CN116618055A - Carbon-modified nickel-based catalyst and application thereof in catalytic hydrogenation of lignin derivatives - Google Patents

Carbon-modified nickel-based catalyst and application thereof in catalytic hydrogenation of lignin derivatives Download PDF

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CN116618055A
CN116618055A CN202310581755.4A CN202310581755A CN116618055A CN 116618055 A CN116618055 A CN 116618055A CN 202310581755 A CN202310581755 A CN 202310581755A CN 116618055 A CN116618055 A CN 116618055A
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carbon
solution
catalyst
precursor
cellulose
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王光辉
潘政宜
张潜
李远征
张珊
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • 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
    • B01J37/16—Reducing
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups

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Abstract

The invention relates to a carbon-modified nickel-based catalyst and application thereof in catalytic hydrogenation of lignin derivatives, belonging to the technical fields of preparation of nano-catalysts and catalytic conversion of biomass derivatives. The invention takes cellulose as a template agent, adopts an in-situ precipitation growth method to synthesize hydrotalcite-like based precursor, and prepares the carbon-modified nickel-based nano catalyst after carbonaceous reduction in inert atmosphere. In addition, the precursor without adding cellulose is physically mixed with cellulose, and is subjected to carbonaceous reduction in an inert atmosphere, or (2) is directly roasted in an inert atmosphere or a reducing atmosphere, and then is subjected to post-carbon supplementing treatment, so that the carbon-modified nickel-based nano catalyst with different particle sizes and carbon contents can be prepared. The carbon-modified nickel-based nano catalyst provided by the invention has general applicability to hydrodeoxygenation reaction of lignin derivatives, and has the characteristics of mild reaction conditions, high conversion rate and selectivity, high reaction rate, good reusability and the like.

Description

Carbon-modified nickel-based catalyst and application thereof in catalytic hydrogenation of lignin derivatives
Technical Field
The invention belongs to the technical field of catalytic hydrogenation of lignin derivatives, and particularly relates to a preparation method of a carbon-modified nickel-based catalyst and application of the catalyst in catalytic hydrogenation upgrading of lignin derivatives.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Carbon in carbon dioxide is fixed by plants through photosynthesis, and about 1700 million tons of lignocellulose can be produced annually. If the renewable resources rich in nature are efficiently converted into the required products, the dependence of human beings on fossil resources and increasingly prominent environmental problems can be effectively relieved. Lignin is one of the main components of lignocellulose (15-30% by weight and 40% by energy), and is also a main byproduct of the paper industry and the ethanol industry by hydrolysis and fermentation of lignocellulose biomass, but is largely changed into environmental pollutants due to insufficient utilization. Lignin is the only non-petroleum resource in nature that can provide renewable aryl compounds and can be broken down into phenolic compounds (known as bio-oils) by a variety of routes. However, the high oxygen content in lignin molecules results in low energy density, high viscosity and unstable combustion of bio-oil produced by decomposition of lignin, which is difficult to directly use. For example, vanillin (4-hydroxy-3-methoxybenzaldehyde) contains three typical functional groups (aldehyde, ether and hydroxy) in lignin fraction, and is a typical component extracted from lignin fraction, but vanillin molecule contains phenolic hydroxy and aromatic aldehyde group is substituted at para position, so that vanillin molecule has reducibility, is easily oxidized and has poor thermal stability. Therefore, developing efficient biomass conversion technology to convert lignin into chemicals or liquid fuels with high added value will help to avoid resource waste, protect environment and reduce human dependence on fossil resources.
The Hydrodeoxygenation (HDO) technology is an effective method for upgrading biological oil, and has the advantages of high heat value of products, less coking and the like. Vanillin can be converted to 2-methoxy-4-methylphenol (MMP) by the HDO reaction. MMPs are widely used as intermediates for perfumes, pharmaceuticals and other valuable chemicals, and are also a potential biomass fuel. Therefore, the HDO reaction of vanillin can be used as an important model reaction for researching the increment of lignin-based biomass resources, and has important significance for the increment of lignin-based biomass resources. However, in catalytic HDO systems, the side reactions associated therewith (further demethylation to 2-methoxyphenol) reduce MMP selectivity. Therefore, it is necessary to design a catalyst system for synthesizing vanillin with high activity and high selectivity to realize directional conversion of vanillin.
The vanillin HDO catalyst is gamma-Al used for refining petroleum 2 O 3 CoMo (NiMo) sulfide supported catalysts, however, sulfur loss during use of sulfide catalysts can lead to product contamination, reduced quality, and sulfide interactions with oxygen can cause structural changes, and even deactivation, of the catalyst; noble metal catalysts such as Pt and Pd have high catalytic activity, but have high cost and scarce resources, and are difficult to apply on a large scale. In recent years, transition metal Ni catalysts are widely applied to phenolic HDO reactions, become an important direction in the research field of biological oil HDO catalysts, and are easy to react with benzene rings although the Ni catalysts have higher activityCarrying out saturated hydrogenation; in addition, since water is often used as a green solvent, biomass upgrading in the aqueous phase is a development direction of green chemistry and sustainable chemistry in the future, however, ni catalysts are prone to sintering, loss and oxidation of metal active sites during the recycling of the aqueous phase, resulting in catalyst deactivation. Thus, transition metal Ni catalysts still have challenges in catalyzing highly efficient directional HDO of vanillin in water.
