60 minutes, adding 37.68 g of deionized water, and stirring for 30 minutes to prepare titanium-silica sol; placing the obtained titanium-silicon gel in a water bath at 60 ℃, heating and stirring for 150 minutes, and removing alcohol 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 mixture into the titanium-silicon gel, and stirring for 1 hour; the titanium-silicon gel is put into a reaction kettle and crystallized for 48 hours at 170 ℃, cooled to room temperature after crystallization is finished, the obtained product is centrifuged, dried for 6 hours at 100 ℃, and roasted for 6 hours at 550 ℃; adding the obtained product into 1 mol/L sodium nitrate solution, heating to 90 ℃, carrying out 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%), and reducing for 1 hour at the temperature of 400 ℃ 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 figure 1a, and as can be seen from the figure, copper nanoparticles with the average particle size 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 results of the obtained Na-Cu @ TS-1 catalyst are shown in Table 1, and NH3TPD (temperature-temperature detection) shows that the total acid amount of example 1 is 0.054mmol/g, pyridine infrared characterization shows that the weak acid amount of example 1 at a desorption temperature of 200 ℃ is 0.034mmol/g, and the strong acid amount at a desorption temperature of 350 ℃ is 0.019 mmol/g.
Comparative example 1 preparation of 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 silica sol, adding 1.08 g of butyl titanate into 13.1 g of isopropanol, stirring for 5 minutes, adding the mixture into the silica sol, stirring for 60 minutes, adding 37.68 g of deionized water, and stirring for 30 minutes to prepare titanium silica sol; placing the obtained titanium silicagel in a water bath at 60 ℃, heating and stirring for 150 minutes, and removing alcohol to obtain 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 mixture into titanium silicagel, and stirring for 1 hour; the titanium silicagel is put into a reaction kettle and crystallized for 48 hours at 170 ℃, the titanium silicagel is cooled to room temperature after the crystallization is finished, the obtained product is centrifuged, dried for 6 hours at 100 ℃, and roasted 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%), and reducing for 1 hour at the temperature of 400 ℃ to obtain the Cu @ TS-1 molecular sieve catalyst.
The scanning transmission electron microscope of the obtained Cu @ TS-1 catalyst is shown in figure 1b, and it can be seen from the figure that comparative example 1 obtains 1-2 nm of copper nanoparticles and is highly dispersed in the TS-1 molecular sieve.
The Cu LMM Auger electron energy spectrum of the obtained Cu @ TS-1 catalyst is shown in figure 2, and the content of the monovalent copper in the copper nano-particles obtained in the comparative example 1 is 83%, which is obviously higher than the monovalent copper proportion (72%) in the example 1.
The results of the characterization of the acid sites of the obtained Cu @ TS-1 catalyst are shown in Table 1, NH3TPD characterisation the total acid obtained in comparative example 1 was found to be 0.060mmol/g, which is significantly higher than the total acid in example 1 (0.054 mmol/g). This comparative example illustrates that the introduction of Na ions reduces the number of acid sites of the catalyst.
Comparative example 2 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 silica sol, adding 1.08 g of butyl titanate into 13.1 g of isopropanol, stirring for 5 minutes, adding the mixture into the silica sol, stirring for 60 minutes, adding 37.68 g of deionized water, and stirring for 30 minutes to prepare titanium silica sol; placing the obtained titanium silicagel in a water bath at 60 ℃, heating and stirring for 150 minutes, and removing alcohol to obtain titanium silicagel; the titanium silicagel is put into a reaction kettle and crystallized for 48 hours at 170 ℃, the titanium silicagel is cooled to room temperature after crystallization, the obtained product is centrifuged, dried for 6 hours at 100 ℃, and roasted for 6 hours at 550 ℃ to obtain the TS-1 molecular sieve; weighing 0.076 g of solid copper nitrate nonahydrate, adding 1.32 ml of water to dissolve the solid copper nitrate nonahydrate according to the water absorption capacity of 1 g of TS-1 molecular sieve, then weighing 1 g of TS-1 molecular sieve, mixing the solution and the molecular sieve by adopting an isovolumetric impregnation method, uniformly stirring, 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 ℃, carrying out 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%), and reducing for 1 hour at the temperature of 400 ℃ 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 figure 1c, and it can be seen from the figure that comparative example 2 obtains copper nanoparticles of 5.0 nm, and the aggregation phenomenon can be obviously observed.
The Cu LMM Auger electron energy spectrum of the obtained Na-Cu/TS-1 catalyst is shown in figure 2, and the content of monovalent copper in the copper nanoparticles obtained in comparative example 2 is 49%.
The results of the characterization of the acid sites of the obtained Na-Cu/TS-1 catalyst are shown in Table 1, NH3TPD characterisation the total acid obtained in comparative example 2 was found to be 0.036 mmol/g. This comparative example shows that the size of the catalyst Cu particle without the coating structure becomes large and the introduction of Na ion greatly reduces the content of monovalent copper and the acid site.
