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CN116571263A - Preparation method of silicon dioxide supported nickel-based catalyst and application of catalyst in hydrogenation of5-hydroxymethylfurfural - Google Patents

Preparation method of silicon dioxide supported nickel-based catalyst and application of catalyst in hydrogenation of5-hydroxymethylfurfural Download PDF

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CN116571263A
CN116571263A CN202310540005.2A CN202310540005A CN116571263A CN 116571263 A CN116571263 A CN 116571263A CN 202310540005 A CN202310540005 A CN 202310540005A CN 116571263 A CN116571263 A CN 116571263A
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catalyst
nickel
supported nickel
hydroxymethylfurfural
hydrogenation
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CN116571263B (en
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曾宪海
黄仁杰
陈炳霖
田野
李铮
林鹿
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Xiamen University
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Abstract

The invention relates to the field of catalysts, in particular to a method for preparing a silicon dioxide supported nickel-based catalyst and application thereof in hydrogenation of biomass platform molecules 5-hydroxymethylfurfural. By Ni 2+ And (3) coordinating with dimethylimidazole to form a Ni-ZIF polymer, adding triethylamine to enable the solution to be alkaline, and then dropwise adding tetraethyl silicate to enable the solution to be slowly hydrolyzed in the solution to prepare the silicon dioxide-loaded Ni catalyst precursor. The precursor is then calcined at high temperature under nitrogen to produce the silica supported nickel-based catalyst. The catalyst can catalyze the hydrogenation of5-hydroxymethylfurfural at room temperature to prepare polymer monomers 2, 5-furandimethanol and 2, 5-dimethyloltetrahydrofuran. The catalyst of the invention not only can catalyze the rapid reaction of5-hydroxymethylfurfural in the presence of water as a solvent, but also can directly catalyze the hydrogenation of5-hydroxymethylfurfural in the absence of solvent, and can catalyze the catalyst containing nitrateSubstrates having unsaturated groups such as a group, carbonyl group, carbon-carbon double bond, etc., exhibit good activity.

Description

Preparation method of silicon dioxide supported nickel-based catalyst and application of catalyst in hydrogenation of5-hydroxymethylfurfural
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for preparing 2, 5-furandimethanol and 2, 5-dimethyloltetrahydrofuran by catalyzing 5-hydroxymethylfurfural at room temperature without a solvent.
Background
With the development of socioeconomic performance, fossil resources dominate the traditional energy structure, but excessive reliance on fossil energy presents a series of economic, social and environmental problems. In order to reduce the dependence on fossil fuel resources, the development of renewable resources such as solar energy, wind energy, biomass energy and the like has important significance. Biomass energy is taken as the only renewable carbon source, and has good prospect for research and development. In biomass, 5-Hydroxymethylfurfural (HMF) as an important platform compound can be converted into a variety of high value-added chemicals such as polymer monomers, fine chemicals, fuel additives, liquid fuels, and the like. HMF hydro-reduction can produce a variety of chemicals such as 2, 5-furandimethanol (BHMF), 2, 5-dimethyloltetrahydrofuran (BHMTHF), 5-Methyl Furfuryl Alcohol (MFA), 2, 5-dimethylfuran, 2, 5-dimethyltetrahydrofuran (BMTHF).
Among the hydrogenated products of HMF, BHMF and BHMTHF are unique glycol industrial intermediates, have wide application prospects in biomass conversion, and can be used for preparing artificial receptors in molecular recognition and preparing artificial fibers, polyamides, polyethers, medicines, adhesives, furanyl resins and other high-added-value fine chemicals [ Hou q., et al biorefinery roadmap based on catalytic production and upgrading-hydroxyymethyl furfurals ]]. In recent years, selective hydrogenation of HMF to BHMF and BHMTHF has been reported in numerous catalytic systems, noble metal catalytic systems such as Pd, pt, ru and Ir and non-noble metals such as Co, ni and Cu and the like to selectively hydrogenate HMF to BHMF and BHMTHF [ Jiang Z.chemical transformations of5-hydroxymethylfurfural to highly added value products: present and future]. In noble metal catalytic systems, it is possible to use a relatively mild H 2 High selectivity conversion of HMF is achieved under conditions. But due to noble metalsThe reserves are low, the price is high, and the supply relation is greatly affected by market fluctuation, so that the development and practical industrial application of the noble metal catalyst are limited. In addition, under relatively harsh