Related studies have shown that the method of doping or depositing carbon onto and modifying a metal-based catalyst will help to increase the activity, selectivity and stability of the metal-based catalyst. Cellulose is a polysaccharide with the widest distribution and the highest content in the natural world, and accounts for more than 50% of the carbon content in the plant world. If cellulose is used as a carbon source to modify the Ni-based catalyst and applied to the vanillin HDO reaction, the method is expected to provide a new method for green catalytic conversion of 'extracted wood and used wood' for full utilization and high-value conversion of lignocellulose biomass resources. Previous studies by the inventors have provided a Ni-based catalyst, a method for its preparation and its use in reductive amination (application No. 202110919247.3). However, in the patent, phenolic resin balls with the size of about 180nm are used as a template agent, hydrotalcite is coated on the outer layer, the phenolic resin balls used in the method are small in size and are easy to embed into the hydrotalcite, and the particle size of cellulose is large, at least in the micron level, so that the corresponding hydrotalcite coating layer is formed with great technical difficulty. In addition, the catalysts of the above patents are applied to the hydrogenation reduction of aldehyde/ketone compounds, and cannot realize the catalytic effect in aqueous phase solvents.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a carbon-modified nickel-based nano catalyst, a preparation method thereof and application thereof in lignin derivative HDO. In addition, the precursor (1) which is not added with cellulose for synthesis is physically mixed with cellulose and is subjected to carbonaceous reduction in an inert atmosphere, or (2) is directly roasted in the inert atmosphere or in a reducing atmosphere, and then the carbon-modified nickel-based nano catalyst with controllable carbon content and uniform size can be prepared through post-carbon supplementing treatment. The carbon-modified nickel-based nano catalyst provided by the invention adopts a novel method of 'taking wood and using wood' for green catalytic conversion, has universal applicability to the HDO reaction of lignin derivatives in water, and has the characteristics of mild reaction conditions, high reaction rate, high conversion rate and selectivity, good catalyst recycling property and the like.
In a first aspect, a method for preparing a small-sized carbon-modified nickel-based nanocatalyst is provided, comprising the steps of:
adding a metal precursor solution and alkali liquor into a modified cellulose solution to obtain a precursor I solution, aging, filtering, washing and drying to obtain a catalyst precursor I, and carrying out carbonaceous reduction treatment on the precursor I in an inert atmosphere to obtain a carbon-modified nickel-based nano catalyst;
the preparation method of the modified cellulose comprises the following steps: mixing cellulose, a metal salt M auxiliary agent and an ammonia solution, and heating, wherein metal elements in the metal salt M auxiliary agent are selected from one or more of Ni, co, mg, cu, zn, al, fe, zr, ti;
the metal precursor solution is a solution containing Ni and X elements, wherein X is selected from one or more of Al, fe, zr, ti;
the alkali liquor is selected from 0.05-2.5 mol/L NaOH and 0.2-3.2 mol/L Na 2 CO 3 、0.05～3.2mol/L NaHCO 3 One of them, or a mixed solution of both.
The cellulose has a particle size of about 25 microns and has the characteristics of large particle size and large surface area compared with the phenolic resin balls in the prior patent. It is difficult for those skilled in the art to expect that the cellulose surface will form a uniformly covered water-stone layer. In the research of the invention, the inventor finds that the cellulose modified by the metal ions can lead the metal Ni to be based on the strong electrostatic action 2+ 、X n+ And other metal ion assistants are uniformly adsorbed on the surface of cellulose, so that the uniformly distributed hydrotalcite-like surface is obtained.
In the preparation of the modified cellulose described above, the present invention also has the following preferred embodiments:
the metal salt M auxiliary agent is selected from one or more of nitrate, chloride, acetate, acetylacetonate, cyanide, carbonyl salt and the like.
Since the content of cellulose affects the particle size and carbon content of the finally obtained carbon-modified nickel-based nanocatalyst, in a preferred embodiment, the concentration of cellulose is 0 to 100g/L, preferably 15 to 25g/L;
the concentration of the metal salt M auxiliary is 0.06-2.5 mmol/L, more preferably 0.06-1.5 mmol/L, still more preferably 0.3-0.8 mmol/L.
The ammonia solution is prepared by mixing concentrated ammonia water and water, wherein the concentrated ammonia water is 25-32% ammonia water, and the volume ratio of the concentrated ammonia water to the water is 1 (1-40), preferably 1 (5-15).