Table 1 acid site characterization of different catalysts
Figure BDA0002726901180000061
Example 2 reaction of selective hydrogenation of furfural to furfuryl alcohol with Na-Cu @ TS-1 catalyst
The reaction for preparing furfuryl alcohol by selective hydrogenation of furfural is carried out in a high-pressure reaction kettle which is provided with a heating sleeve. Firstly, adding 0.3 g of furfural, 0.3 g of Na-Cu @ TS-1 catalyst and 23.56 g of isopropanol into a 100 ml high-pressure reaction kettle at room temperature, introducing nitrogen for three times of replacement, introducing hydrogen for three times of replacement, setting the hydrogen pressure to 1 MPa, stirring at the speed of 200 revolutions per minute, simultaneously heating to 110 ℃, adjusting the rotating speed to 1000 revolutions per minute, and reacting for 1 hour. After the reaction is finished, stopping stirring, cooling to below 20 ℃, taking a proper amount of reaction liquid for centrifugal separation, and performing gas chromatography analysis. The reaction results are shown in Table 2.
Example 3 reaction of selective hydrogenation of Furfural to furfuryl alcohol with Na-Cu @ TS-1 catalyst
The reaction for preparing furfuryl alcohol by selective hydrogenation of furfural is carried out in a high-pressure reaction kettle which is provided with a heating sleeve. Firstly, adding 0.3 g of furfural, 0.3 g of Na-Cu @ TS-1 catalyst and 23.56 g of isopropanol into a 100 ml high-pressure reaction kettle at room temperature, introducing nitrogen for three times of replacement, introducing hydrogen for three times of replacement, setting the hydrogen pressure to 1 MPa, stirring at the speed of 200 revolutions per minute, simultaneously heating to 110 ℃, adjusting the rotating speed to 1000 revolutions per minute, and reacting for 2 hours. After the reaction is finished, stopping stirring, cooling to below 20 ℃, taking a proper amount of reaction liquid for centrifugal separation, and performing gas chromatography analysis. The reaction results are shown in Table 2.
Example 4 preparation of furfuryl alcohol by Selective hydrogenation of Furfural with Na-Cu @ TS-1 catalyst
The reaction for preparing furfuryl alcohol by selective hydrogenation of furfural is carried out in a high-pressure reaction kettle which is provided with a heating sleeve. Firstly, adding 0.3 g of furfural, 0.3 g of Na-Cu @ TS-1 catalyst and 23.56 g of isopropanol into a 100 ml high-pressure reaction kettle at room temperature, introducing nitrogen for three times of replacement, introducing hydrogen for three times of replacement, setting the hydrogen pressure to 1 MPa, stirring at the speed of 200 revolutions per minute, simultaneously heating to 110 ℃, adjusting the rotating speed to 1000 revolutions per minute, and reacting for 3 hours. After the reaction is finished, stopping stirring, cooling to below 20 ℃, taking a proper amount of reaction liquid for centrifugal separation, and performing gas chromatography analysis. The reaction results are shown in Table 2.
Example 5 preparation of furfuryl alcohol by Selective hydrogenation of Furfural with Na-Cu @ TS-1 catalyst
The reaction for preparing furfuryl alcohol by selective hydrogenation of furfural is carried out in a high-pressure reaction kettle which is provided with a heating sleeve. Firstly, adding 0.3 g of furfural, 0.3 g of Na-Cu @ TS-1 catalyst and 23.56 g of isopropanol into a 100 ml high-pressure reaction kettle at room temperature, introducing nitrogen for three times of replacement, introducing hydrogen for three times of replacement, setting the hydrogen pressure to 1 MPa, stirring at the speed of 200 revolutions per minute, simultaneously heating to 110 ℃, adjusting the rotating speed to 1000 revolutions per minute, and reacting for 4 hours. After the reaction is finished, stopping stirring, cooling to below 20 ℃, taking a proper amount of reaction liquid for centrifugal separation, and performing gas chromatography analysis. The reaction results are shown in Table 2.
Example 6 preparation of furfuryl alcohol by Selective hydrogenation of Furfural with Na-Cu @ TS-1 catalyst
The reaction for preparing furfuryl alcohol by selective hydrogenation of furfural is carried out in a high-pressure reaction kettle which is provided with a heating sleeve. Firstly, adding 0.3 g of furfural, 0.3 g of Na-Cu @ TS-1 catalyst and 23.56 g of isopropanol into a 100 ml high-pressure reaction kettle at room temperature, introducing nitrogen for three times of replacement, introducing hydrogen for three times of replacement, setting the hydrogen pressure to 1 MPa, stirring at the speed of 200 revolutions per minute, simultaneously heating to 120 ℃, adjusting the rotating speed to 1000 revolutions per minute, and reacting for 1 hour. After the reaction is finished, stopping stirring, cooling to below 20 ℃, taking a proper amount of reaction liquid for centrifugal separation, and performing gas chromatography analysis. The reaction results are shown in Table 2.