conditions, non-noble metal catalyst systems can also achieve efficient conversion of HMF and yield high yields comparable to noble metal catalysts. Such as Zhang et al [ Zhang et al, catalytic selective hydrogenation and rearrangement of5-hydroxymethylfurfural to, 3-hydroxyymethyl-cyclopentone over a bimetallic nickel-copper catalyst in water ]]The 2, 5-dihydroxyterephthalic acid is adopted as an organic ligand and Ni, co, cu, fe is adopted as a metal node, a series of MOF-74 derived single/double metal catalysts (Ni/C, cu/C, fe/C, co/C, ni-Cu, ni-Co, ni-Fe) are prepared, and the temperature is 140 ℃ and the pressure is 20bar H 2 The reaction is carried out for 5 hours, and only the HMF has the conversion rate of more than 99 percent and the BHMTHF yield of 79.1 percent under the catalysis of the Ni/C catalyst. Likozar et Al [ B.Likozaret Al process condition-based tuneable selective catalysis of Hydroxymethylfurfural (HMF) hydrogenation reactions to aromatic, saturated cyclic and linear poly-functional alcohols over Ni-Ce/Al 2 O 3 .]By Ni-Ce/Al 2 O 3 As a catalyst, by adjusting the reaction temperature and the solvent in a mixed system of water and THF, 140 ℃ and 50bar H 2 96% BHMF was obtained. At 190℃and 50bar H in n-butanol as solvent 2 88% BHMTHF was obtained. Zhu et al (Zhu Y, et al, radial design of Ni-based catalysts derived from hydrotalcite for selective hydrogenation of 5-hydroxyymethylfurfural).]Develops a milder catalytic system by utilizing Ni and a carrier Al 2 O 3 Is strong in interaction with the Ni to prepare Ni-Al with the grain size of 3.7nm 2 O 3 Catalyst at 60℃and 60bar H 2 In the following, 100% conversion of HMF and 90.5% yield of BHMTHF were achieved, but there was a problem of serious catalytic deactivation. Patent publication No. CN 113773284A discloses a Co-Ni/SiO 2 Method for preparing BHMTHF by catalyzing 5-hydroxymethylfurfural by using water as solvent at 110 ℃ and 30bar H 2 The reaction was carried out for 4 hours, the yield of BHMTHF was 82.9%, but the reaction temperature was relatively high. The non-noble metal has rich reserve and low priceThe raw materials are relatively easy to obtain, and the like, however, under severe conditions, the HMF is easy to generate various side reactions such as hydrogenolysis, ring opening, polymerization and the like, and the preparation method brings great challenges for obtaining the BHMF and the BHMTHF with high yield and selectivity. Meanwhile, in the production process, a large amount of energy and funds are consumed for product separation and purification, so that the production cost of the product is increased, the HMF has good water solubility, and the environment-friendly and sustainable chemistry principle is considered, water is used as a reaction medium, or solvent-free reaction is directly adopted, so that the cost can be greatly reduced compared with expensive organic solvents. Therefore, the development of the high-efficiency and stable non-noble metal catalyst realizes the selective preparation of BHMF and BHMTHF under mild conditions, and can reduce the separation cost of the products, thereby having important scientific research value and industrial application significance.
Disclosure of Invention
To solve the problems in the prior art, the invention provides a silica supported nickel-based catalyst (Ni-NC/SiO 2 ) Is applied to the preparation of 2, 5-furandimethanol and 2, 5-dimethyloltetrahydrofuran in 5-hydroxymethylfurfural. The catalyst is a non-noble metal catalyst, and the preparation method is simple. The method can catalyze the rapid reaction of the 5-hydroxymethylfurfural in the presence of water as a solvent, and has mild reaction conditions to realize the room-temperature reaction. The catalyst can also directly catalyze the hydrogenation of5-hydroxymethylfurfural under the solvent-free condition, and simultaneously can catalyze substrates containing unsaturated groups such as nitro, carbonyl, carbon-carbon double bonds and the like, and has good activity.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a preparation method of a silicon dioxide supported nickel-based catalyst, which comprises the following steps:
(1) First, nickel acetate and P123 are dissolved in ethanol solution, and the solid is dissolved by ultrasonic treatment for a certain time and fully mixed and coordinated.
(2) Then, the dimethyl imidazole is dissolved in a certain amount of deionized water, and the magnetic stirring is uniform.
(3) And (3) rapidly pouring the solution obtained in the step (1) into the solution obtained in the step (2), magnetically stirring in a water bath for 0.5-2h, rapidly adding triethylamine, and continuously stirring for 0.5-2h. Slowly dripping tetraethyl orthosilicate into the solution, and stirring in a water bath for 10-20h. Then filtering, collecting filter cake, washing, vacuum drying to obtain light blue precursor (Ni-ZIF/SiO 2).