In a further preferred embodiment, the preparation of the modified cellulose can be achieved by heating at a temperature of 50 to 160 ℃, preferably 80 to 130 ℃; the heating time is 6 to 25 hours, preferably at least 1 hour, further preferably at least 4 hours, to achieve uniform adsorption of the metal ions on the cellulose surface, and is generally not more than 8 hours, preferably not more than 6 hours, in view of energy consumption cost.
It has been verified that the cellulose modified in the above manner can be dispersed in water or an alcohol solvent to form a uniform solution, and therefore, the solvent in the modified cellulose solution is selected from one or more of water, methanol, ethanol, n-propanol, isopropanol, and isobutanol, preferably methanol.
Regarding the above metal precursor solution, the present invention is also preferred as follows:
in one embodiment, the Ni, X precursor is selected from one or more of nitrate, chloride, acetate, acetylacetonate, cyanide, carbonyl salts; wherein: the molar ratio of Ni to X is (1-8): 1, preferably (3-6): 1, more preferably 3:1;
when the total concentration of the Ni and X precursors is 0.05-10 mol/L and the total concentration of metals of the Ni and X precursors is lower than 0.05mol/L, the metal loading is extremely low, the method is not suitable for practical production and application, the concentration of metal salt is higher than 10mol/L, the metal loading is extremely high, and active components are easy to sinter. Further preferably, the total metal concentration of Ni and X precursor I is between 0.6 and 5mol/L.
In yet another embodiment, the metal precursor solution contains a Y precursor in addition to Ni and X precursors, wherein Y is one or more selected from Co, mg, cu, zn and the like, and the Y precursor is a divalent metal salt, Y 2+ Metal ion and Ni 2+ Similarly hydrotalcite structures can be formed.
When the solution B contains Ni, X and Y precursors, the Ni, X and Y precursors can be respectively selected from one or more of nitrate, chloride, acetate, acetylacetonate, cyanide, carbonyl salt and the like; wherein the molar ratio of (Ni+Y) to X is (1-8): 1, preferably (3-6): 1; the molar ratio of Y to Ni is (0-50): 1, preferably (5-15): 1; the total concentration of the Ni, X and Y precursors is 0.01-10 mol/L, preferably 0.6-5 mol/L.
In addition, the solvent of the metal precursor solution is an alcohol solution, the alcohol is selected from one or more of methanol, ethanol, n-propanol, isopropanol, isobutanol, n-butanol, 2-butanol, cyclohexanol, ethylene glycol and the like, preferably methanol, and the volume ratio of the alcohol to water in the alcohol solution is (0-20): 1-30.
In the preparation of the precursor I solution, the metal precursor solution and the alkali solution should be added into the modified cellulose solution at the same time in a dropwise manner, wherein the dropping speed is 10-100 mL/min, preferably 20-40 mL/min, and more preferably 25-35 mL/min; the dropping process can be properly warmed up to improve the dispersing effect, and the dropping temperature is 40-70 ℃.
In addition, the pH of the precursor I solution needs to be adjusted in the dripping process, and the pH is controlled between 7 and 11. The pH value can be determined according to Ni 2+ 、X n+ The Ksp value of the complete precipitation was determined. Too low an amount of alkali, ions in the solution cannot be completely precipitated; the proper excess of alkali is beneficial to better coprecipitation; but the alkali content is too high and the grains are larger. Further preferably, the pH is controlled between 9 and 10.
The aging temperature of the precursor I solution is 30-160 ℃, preferably 50-110 ℃, and more preferably 50-65 ℃; the aging time is 8 to 48 hours, more preferably 10 to 18 hours.
The inert gas is one or more of nitrogen, argon and helium.
The carbonaceous reduction temperature is: 200 to 1100 ℃, preferably 400 to 1000 ℃, more preferably 500 to 950 ℃, still more preferably 550 to 850 ℃.
In a second aspect, a method for preparing a large particle size carbon-modified nickel-based nanocatalyst is provided, comprising the steps of: adding a metal precursor solution and alkali liquor into an alcohol solvent simultaneously to obtain a precursor II solution, physically mixing the precursor II with cellulose, and obtaining the carbon-modified nickel-based nano catalyst by adopting any one of the following treatment modes:
(1) Roasting in inert atmosphere;
(2) Roasting the precursor II in an inert atmosphere, and performing later carbon supplementing treatment;
(3) And roasting and reducing the precursor II in a reducing atmosphere, and then carrying out post carbon supplementing treatment.
In the configuration mode of the precursor solution II, the arrangement mode of the metal precursor solution, alkali liquor and alcohol solvent is the same as that of the first aspect, namely the precursor solution II is different from the precursor solution I only in that modified cellulose is not added.
The three treatment modes can obtain the carbon-modified nickel-based nano catalyst, but the sizes and the carbon contents of the catalysts are different, in the schemes (1) and (2), the catalyst with larger particle size of the carbon-modified nickel-based catalyst is obtained in an inert atmosphere, and the main product of catalytic vanillin hydrogenation is vanillin (HMP); in the scheme (3), the catalyst with smaller particle size of carbon-modified nickel-based obtained in the reducing atmosphere is used for catalyzing the hydrogenation of vanillin, and the main product is MMP.