Example 7 Na-Cu @ TS-1 catalyst for Furfural Selective hydrogenation to furfuryl alcohol
The reaction for preparing furfuryl alcohol by selective hydrogenation of furfural is carried out in a high-pressure reaction kettle which is provided with a heating sleeve. Firstly, adding 0.3 g of furfural, 0.3 g of Na-Cu @ TS-1 catalyst and 23.56 g of isopropanol into a 100 ml high-pressure reaction kettle at room temperature, introducing nitrogen for three times of replacement, introducing hydrogen for three times of replacement, setting the hydrogen pressure to 1 MPa, stirring at the speed of 200 revolutions per minute, simultaneously heating to 130 ℃, adjusting the rotating speed to 1000 revolutions per minute, and reacting for 1 hour. After the reaction is finished, stopping stirring, cooling to below 20 ℃, taking a proper amount of reaction liquid for centrifugal separation, and performing gas chromatography analysis. The reaction results are shown in Table 2.
Example 8 reaction of selective hydrogenation of Furfural to furfuryl alcohol with Na-Cu @ TS-1 catalyst
The reaction for preparing furfuryl alcohol by selective hydrogenation of furfural is carried out in a high-pressure reaction kettle which is provided with a heating sleeve. Firstly, adding 0.3 g of furfural, 0.3 g of Na-Cu @ TS-1 catalyst and 23.56 g of isopropanol into a 100 ml high-pressure reaction kettle at room temperature, introducing nitrogen for three times of replacement, introducing hydrogen for three times of replacement, setting the hydrogen pressure to 1 MPa, stirring at the speed of 200 revolutions per minute, simultaneously heating to 140 ℃, adjusting the rotating speed to 1000 revolutions per minute, and reacting for 1 hour. After the reaction is finished, stopping stirring, cooling to below 20 ℃, taking a proper amount of reaction liquid for centrifugal separation, and performing gas chromatography analysis. The reaction results are shown in Table 2.
TABLE 2 catalytic reaction results
Figure BDA0002726901180000081
Example 9 comparison of catalytic reaction Performance of catalysts
The reaction performances of Na-Cu @ TS-1, Cu @ TS-1 and Na-Cu/TS-1 catalysts for preparing furfuryl alcohol by selective hydrogenation of furfural are compared, the reaction conditions are the same as those in example 2, and the reaction results are shown in Table 3.
TABLE 3 comparison of catalytic Properties of different catalysts
Figure BDA0002726901180000082
As can be seen from Table 3, the Na-Cu @ TS-1 catalyst has the highest reactivity and furfuryl alcohol selectivity.

Claims (10)

1. A titanium-silicon molecular sieve packaged nano-copper catalyst comprises a molecular sieve carrier, an active component and a catalytic assistant, wherein the active component and the catalytic assistant are loaded on the molecular sieve carrier, and the molecular sieve carrier is TS-1; the active component is metallic copper; the catalytic promoter is sodium.
2. The catalyst according to claim 1, wherein the mass percentage of the active component metallic copper is 0.5-3 wt%, wherein the monovalent copper accounts for 60-80%, and the zero-valent copper accounts for 20-40%.
3. The catalyst according to claim 1, wherein the mass percent of the catalytic promoter sodium is 0.05 wt% to 0.25 wt%.
4. A method for preparing a catalyst as claimed in any one of claims 1 to 3, comprising the steps of:
(1) uniformly mixing ethyl orthosilicate 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-silica sol at 30-90 ℃ to obtain titanium-silica gel;
(2) dissolving copper nitrate trihydrate into deionized water, adding tetraethylenepentamine, 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) putting 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 is finished; centrifuging the cooled product, drying at 60-100 ℃ for 2-12 hours, and roasting at 550-600 ℃ for 6-12 hours 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, then performing centrifugal operation, and drying the molecular sieve obtained by centrifugation at 60-100 ℃ for 2-12 hours; and (3) placing the dried molecular sieve in hydrogen/nitrogen mixed gas with the hydrogen volume fraction of 5%, and reducing for 1-4 hours at 250-450 ℃ to obtain the target catalyst.
5. The method for preparing a catalyst according to claim 4, wherein in the step (1), the molar ratio of tetrapropylammonium hydroxide to tetraethoxysilane is 0.1-2; the molar ratio of the isopropanol to the butyl titanate is 10-100.
6. The method of preparing a catalyst according to claim 4, wherein in the step (2), the molar ratio of tetravinyl pentamine to copper nitrate trihydrate is 0.1 to 3.
7. Use of a catalyst according to any one of claims 1 to 3 in the selective hydrogenation of furfural to furfuryl alcohol.
8. The application of the method according to claim 7, wherein the reaction for preparing furfuryl alcohol by selective hydrogenation of furfural is carried out in a closed high-pressure reaction kettle by stirring, the reactant is furfural, the solvent is ethanol or isopropanol, and the concentration of the reaction solution is 0.05-0.5 mol/L.
9. The application of the method according to claim 7, wherein the reaction temperature of the selective hydrogenation reaction of furfural to prepare furfuryl alcohol is 100-140 ℃; the reaction time is 0.5 to 4 hours.
10. The application of claim 7, wherein the hydrogen pressure in the selective hydrogenation reaction of furfural to furfuryl alcohol is 0.5-2 MPa.
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