(4) The catalyst precursor (Ni-ZIF/SiO) obtained in the step (3) 2 ) The reduction is carried out in nitrogen atmosphere at 900 ℃ to obtain the nickel catalyst loaded by silicon dioxide.
The addition ratio of the nickel acetate to the P123 to the dimethylimidazole to the triethylamine to the tetraethyl orthosilicate to the ethanol to the deionized water is (0.05-1) g (0.1-3) g (0.1-2) g (0.05-1) g (0.05-2) g (10-50) mL. Preferably (0.1-0.5) g (0.5-2) g (0.5-1) g (0.2-1) g (0.5-1) g (15-25) mL.
Further, the ultrasonic time in the step (1) is 0.1 to 1h, and the preferable result is 0.5h.
Further, the water bath temperature in step (3) is 30-50 ℃, preferably 40 ℃.
Further, the preferable results of the stirring time in the step (3) are 0.5h, 1h, 15h, respectively.
Further, the reduction process in the step (4) is as follows: heating to 400 ℃ at a speed of5 ℃/min in a tube furnace filled with nitrogen, preserving heat for 0.5h, then continuously heating to 900 ℃ at a speed of 2 ℃/min, preserving heat for 2h, then programming to cool to 400 ℃ at a speed of 10 ℃/min, and then naturally cooling to room temperature.
The invention provides the silicon dioxide supported nickel catalyst prepared by the method.
The invention also provides a silica supported nickel catalyst (Ni-NC/SiO) 2 ) The method is applied to the preparation of 2, 5-dihydroxymethyl tetrahydrofuran by hydrogenating 5-hydroxy furfural.
Adding a catalyst, water and 5-hydroxymethylfurfural into a high-pressure-resistant hastelloy reaction kettle according to the dosage ratio of (10-50) mg (10-20) mL to 1mmol, sealing the reaction kettle, filling 1-50bar of hydrogen, and reacting for 1-12h at 25-60 ℃ under magnetic stirring to obtain 2, 5-dimethyloltetrahydrofuran.
Preferably, it is: adding a catalyst, water and 5-hydroxymethylfurfural into a high-pressure-resistant hastelloy reaction kettle according to the dosage ratio of 40mg to 10mL to 1mmol, sealing the reaction kettle, filling 40bar hydrogen, and reacting for 11h at 30 ℃ under magnetic stirring to obtain 2, 5-dimethyloltetrahydrofuran.
The invention also provides a nickel catalyst (Ni-NC/SiO) loaded by the silicon dioxide 2 ) The catalyst is applied to catalyzing the hydrogenation of substrates containing nitro, carbonyl, carbon-carbon double bonds and other unsaturated groups.
Adding a catalyst and a substrate containing unsaturated groups such as nitro, carbonyl, carbon-carbon double bonds and the like into a high-pressure-resistant hastelloy reaction kettle according to the dosage ratio (50-120 mg:5 mmol), sealing the reaction kettle, then filling 1bar-50bar hydrogen, and reacting for 1-12h under magnetic stirring at 25-80 ℃ to obtain a corresponding hydrogenation product.
Preferably, it is: adding a catalyst and a substrate containing unsaturated groups such as nitro, carbonyl, carbon-carbon double bonds and the like into a high-pressure-resistant hastelloy reaction kettle according to the proportion of 100mg to 5mmol, sealing the reaction kettle, then filling 40bar hydrogen, and reacting for 11 hours at 30-80 ℃ under magnetic stirring to obtain a corresponding hydrogenation product. The substrate containing unsaturated groups such as nitro, carbonyl, carbon-carbon double bond and the like is:nitrobenzene, & gtof>5-hydroxymethylfurfural,>furfural, furaldehyde,Benzaldehyde, (-) -benzene>Cinnamaldehyde, & lt & gt>Heptaldehyde, & gt>Pyridine-2-carbaldehyde,Cyclopentanone, < - > or->1-acetophenone, < >>Any one of styrene.
Compared with the prior art, the invention has the following advantages and effects:
1. the invention uses Ni 2+ The catalyst is coordinated with dimethyl imidazole to form a Ni-ZIF polymer, so that the problem of migration and aggregation of metals in the roasting reduction process is solved, and meanwhile, silicon dioxide is adopted as a carrier, so that the content of nickel metal can be effectively reduced, the higher atom utilization rate is realized, the stability of the catalyst can be effectively improved, and the oxidation of the catalyst in air is reduced. The storage time of the catalyst is prolonged.
2. The catalyst prepared by the method is used for catalyzing the water phase hydrogenation of the 5-hydroxymethylfurfural. Compared with the existing method, the method is relatively friendly to the environment, has milder reaction temperature, and can realize the room temperature catalysis of the non-noble metal to prepare the 2, 5-dimethylolfuran by the 5-hydroxymethylfurfural.