In the above-mentioned schemes (1) to (3), the firing and carbon supplying temperatures are 200 to 1100 ℃, preferably 400 to 1000 ℃, more preferably 500 to 950 ℃, still more preferably 550 to 850 ℃; the calcination and carbon supply time is 0.8 to 20 hours, more preferably 1.2 to 12 hours, still more preferably 2 to 4 hours. In order to achieve sufficient calcination and carbon make-up, the calcination and carbon make-up time is generally at least 0.8h, more preferably at least 2h. In view of energy consumption costs, it is generally not more than 12 hours, preferably not more than 4 hours.
In the above schemes (1) and (2), the inert gas is one or more of nitrogen, argon and helium.
In the above schemes (2) and (3), the reducing gas is methanol volatile gas, ethanol volatile gas, isopropanol volatile gas, hydrogen, CO, CH 4 One or more of the following; the carbon source for supplementing carbon is cellulose, polymer, CO and CH 4 One or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, polymethyl methacrylate, citric acid, oleic acid, maleic acid, fumaric acid, succinic acid, tartaric acid, malic acid, gluconic acid, trimesic acid, wood dust and straw.
In a third aspect, there is provided a small-sized carbon-modified nickel-based nanocatalyst prepared by the method of the first aspect, or a large-sized carbon-modified nickel-based nanocatalyst prepared by the method of the second aspect.
In a fourth aspect, a catalytic hydrogenation method for lignin derivatives is provided, wherein water is used as a solvent, the carbon-modified nickel-based nano catalyst in the third aspect is added into the lignin derivatives as a substrate, and hydrogen is introduced into the lignin derivatives for reaction.
The lignin derivative is one or more of vanillin, benzaldehyde, syringaldehyde, terephthalyl ether, vanillyl ethanone and benzyl phenyl ether, and the products obtained by the method are MMP, toluene, 3, 5-dimethoxy-4-hydroxytoluene, paraxylene, 4-ethyl guaiacol, toluene and phenol in sequence.
Preferably, the mass ratio of the carbon-modified nickel-based nanocatalyst to the lignin derivative is 1 (0.05-25), preferably 1 (5-12), and more preferably 1 (6-10).
The concentration of lignin derivatives is preferably 0.1 to 10mol/L.
The reaction temperature is preferably 80 to 150 ℃.
The reaction time is preferably 0.5 to 10 hours at the reaction temperature. In order to achieve a sufficient reaction, the reaction time is generally at least 0.5h, more preferably at least 1.5h. In view of cost, it is generally not more than 10 hours, preferably not more than 6 hours, more preferably not more than 4 hours. The specific reaction time may be adjusted depending on the reaction temperature and the composition of the solution.
As a preferred embodiment, the method further comprises the step of catalyst regeneration: after the reaction, centrifugally recovering the catalyst, washing the catalyst with water for 1 to 3 times, washing the catalyst with alcohol for 1 to 3 times, and drying the catalyst to obtain a regenerated catalyst;
preferably, the alcohol detergent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol and cyclohexanol.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a synthetic route to a carbon-modified nickel-based catalyst according to the present invention;
FIG. 2 is a TEM image of carbon-modified nickel-based catalysts of examples 1-4 having a particle size of about 8nm and a carbon content of about 0.7 wt%;
FIG. 3 is a TEM image of a carbon-modified nickel-based catalyst of examples 1-5 having a particle size of about 18nm and a carbon content of about 0.8 wt%;
FIG. 4 shows XPS spectra of a nickel catalyst prepared by a conventional hydrogen reduction method and a carbon-modified nickel catalyst prepared by the present patent before and after 10 cycles of recycling;
FIG. 5 is an SEM image of a carbon-modified nickel-based catalyst according to the present invention;
wherein, (a) is cellulose with the surface uniformly covered with hydrotalcite, and (b) is a partial enlarged view of the surface;
FIG. 6 is a graph comparing the recycling performance of the carbon-modified nickel-based catalyst of the present invention;
wherein (a) is the carbon modified nickel-based catalyst in the invention, and (b) is the recycling performance of the traditional nickel catalyst.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1-1
In this embodiment, a carbon-modified nickel-based catalyst and a vanillin catalytic hydrogenation method based on the catalyst are provided:
adding 0.1g of cellulose, 0.010mmol of metal salt M auxiliary agent (one of Co, fe or Ni nitrate), 8mL of concentrated ammonia water and 30mL of deionized water into a dry container, reacting for 4 hours at 60 ℃, filtering after the reaction, washing and drying to obtain the surface modified cellulose. The surface-modified cellulose was dispersed in 50mL of methanol to obtain a cellulose dispersion A.
According to [ Ni ] 2+ ]And [ Al ] 3+ ]Preparing a mixed salt solution with the total metal concentration of 0.2mol/L, wherein the volume ratio of methanol to water is 1:20, and obtaining a solution B.