3. The catalyst can realize solvent-free hydrogenation of5-hydroxymethylfurfural, and reduce energy consumption for separation and purification. And can catalyze unsaturated group substrates containing nitro, carbonyl, carbon-carbon double bond and the like to hydrogenate, and the catalyst has higher universality.
Drawings
FIG. 1 is a schematic flow chart of a catalyst preparation method of the present invention.
FIG. 2 is a silica supported nickel catalyst precursor (Ni-ZIF/SiO) prepared in example 1 2 ) Is a thermal weight graph of (2).
FIG. 3 silica supported nickel catalyst precursor (Ni-ZIF/SiO) prepared in example 1 2 ) X-ray diffraction pattern (XRD pattern).
FIG. 4 is a silica supported nickel catalyst (Ni-ZIF/SiO) prepared in example 1 2 ) Is a scanning electron microscope image of (c).
FIG. 5 silica supported nickel catalyst prepared in example 1 (Ni-NC/SiO 2 ) X-ray diffraction pattern (XRD pattern).
FIG. 6 silica supported nickel catalyst prepared in example 1 (Ni-NC/SiO 2 ) Nitrogen isothermal adsorption desorption curve and pore size distribution diagram.
FIG. 7 is a silica supported nickel catalyst (Ni-NC/SiO) prepared in example 1 2 ) Transmission electron microscopy images of (c).
FIG. 8 is a silica supported nickel catalyst (Ni-NC/SiO) prepared in example 1 2 ) Particle size distribution of nickel nanoparticles.
FIG. 9 is a silica supported nickel catalyst (Ni-NC/SiO) prepared in example 1 2 ) Scanning electron microscope-EDS (electron microscope-electron microscope) energy spectrum
FIG. 10 silica supported nickel catalyst prepared in example 1 (Ni-NC/SiO 2 ) X-ray photoelectron spectrum (XPS spectrum) Ni2p spectrum.
FIG. 11 silica supported nickel catalyst prepared in example 1 (Ni-NC/SiO 2 ) Is a hydrogen overflow detection object diagram.
FIG. 12 silica supported nickel catalyst prepared in example 1 (Ni-NC/SiO 2 ) Purifying the physical diagram after solvent-free reaction.
Detailed Description
The following detailed description of the embodiments of the present invention refers to the accompanying drawings, which are not intended to limit the scope of the invention.
Unless otherwise specified, reagents and equipment used in the following examples are commercially available products. The specific implementation cases are as follows:
example 1 preparation of silica supported nickel catalyst (Ni-NC/SiO 2):
the reaction process shown in FIG. 1 is specifically prepared by the following method.
(1) First, 0.18 of nickel acetate and 1gP123 were dissolvedDissolving in 20ml ethanol solution, and ultrasonic treating for 0.5 hr to dissolve solid completely and make Ni 2+ And P123.
(2) Then, 0.8g of dimethylimidazole was dissolved in 20ml of deionized water and stirred magnetically well.
(3) And (3) rapidly pouring the solution obtained in the step (1) into the solution obtained in the step (2), magnetically stirring in a water bath for 1h, rapidly adding 0.5g of triethylamine, and continuously stirring for 1h. Slowly dripping 0.45 g or 0.9g or 1.8g tetraethyl orthosilicate into the solution, and stirring in a water bath for 15h. Filtering, collecting filter cake, washing with absolute ethanol, and vacuum drying at 70deg.C to obtain light blue precursor (Ni-ZIF/SiO) 2 )。
(4) The catalyst precursor (Ni-ZIF/SiO) obtained in the step (3) 2 ) In nitrogen atmosphere, the temperature is programmed to 400 ℃ at a temperature rising rate of5 ℃/min, the mixture is kept for 0.5h, the temperature is continuously increased to 900 ℃ at a temperature rising rate of 2 ℃/min, the mixture is kept for 2h, and then the mixture is naturally cooled to room temperature after being programmed to 400 ℃ at a temperature of 10 ℃/min, so as to obtain the nickel catalyst loaded by silicon dioxide.
The silica supported nickel catalyst precursor prepared in example 1 (Ni-ZIF/SiO 2 ) Thermogravimetric analysis was performed. The obtained Ni-ZIF/SiO 2 The thermal decomposition diagram is shown in FIG. 2, and the test data shows that Ni-ZIF/SiO increases with increasing temperature 2 There are three rapid weight loss zones, 30 ℃ to 200 ℃ being the first weight loss zone, and the sample loses weight most rapidly around 197 ℃, which is likely to be the volatilization of water and residual P123 adsorbed by the material. The second rapid weight loss zone is 200-400 ℃, the weight loss speed is the fastest at 370 ℃, the Ni-ZIF structure may begin to collapse in the temperature zone, and partial carbon and nitrogen-containing substances begin to decompose. A rapid loss of weight peak also occurred at around 423 c, indicating further rapid collapse of the Ni-ZIF structure. Then along with the temperature rise, the weight of the material is slowly lost, the carbon material is possibly decomposed continuously at high temperature, nickel metal is reduced, the weight of Ni-ZIF/SiO2 is completely lost by 33.14 percent when the temperature reaches 900 ℃,
FIG. 3 is Ni-ZIF/SiO 2 XRD diffractograms, and physical patterns of different nickel contents. Along with the difference of the using amount of tetraethyl orthosilicate, the dioxygen obtained by hydrolysisThe amount of silicon carbide varies, as does the nickel content of the catalyst. Ni-ZIF/SiO catalyst with high nickel content 2 (H) Darker color, 2θ= 33.84 °,60.06 ° is the relevant diffraction peak of nickel, and its peak intensity is also stronger.
FIG. 4 is a Ni-ZIF/SiO 2 SEM characterization of the catalyst from which it can be seen that the precursors are dendritic with irregular particles cross-linked to each other, and are intricate and stacked on each other. Possibly this is Ni-NC/SiO 2 The reason for the large specific surface area of the catalyst. It is well known that catalysts have a large specific surface area and provide a large number of active sites per unit mass of catalyst in contact with the substrate, which increases the conversion rate of the substrate.
FIG. 5 is a silica supported nickel catalyst (Ni-NC/SiO) prepared in example 1 2 ) X-ray diffraction pattern (XRD pattern). The diffraction pattern of the catalyst and the nickel PDF card were well matched by comparison with the PDF card database (JCPDS, PDF # 04-0850). Characteristic peaks 2θ=44.4 °, 51.9 °, 76.5 ° correspond to (111), (200), and (220) crystal planes of nickel, respectively, and as the nickel content increases, the intensity of diffraction peaks is also stronger. In Ni-NC/SiO 2 In the XRD diffractogram of the catalyst, the strong peak 2θ=21.3° is a characteristic peak of silica. XRD results indicate that the silica supported nickel catalyst has been successfully prepared.
FIG. 6 is a silica supported nickel catalyst precursor (Ni-ZIF/SiO) prepared in example 1 2 ) And calcined catalyst (Ni-NC/SiO) 2 ) N of (2) 2 Adsorption-desorption and pore size distribution. Ni-NC/SiO 2 The nitrogen adsorption isotherm of the catalyst shows an adsorption-desorption isotherm of type IV of the H4 hysteresis loop, which indicates Ni-NC/SiO 2 The catalyst has mesoporous and irregular pore structure, and is slit-pore type. And Ni-ZIF/SiO 2 In contrast, after calcination, ni-NC/SiO 2 The specific surface area of the catalyst becomes smaller, which may be caused by collapse of the catalyst structure during calcination.
The silica supported nickel catalyst prepared in example 1 (Ni-NC/SiO 2 ) Scanning with a Transmission Electron Microscope (TEM), and obtaining a transmission electron microscope spectrum and a particle diameter distribution chart after treatment as shown in FIGS. 7 and 8, from the figuresIt can be found that: it is clear from the TEM image that the nickel nanoparticles are uniformly distributed on the silica support, have uniform size, and do not cause obvious agglomeration. The particle size distribution of the nickel nanoparticles is shown in FIG. 8, with an average particle size of 9.26nm. Consistent with the nickel nanoparticle particles calculated using the Scherrer equation after XRD data (calculated size: 9.18 nm). It should be noted that Ni-NC/SiO 2 The nickel nanoparticles in the TEM image of the catalyst did not significantly agglomerate, which is attributable to the coordination of nickel and dimethylimidazole in the precursor, resulting in high dispersion of nickel. It is demonstrated that highly dispersed silica supported nickel catalysts can be prepared by this method.
FIG. 9 is a silica supported nickel catalyst (Ni-NC/SiO) prepared in example 1 2 ) Is a scanning electron microscope-EDS spectrogram of (c). It can be seen that nickel element is uniformly distributed in the catalyst, and that part of nitrogen and carbon elements remain partially after the Ni-ZIF is roasted. This may be the reason for the high dispersion of nickel nanoparticles in the catalyst without significant agglomeration.