Preparing 0.2mol/L NaOH and 0.4mol/L Na 2 CO 3 Mixing the alkali solution as a precipitator to obtain solution C.
Solutions B and C were simultaneously added dropwise to dispersion A at 70℃and the drop rate of solution C was controlled to 20mL/min, maintaining the pH of the mixed solution at 10.0. After the completion of the dropwise addition of the solution B, the aging was continued for 12 hours. And filtering, washing and vacuum drying the aged suspension for 8 hours at 60 ℃ to obtain the catalyst precursor.
And (3) placing the prepared catalyst precursor into a quartz tube of a tube furnace, reducing the carbon at 800 ℃ for 3 hours in an argon atmosphere, cooling to room temperature, and passivating for 1 hour to obtain the carbon-modified nickel-based catalyst.
To the reaction vessel were added 0.02g of the carbon-modified nickel-based catalyst obtained above, 1mmol of vanillin, 10mL of water, and a hydrogen pressure of 1.0MPa, and the mixture was heated at 130℃for 2 hours. After the reaction is finished, the solid catalyst is separated by magnetic separation. The contents of the components in the reaction mixture were measured by gas chromatography, and the results are shown in Table 1.
Examples 1 to 2
The difference from example 1-1 is that the metal M promoter is 0.010mmol nickel nitrate. In addition to the nickel nitrate and aluminum nitrate atomic ratios of 3:1 (example 1-1), 2:1 and 4:1 were also examined. The synthesis conditions of the rest of the catalysts and the catalytic hydrogenation reaction conditions of vanillin are the same as those of the example 1-1.
Examples 1 to 3
The catalyst precursor was prepared as in examples 1-2.
And (3) placing the prepared catalyst precursor into a quartz tube of a tube furnace, reducing the carbon at 300-600 ℃ for 3 hours in an argon atmosphere, cooling to room temperature and passivating for 2 hours to obtain the carbon modified nickel catalyst.
The synthesis conditions of the rest of the catalysts and the catalytic hydrogenation reaction conditions of vanillin are the same as those of the example 1-1.
Examples 1 to 4
The difference from example 1-1 is that the metal M promoter is 0.010mmol nickel nitrate; the other catalyst synthesis conditions were the same as in example 1-1, and a carbon-modified nickel catalyst having a particle size of about 8nm and a carbon content of about 0.7wt% was obtained, and the specific morphology thereof was as shown in FIG. 2.
To the reaction vessel, 0.02g of the carbon-modified nickel catalyst obtained above, 1mmol of benzaldehyde, syringaldehyde, terephthalyl ether, vanillyl ketone, benzyl phenyl ether, 10mL of water, and a hydrogen pressure of 1.0MPa were added, and the mixture was heated at 130 to 150℃for 1 to 6 hours. After the reaction is finished, the solid catalyst is separated by magnetic separation. The contents of the components in the reaction mixture were measured by gas chromatography, and the results are shown in Table 1.
Examples 1 to 5
In this example, the preparation of the catalyst precursor was the same as in examples 1-2, except that cellulose was not added, the catalyst precursor prepared above was physically mixed with 0.1g of cellulose uniformly, placed in a quartz tube of a tube furnace, carbonaceous reduced at 800 ℃ for 3 hours under an argon atmosphere, cooled to room temperature and passivated for 1 hour to obtain a carbon-modified nickel catalyst having a particle size of about 18nm and a carbon content of about 0.8wt%, the specific morphology of which is shown in fig. 3.
The vanillin catalytic hydrogenation conditions were the same as in example 1-1, except that the heating time was 6h. The contents of the components in the reaction mixture were measured by gas chromatography, and the results are shown in Table 1.
Examples 1 to 6
The carbon-modified nickel catalysts were prepared as in examples 1-4.
To the reaction vessel were added 0.02g of a carbon-modified nickel catalyst, 1mmol of vanillin, 10mL of water, and a hydrogen pressure of 1.0MPa, and heated at 130℃for 1h and 4h, respectively. After the reaction is finished, the solid catalyst is separated by magnetic separation. The contents of the components in the reaction mixture were measured by gas chromatography, and the results are shown in Table 1.
Example 2-1
Adding 0.1g of cellulose, 0.010mmol of metal salt M auxiliary agent (one of cobalt, iron or zirconium nitrate), 8mL of concentrated ammonia water and 30mL of deionized water into a dry container, reacting for 4 hours at 60 ℃, filtering after the reaction, washing and drying to obtain the surface modified cellulose. The surface-modified cellulose was dispersed in 50mL of methanol to obtain a cellulose dispersion A.
According to [ Ni ] 2+ ]And [ Fe ] 3+ ]Preparing a mixed salt solution with the total metal concentration of 0.2mol/L, wherein the volume ratio of methanol to water is 1:30, and obtaining a solution B.
Preparing 0.2mol/L NaOH and 0.4mol/L Na 2 CO 3 Mixing the alkali solution as a precipitator to obtain solution C.
Solutions B and C were simultaneously added dropwise to dispersion A at 70℃and the drop rate of solution C was controlled to 25mL/min, maintaining the pH of the mixed solution at 9.8. After the completion of the dropwise addition of the solution B, the aging was continued for 12 hours. And filtering, washing and drying the aged suspension for 8 hours at 60 ℃ to obtain the catalyst precursor.
And (3) placing the prepared catalyst precursor into a quartz tube of a tube furnace, reducing the carbon at 800 ℃ for 3 hours in an argon atmosphere, cooling to room temperature and passivating for 1 hour to obtain the NiFeC-based catalyst.
To the reaction vessel were added 0.1g of the above-obtained NiFeC-based catalyst, 1mmol of vanillin, 10mL of water, and a hydrogen pressure of 1.0MPa, and the mixture was heated at 130℃for 1 hour. After the reaction is finished, the solid catalyst is separated by magnetic separation. The contents of the respective components in the reaction mixture were measured by gas chromatography, and the results are shown in Table 2.
Example 2-2
The difference from example 2-1 is that the metal salt M auxiliary is nickel nitrate, the [ Ni ] 2+ ]And [ Fe ] 3+ ]The atomic ratio is (2-4): 1, and the synthesis conditions of the rest of the catalysts and the synthesis conditions of the vanillin catalysis are the same as those of the example 2-1.
Example 3
Adding 0.1g of cellulose, 0.010mmol of nickel nitrate, 8mL of concentrated ammonia water and 30mL of deionized water into a dry container, reacting for 4 hours at 60 ℃, filtering after the reaction, washing and drying to obtain the surface modified cellulose. The surface-modified cellulose was dispersed in 50mL of methanol to obtain a cellulose dispersion A.
According to [ Ni ] 2+ ]And [ X ] n+ ]Atomic ratio of 3:1 (specific X n+ See Table 3) to prepare a mixed salt solution with a total metal concentration of 0.2mol/L, wherein the volume ratio of methanol to water is 1:30, to obtain a solution B.
Preparing 0.2mol/L NaOH and 0.4mol/L Na 2 CO 3 Mixing the alkali solution as a precipitator to obtain solution C.
Solutions B and C were simultaneously added dropwise to dispersion A at 70℃and the drop rate of solution C was controlled to 25mL/min, maintaining the pH of the mixed solution at 9.8. After the completion of the dropwise addition of the solution B, the aging was continued for 12 hours. And filtering, washing and drying the aged suspension for 8 hours at 60 ℃ to obtain the catalyst precursor.
And (3) placing the prepared catalyst precursor into a quartz tube of a tube furnace, reducing the carbon at 800 ℃ for 3 hours under the argon atmosphere, cooling to room temperature and passivating for 1 hour to obtain the Ni-XC-based catalyst.
To the reaction vessel was added 0.1g of Ni-XC based catalyst, 1mmol of vanillin, 10mL of water, and a hydrogen pressure of 1.0MPa, and the mixture was heated at 130℃for 1 hour. After the reaction is finished, the solid catalyst is separated by magnetic separation. The contents of the components in the reaction mixture were measured by gas chromatography, and the results are shown in Table 3.
Example 4
The difference from example 3 is that according to [ Ni ] 2+ ]:[Y 2+ ]:[Xn + ]An atomic ratio of 2:1:1 (specific Y and X are shown in Table 4) to obtain a Ni-X-YC-based catalyst, and the rest was the same as in example 3.
Example 5-1
To a dry vessel was added 50mL of methanol to give solvent A.
According to [ Ni ] 2+ ]And [ Al ] 3+ ]Preparing a mixed salt solution with the total metal concentration of 0.2mol/L, wherein the volume ratio of methanol to water is 1:20, and obtaining a solution B.
Preparing 0.2mol/L NaOH and 0.4mol/L Na 2 CO 3 Mixing the alkali solution as a precipitator to obtain solution C.
Solutions B and C were simultaneously added dropwise to dispersion A at 70℃and the drop rate of solution C was controlled to 20mL/min, maintaining the pH of the mixed solution at 10.0. After the completion of the dropwise addition of the solution B, the aging was continued for 12 hours. And filtering, washing and vacuum drying the aged suspension for 8 hours at 60 ℃ to obtain the catalyst precursor.
And placing the prepared catalyst precursor into a quartz tube of a tube furnace, roasting for 3 hours at 800 ℃ in an argon atmosphere, cooling to room temperature and passivating for 1 hour, and adding 0.1g of cellulose for carbon supplementing treatment to obtain the carbon modified nickel catalyst with larger particle size.
To the reaction vessel were added 0.02g of the carbon-modified nickel catalyst obtained above, 1mmol of vanillin, 10mL of water, and a hydrogen pressure of 1.0MPa, and the mixture was heated at 130℃for 2 hours. After the reaction is finished, the solid catalyst is separated by magnetic separation. The contents of the respective components in the reaction mixture were measured by gas chromatography, and the results are shown in Table 5.