FIG. 10 is an X-ray photoelectron spectrum (XPS spectrum) Ni2p spectrum of a silica-supported nickel catalyst (Ni-NC/SiO 2) prepared in example 1. Peak at 852.6eV binding energy with metallic Ni 0 In relation, the 855.5eV binding energy is attributable to Ni in the oxidized state 2+ The 856.2eV binding energy is attributable to Ni-O-Si. Ni-NC/SiO compared with silicon dioxide directly loaded with nickel 2 Ni in the catalyst 0 The metal content is higher, the oxidation state content is only 15.5%, and the Ni-O-Si state content is also higher, which indicates that the interaction between nickel and the carrier is stronger, and the nickel nano-particles are more stable.
FIG. 11 silica supported nickel catalyst prepared in example 1 (Ni-NC/SiO 2 ) Hydrogen overflow detection graph of (2). Tungsten oxide is unreactive with hydrogen molecules at low temperatures (fig. 11-a, b), and high temperatures of 400 ℃ are required to react. When Ni-NC/SiO 2 Catalyst and WO 3 After mixing, the color of the mixed sample changed significantly from pale yellow to olive after 10min of treatment in a hydrogen atmosphere at 30 ℃ (FIG. 11-d), indicating that active hydrogen species transferred to WO under this condition 3 The catalyst showed that hydrogen flooding occurred. And the sample is treated at 60deg.C for 10minThe color of the sample is obviously deepened, which indicates that more hydrogen is dissociated from the active center of the catalyst under the high temperature condition, and more active hydrogen species overflows to WO 3 And thereby causes the color of the sample to change to a greyish green (fig. 11-e). When the sample was treated overnight at 30℃the colour of the sample changed to dark grey-green (FIG. 11-f), as can be explained by more active hydrogen species and WO 3 Combine to form H x WO 3 Experimental results confirm that hydrogen spills exist on the surface of the catalyst, so that the carrier can become an active center, and the contact probability of the reaction substrate and the active species is increased, which is probably one of reasons for high activity of the catalyst. Both increasing the temperature and extending the reaction time, more active hydrogen species can be produced, consistent with experimental data.
FIG. 12 is a silica supported nickel catalyst (Ni-NC/SiO) prepared in example 1 2 ) Purification scheme after solvent-free reaction. Adding a catalyst and a substrate containing unsaturated groups such as nitro, carbonyl, carbon-carbon double bonds and the like into a high-pressure-resistant alloy reaction kettle according to the proportion of 100mg to 5mmol, sealing the reaction kettle, filling 40bar hydrogen, magnetically stirring, and reacting for 11h at 30-80 ℃. After the reaction is finished, other purification operations are not needed, and the product can be obtained into a pure product with higher purity through twice centrifugation.
Examples 2 to 6
The silica supported nickel catalyst prepared in example 1 (Ni-NC/SiO 2 ) The method is used for preparing 2, 5-dihydroxymethyl tetrahydrofuran by hydrogenating 5-hydroxy furfural, and comprises the following steps:
Ni-NC/SiO 2 Catalyst (40 mg), 5-hydroxymethylfurfural (1 mmol) and water (10 mL) were added to a high-pressure-resistant hastelloy reaction vessel, the reaction vessel was sealed, the air in the reaction vessel was replaced with hydrogen for 5 to 6 times, then hydrogen was charged under a certain pressure, the autoclave was heated to a set temperature (e.g., 60 ℃ C.) and stirred under magnetic stirring at a rate of 1000RPM (revolutions per minute, r/min) for 5 hours. Waiting for the end of the reaction, cooling the autoclave to room temperature and decompressing, filtering the reaction solution with a 0.45 μm organic filter head, subjecting the reaction solution to ultra-high phase liquid chromatography (Agilent 1260) detection, and identifying the product with a gas mass spectrometer (Trace 1300-ISQ). The reaction results of different hydrogen pressures affect the reaction rate, and are shown in table 1:
TABLE 1
Based on the above results, it is found that the higher the hydrogen pressure, the higher the conversion, the more 89% when the hydrogen pressure reaches 20bar, and the 99% when the hydrogen pressure reaches 30bar, so that the hydrogen pressure is preferably 20bar or more, more preferably 40bar.
Examples 7 to 11
According to the procedure and procedure of example 6, different reaction temperatures were varied to give 2, 5-furandimethanol and 2, 5-dimethyloltetrahydrofuran. As shown in table 2:
TABLE 2
Under the high temperature condition, the catalyst has stronger hydrogen activating capability and is more beneficial to the generation of 2, 5-dihydroxymethyl tetrahydrofuran. High conversion (99%) of HMF can be achieved at lower temperatures (25 ℃) and 62% of 2, 5-dimethyloltetrahydrofuran can be obtained at 30 ℃.2, 5-dihydroxymethyl tetrahydrofuran with 86% yield can be obtained by increasing the temperature to 60 ℃. In view of energy saving and good yield of 2, 5-dihydroxymethyl tetrahydrofuran at low temperature, the subsequent study was continued at 30 ℃.