Example 5-2
The catalyst precursor is the same as in example 5-1, except that the prepared catalyst precursor is placed in a quartz tube of a tube furnace, reduced for 3 hours at 800 ℃ in a hydrogen atmosphere, cooled to room temperature and passivated for 1 hour, and then added with 0.1g of cellulose for carbon supplementing treatment, so as to obtain the carbon modified nickel catalyst with smaller particle size.
The rest of the arrangement is the same as in example 5-1.
Example 6
To a dry vessel was added 50mL of methanol to give solvent A.
According to [ Ni ] 2+ ]And [ Al ] 3+ ]Preparing a mixed salt solution with the total metal concentration of 0.2mol/L, wherein the volume ratio of methanol to water is 1:20, and obtaining a solution B.
Preparing 0.2mol/L NaOH and 0.4mol/L Na 2 CO 3 Mixing the alkali solution as a precipitator to obtain solution C.
Solutions B and C were simultaneously added dropwise to dispersion A at 70℃and the drop rate of solution C was controlled to 20mL/min, maintaining the pH of the mixed solution at 10.0. After the completion of the dropwise addition of the solution B, the aging was continued for 12 hours. And filtering, washing and vacuum drying the aged suspension for 8 hours at 60 ℃ to obtain the catalyst precursor.
And placing the prepared catalyst precursor into a quartz tube of a tube furnace, roasting for 3 hours at 800 ℃ in an air atmosphere, cooling to room temperature and passivating for 1 hour to obtain the Ni-Al-based metal oxide catalyst.
To the reaction vessel were added 0.02g of the Ni-Al-based metal oxide catalyst obtained above, 1mmol of vanillin, 10mL of water, and a hydrogen pressure of 1.0MPa, and the mixture was heated at 130℃for 2 hours. After the reaction is finished, the solid catalyst is separated by magnetic separation. The content of each component in the reaction mixture was measured by gas chromatography, the results are shown in Table 5, and the hydrodeoxygenation product was not found as shown in Table 5.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
The invention also examines the stability of the carbon-modified nickel catalyst, and the XPS (figure 4) and SEM (figure 5) charts of the nickel catalyst prepared by the traditional hydrogen reduction method and the carbon-modified nickel catalyst prepared in the example 1-1 are drawn before and after 10 cycles of recycling. As shown in fig. 4, XPS results indicate that the catalyst of the present invention successfully realizes carbon modification and that a peak of nickel carbide appears clearly in the prepared catalyst; second, compared with the nickel catalyst prepared by the conventional hydrogen reduction method, the catalyst prepared by the method has good stability (figure 6), and the structure of the catalyst is not changed basically after multiple uses.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method for modifying a nickel-based nano catalyst by small-size carbon, which is characterized by comprising the following steps: adding a metal precursor solution and alkali liquor into a modified cellulose solution to obtain a precursor I solution, aging, filtering, washing and drying to obtain a catalyst precursor I, and carrying out carbonaceous reduction treatment on the precursor I in an inert atmosphere to obtain a carbon-modified nickel-based nano catalyst;
the preparation method of the modified cellulose comprises the following steps: mixing cellulose, metal salt M auxiliary agent and ammonia solution, and heating, wherein the metal salt M auxiliary agent is one or more selected from nitrate, chloride, acetate, acetylacetonate, cyanide, carbonyl salt and the like;
the metal precursor solution is a solution containing Ni and X elements, wherein X is selected from one or more of Al, fe, zr, ti;
the alkali liquor is selected from 0.05-2.5 mol/L NaOH and 0.2-3.2 mol/L Na 2 CO 3 、0.05～3.2mol/L NaHCO 3 One of them, or a mixed solution of both.
2. The method of small-sized carbon-modified nickel-based nanocatalyst according to claim 1, characterized in that the concentration of the metal salt M promoter is 0.06-2.5 mmol/L, more preferably between 0.06-1.5 mmol/L, still more preferably 0.3-0.8 mmol/L;
or, the concentration of the cellulose is 0-100 g/L;
or, the ammonia solution is prepared by mixing concentrated ammonia water and water, wherein the concentrated ammonia water is 25-32% ammonia water, and the volume ratio of the concentrated ammonia water to the water is 1 (1-40);
or the preparation process of the modified cellulose needs to be heated, the heating temperature is 50-160 ℃, and the heating time is 6-25 h;
or the solvent in the modified cellulose solution is selected from one or more of water, methanol, ethanol, n-propanol, isopropanol and isobutanol.