Examples 12 to 18
The same procedure and procedure as in example 8 were followed, except that the reaction temperature was fixed at 30℃and the hydrogen pressure at 40bar, and the reaction time was changed, 2.5-furandimethanol and 2, 5-dimethyloltetrahydrofuran were also obtained, but the conversion and the yield were different, as shown in Table 3:
TABLE 3 Table 3
At the initial stage of the reaction, the HMF is rapidly converted, and the conversion rate of the HMF can reach 94% within 0.5h. The yields of BHMF and BHMTHF were 59% and 16%, respectively, and after the reaction time was extended to 1h, the HMF conversion was >99%, yielding 55% BHMF and 25% bhmth, and further extended to 11h over time, yielding 88% BHMTHF.
Examples 19 to 28
Silica-supported nickel catalyst prepared in example 1 (Ni-NC/SiO 2 ) The method is applied to solvent-free catalysis of5-hydroxy furfural and catalysis of hydrogenation of substrates containing unsaturated groups such as nitro, carbonyl, carbon-carbon double bonds and the like, and comprises the following steps: adding one of a catalyst and a substrate containing unsaturated groups such as nitro, carbonyl, carbon-carbon double bonds and the like into a Hastelloy reaction kettle with high pressure resistance according to the proportion of 100mg to 5mmol, sealing the reaction kettle, replacing air in the reaction kettle with hydrogen for 5-6 times, then filling hydrogen with certain pressure, heating the reaction kettle to a set temperature (such as 30 ℃), and stirring for reaction for 11h at the speed of 1000RPM (rotating speed per minute, r/min) under magnetic stirring. After the reaction was completed, the autoclave was cooled to room temperature and depressurized, the autoclave was opened, the reaction mixture was filtered with an organic filter head of 0.45 μm, and the reaction mixture was subjected to gas chromatography (Agilen 7890B) and the product was identified by a gas mass spectrometer (Trace 1300-ISQ). As shown in table 4:
table 4 results of catalysts for different substrates

Claims (10)

1. A method for preparing a silica supported nickel-based catalyst, comprising the steps of:
(1) Dissolving nickel acetate and P123 in ethanol solution, and carrying out ultrasonic treatment to dissolve the solid and fully and uniformly mixing and coordinating;
(2) Dissolving dimethyl imidazole in deionized water, and magnetically stirring uniformly;
(3) Pouring the solution obtained in the step (1) into the solution obtained in the step (2) rapidly, magnetically stirring in a water bath for 0.5-2h, rapidly adding triethylamine, and continuously stirring for 0.5-2h; slowly dripping tetraethyl orthosilicate into the solution, and stirring in a water bath for 10-20h; filtering, collecting filter cake, washing, vacuum drying to obtain light blue precursor Ni-ZIF/SiO 2 ；
(4) The catalyst precursor Ni-ZIF/SiO obtained in the step (3) is prepared 2 Reducing in nitrogen atmosphere at 900-1000 deg.c to obtain nickel catalyst supported by silica;
wherein the addition ratio of the nickel acetate to the P123 to the dimethylimidazole to the triethylamine to the tetraethyl orthosilicate to the ethanol to the deionized water is 0.05-1g to 0.1-3g to 0.1-2g to 0.05-1g to 0.05-2g to 10-50mL.
2. The method for preparing a silica supported nickel-based catalyst according to claim 1, wherein the ultrasonic time in step (1) is 0.1 to 1h, preferably 0.5h;
the water bath temperature in the step (3) is 30-50 ℃, preferably 40 ℃;
and (3) stirring for 0.5h, 1h and 15h respectively.
3. The method for preparing a silica supported nickel-based catalyst according to claim 1, wherein: the addition ratio of the nickel acetate to the P123 to the dimethylimidazole to the triethylamine to the tetraethyl orthosilicate to the ethanol to the deionized water is 0.1-0.5g to 0.5-2g to 0.5-1g to 0.2-1g to 0.5-1g to 15-25mL.
4. The method for preparing a silica supported nickel-based catalyst according to claim 1, wherein: the reduction process in the step (4) is as follows: heating to 400 ℃ at a speed of5 ℃/min in a tube furnace filled with nitrogen, preserving heat for 0.5h, then continuously heating to 900 ℃ at a speed of 2 ℃/min, preserving heat for 2h, then programming to cool to 400 ℃ at a speed of 10 ℃/min, and then naturally cooling to room temperature.
5. A silica-supported nickel-based catalyst obtained by the method for producing a silica-supported nickel-based catalyst according to any one of claims 1 to 4.
6. The use of the silica supported nickel catalyst according to claim 5 in the preparation of 2, 5-dimethyloltetrahydrofuran by hydrogenation of5-hydroxy furfural.
7. The application according to claim 6, characterized in that it comprises the steps of:
adding a catalyst, water and 5-hydroxymethylfurfural into a high-pressure-resistant hastelloy reaction kettle according to the dosage ratio of 10-50mg to 10-20mL to 1mmol, sealing the reaction kettle, filling 1bar-50bar hydrogen, and reacting for 1-12h at 25-80 ℃ under magnetic stirring to obtain 2, 5-dimethyloltetrahydrofuran.
8. The use of the silica supported nickel catalyst according to claim 5 for catalyzing hydrogenation of substrates containing nitro, carbonyl, carbon-carbon double bond unsaturated groups.
9. The application according to claim 8, characterized in that it comprises the steps of:
adding a catalyst and a substrate containing nitro, carbonyl and carbon double bond unsaturated groups into a high-pressure-resistant hastelloy reaction kettle according to the proportion of 50-120mg to 5mmol, sealing the reaction kettle, filling 1bar-50bar hydrogen, magnetically stirring, and reacting at 25-80 ℃ for 1-12h to obtain a corresponding hydrogenation product.
10. Use according to claim 9, whichCharacterized in that the substrate containing nitro, carbonyl and carbon-carbon double bond unsaturated groups is:nitrobenzene, & gtof>5-hydroxymethylfurfural,>furfural, & lt & gt>Benzaldehyde, (-) -benzene>Cinnamaldehyde, & lt & gt>Heptaldehyde, & gt>Pyridine-2-carbaldehyde, < - > and->Cyclopentanone (C),1-acetophenone, < >>Any one of styrene.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108502895A (en) * 2018-05-14 2018-09-07 浙江海洋大学 A kind of silica@ZIF-8 nano materials and preparation method for transmitting active constituent
CN110227551A (en) * 2019-07-01 2019-09-13 湘潭大学 A kind of nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified2The method for preparing cinnamyl alcohol for cinnamic acid transfer hydrogenation
CN110496614A (en) * 2018-05-16 2019-11-26 中国科学院大连化学物理研究所 Metallic catalyst, preparation method and the application in furfuryl alcohol is prepared in aqueous catalysis furfural hydrogenation
CN112371153A (en) * 2020-11-03 2021-02-19 湖北大学 Bimetallic CoNi-ZIF derived CoNi @ CN catalyst, preparation method and catalytic hydrogenation application thereof
CN113061122A (en) * 2021-03-15 2021-07-02 昆明理工大学 Preparation method of 2, 5-dihydroxymethyl tetrahydrofuran
CN115678028A (en) * 2022-10-27 2023-02-03 常熟理工学院 Nano flower-shaped Ni-ZIF material and preparation method and application thereof
CN116060012A (en) * 2021-10-29 2023-05-05 中国石油化工股份有限公司 SiO (silicon dioxide) 2 Supported Ni catalyst, preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108502895A (en) * 2018-05-14 2018-09-07 浙江海洋大学 A kind of silica@ZIF-8 nano materials and preparation method for transmitting active constituent
CN110496614A (en) * 2018-05-16 2019-11-26 中国科学院大连化学物理研究所 Metallic catalyst, preparation method and the application in furfuryl alcohol is prepared in aqueous catalysis furfural hydrogenation
CN110227551A (en) * 2019-07-01 2019-09-13 湘潭大学 A kind of nucleocapsid catalyst ZIF-67@SiO of hydrophobically modified2The method for preparing cinnamyl alcohol for cinnamic acid transfer hydrogenation
CN112371153A (en) * 2020-11-03 2021-02-19 湖北大学 Bimetallic CoNi-ZIF derived CoNi @ CN catalyst, preparation method and catalytic hydrogenation application thereof
CN113061122A (en) * 2021-03-15 2021-07-02 昆明理工大学 Preparation method of 2, 5-dihydroxymethyl tetrahydrofuran
CN116060012A (en) * 2021-10-29 2023-05-05 中国石油化工股份有限公司 SiO (silicon dioxide) 2 Supported Ni catalyst, preparation method and application thereof
CN115678028A (en) * 2022-10-27 2023-02-03 常熟理工学院 Nano flower-shaped Ni-ZIF material and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RUN-PING YE ET AL.: "Engineering Ni/SiO2 catalysts for enhanced CO2 methanation", 《FUEL》, vol. 285, pages 81 - 10 *

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