3. The method of small-sized carbon-modified nickel-based nanocatalyst of claim 1, wherein in the metal precursor solution, the Ni, X precursor is selected from one or more of nitrate, chloride, acetate, acetylacetonate, cyanide, carbonyl salts; wherein: the molar ratio of Ni to X is (1-8): 1, preferably (3-6): 1; when the total concentration of the Ni and X precursors is 0.05-10 mol/L and the total concentration of the metals of the Ni and X precursors is lower than 0.05 mol/L;
or, the metal precursor solution contains a Y precursor besides Ni and X precursors, wherein Y is one or more selected from Co, mg, cu, zn, and the Ni, X and Y precursors can be one or more selected from nitrate, chloride, acetate, acetylacetonate, cyanide, carbonyl salt and the like respectively; wherein the molar ratio of (Ni+Y) to X is (1-8): 1; the molar ratio of Y to Ni is (5-15): 1; the total concentration of the Ni, X and Y precursors is 0.01-10 mol/L;
or the solvent of the metal precursor solution is an alcohol solution, and the alcohol is one or more selected from methanol, ethanol, n-propanol, isopropanol, isobutanol, n-butanol, 2-butanol, cyclohexanol, ethylene glycol and the like.
4. The method for preparing the small-size carbon-modified nickel-based nano catalyst according to claim 1, wherein in the preparation of the precursor I solution, a metal precursor solution and an alkali solution are simultaneously dripped into a modified cellulose solution at the dripping speed of 10-100 mL/min and the dripping temperature of 40-70 ℃;
or, the dripping process also needs to adjust the pH of the precursor I solution, and the pH is controlled between 7 and 11.
5. The method for preparing the small-size carbon-modified nickel-based nanocatalyst according to claim 1, wherein the aging temperature of the precursor I solution is 30-160 ℃ and the aging time is 8-48 hours;
the inert gas is one or more of nitrogen, argon and helium;
the carbonaceous reduction temperature is: 200-1100 ℃.
6. A method for modifying a nickel-based nano catalyst by large-particle-size carbon, which is characterized by comprising the following steps: adding a metal precursor solution and alkali liquor into an alcohol solvent simultaneously to obtain a precursor II solution, physically mixing the precursor II with cellulose, and obtaining the carbon-modified nickel-based nano catalyst by adopting any one of the following treatment modes:
(1) Roasting in inert atmosphere;
(2) Roasting the precursor II in an inert atmosphere, and performing later carbon supplementing treatment;
(3) And roasting and reducing the precursor II in a reducing atmosphere, and then carrying out post carbon supplementing treatment.
7. The method for preparing a large particle size carbon-modified nickel-based nanocatalyst of claim 6 wherein in the schemes (1) - (3), the temperature of calcination and carbon replenishment is 200-1100 ℃ and the time of calcination and carbon replenishment is 0.8-20 hours;
or, in the schemes (1) and (2), the inert gas is one or more of nitrogen, argon and helium; or in the schemes (2) and (3), the reducing gas is methanol volatile gas, ethanol volatile gas, isopropanol volatile gas, hydrogen, CO and CH 4 One or more of the following; the carbon source for supplementing carbon is cellulose, polymer, CO and CH 4 One or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, polymethyl methacrylate, citric acid, oleic acid, maleic acid, fumaric acid, succinic acid, tartaric acid, malic acid, gluconic acid, trimesic acid, wood dust and straw.
8. A small-sized carbon-modified nickel-based nanocatalyst prepared by the method of any one of claims 1-5, or a large-sized carbon-modified nickel-based nanocatalyst prepared by the method of claim 6 or 7.
9. A catalytic hydrogenation method of lignin derivatives, which is characterized in that water is used as a solvent, the carbon-modified nickel-based nano catalyst as claimed in claim 8 is added into lignin derivatives as a substrate, and hydrogen is introduced into the lignin derivatives for reaction;
the lignin derivative is one or more of vanillin, benzaldehyde, syringaldehyde, terephthalyl ether, vanillyl ethanone and benzyl phenyl ether.
10. The catalytic hydrogenation process of lignin derivatives according to claim 9 wherein the mass ratio of carbon modified nickel based nanocatalyst to lignin derivatives is 1 (0.05 to 25);
the concentration of lignin derivative is 0.1-10 mol/L;
the reaction temperature is 80-150 ℃;
the reaction time is 0.5-10 h;
or, the method further comprises the step of catalyst regeneration: after the reaction, centrifugally recovering the catalyst, washing the catalyst with water for 1 to 3 times, washing the catalyst with alcohol for 1 to 3 times, and drying the catalyst to obtain a regenerated catalyst; the alcohol detergent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol and cyclohexanol.
CN202310581755.4A 2023-05-22 2023-05-22 Carbon-modified nickel-based catalyst and application thereof in catalytic hydrogenation of lignin derivatives Pending CN116618055A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117960177A (en) * 2024-03-28 2024-05-03 广东工业大学 Preparation method and application of carbon-modified alumina-supported nickel-based catalyst

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117960177A (en) * 2024-03-28 2024-05-03 广东工业大学 Preparation method and application of carbon-modified alumina-supported nickel-based catalyst
CN117960177B (en) * 2024-03-28 2024-06-25 广东工业大学 Preparation method and application of carbon-modified alumina-supported nickel-based catalyst

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