CN113979837A

CN113979837A - Application of cobalt-based catalyst in hydrogenolysis reaction of biomass and derivatives thereof

Info

Publication number: CN113979837A
Application number: CN202111168775.6A
Authority: CN
Inventors: 王艳芹; 相爽; 董琳; 郭勇; 刘晓晖; 岳申之
Original assignee: East China University of Science and Technology
Current assignee: East China University of Science and Technology
Priority date: 2021-09-30
Filing date: 2021-09-30
Publication date: 2022-01-28

Abstract

The disclosure provides an application of a cobalt-based catalyst in hydrogenolysis reaction of biomass and derivatives thereof, wherein the biomass or the derivatives thereof are used as reaction substrates, and the reaction substrates and a hydrogen source are subjected to hydrogenolysis reaction under the catalysis of the cobalt-based catalyst; the cobalt-based catalyst has high catalytic activity, can realize hydrogenolysis of biomass and derivatives thereof at low temperature in a short time to obtain products with high purity, and the obtained products can be used as production raw materials of biomass fuel, degradable plastics, medicines, pesticides and the like and have high added value; in addition, the cobalt-based catalyst has magnetism, is convenient for separation and recycling of the catalyst, and has good industrial application prospect; the cobalt-based catalyst is low in cost, and the industrial cost can be effectively reduced.

Description

Application of cobalt-based catalyst in hydrogenolysis reaction of biomass and derivatives thereof

Technical Field

The disclosure relates to the technical field of industrial catalysis, in particular to application of a cobalt-based catalyst in hydrogenolysis reaction of biomass and derivatives thereof.

Background

At present, hydrogenolysis reaction of biomass and derivatives thereof faces the problem of low catalyst activity, and in order to achieve high yield of target products, longer reaction time or higher reaction temperature is needed; in addition, the catalyst and the product are difficult to separate and recycle, and the method has no industrial potential, thereby influencing the industrial process.

Therefore, a high-efficiency catalytic system is needed to obtain the target product with high yield under low-temperature and short-time conditions.

Disclosure of Invention

In view of the above, the present disclosure is directed to an application of a cobalt-based catalyst in hydrogenolysis reaction of biomass and derivatives thereof.

In view of the above, the present disclosure provides an application of a cobalt-based catalyst in a hydrogenolysis reaction of biomass and derivatives thereof, including that the biomass or derivatives thereof are used as a reaction substrate, and the reaction substrate and a hydrogen source are subjected to a hydrogenolysis reaction under the catalysis of the cobalt-based catalyst.

In some embodiments, the biomass or derivative thereof comprises at least one of furans, higher fatty acids, and lignin;

and/or the hydrogen source comprises at least one of hydrogen and an organic hydrogen source.

In some embodiments, the furanic compounds include at least one of 5-hydroxymethylfurfural, furfural, and furfuryl alcohol;

and/or, the higher fatty acid comprises at least one of palmitic acid, stearic acid, oleic acid, arachidic acid, and ligninic acid;

and/or, the lignin comprises at least one of hardwood lignin, softwood lignin, and herbaceous lignin; preferably, the hardwood lignin comprises at least one of birch lignin, poplar lignin, willow lignin, beech lignin and oak lignin, the softwood lignin comprises at least one of pine lignin, cedar lignin and cedar lignin, and the herbaceous lignin comprises at least one of corn stover lignin, wheat straw lignin and rice straw lignin;

and/or the organic hydrogen source comprises at least one of methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerol, formic acid, acetic acid and cyclohexane, preferably isopropanol.

In some embodiments, the mass ratio of the reaction substrate to the cobalt-based catalyst is 1: (0.01-2);

and/or the reaction temperature is 50-300 ℃, preferably 130-210 ℃;

and/or the reaction time is 0.5-20 h, preferably 2-16 h;

and/or the pressure of the hydrogen is 0.5-5 MPa, preferably 0.5-2 MPa;

and/or the mass ratio of the reaction substrate to the organic hydrogen source is 1 (0.5-20), preferably 1 (1-5).

In some embodiments, the hydrogenolysis reaction is carried out in a reaction medium, wherein the mass ratio of the reaction substrate to the reaction medium is 1 (1-20), preferably 1 (1-5); the reaction medium comprises at least one of water, an ionic liquid, and an organic solvent;

preferably, the organic solvent comprises at least one of dioxane, tetrahydrofuran, cyclohexane, dodecane, methanol, and ethanol.

In some embodiments, the cobalt-based catalyst comprises a core-shell Co @ CoO catalyst having a core of cobalt and an outer shell of cobaltous oxide containing oxygen vacancies.

In some embodiments, the method of preparing the core-shell Co @ CoO catalyst comprises preparing a precursor, and optionally reducing the precursor to obtain the core-shell Co @ CoO catalyst;

preferably, the volume fraction of hydrogen in the reducing gas is 5-30%, more preferably 5-15%;

and/or the flow rate of the reducing gas is 10-100 ml/min, preferably 10-40 ml/min;

and/or the reduction temperature is 100-400 ℃, preferably 200-350 ℃;

and/or the reduction time is 1-6 h, preferably 1-3 h.

In some embodiments, the precursor is prepared by a method comprising preparing a precipitate from a cobalt source and a precipitant by a precipitation method, and optionally calcining the precipitate to obtain the precursor;

preferably, the cobalt source comprises at least one of a salt, an ester and a complex containing cobalt element, more preferably the cobalt source is selected from at least one of cobalt nitrate, cobalt acetate, cobalt carbonyl and cobalt chloride;

and/or the precipitant comprises at least one of an amide, a base and a salt capable of co-precipitating with the cobalt source, preferably the precipitant is selected from at least one of ammonium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, ammonium bicarbonate, urea, sodium hydroxide and potassium hydroxide;

and/or the calcining temperature is 400-450 ℃.

In some embodiments, the preparation method of the precursor comprises preparing the precursor by a cobalt source by adopting a high-temperature thermal decomposition method;

preferably, the cobalt source comprises at least one of a salt, an ester and a complex containing cobalt element, more preferably the cobalt source is selected from at least one of cobalt nitrate and cobalt acetate;

and/or, the conditions of the high-temperature thermal decomposition method comprise: the calcination temperature is 300-600 ℃, preferably 400-550 ℃.

In some embodiments, the cobalt-based catalyst comprises a supported cobalt-based catalyst, the support of which comprises a metal oxide, SiO₂And activated carbon;

preferably, the metal oxide comprises at least one of a group IIIA metal oxide, a group IIA metal oxide, a group IVB metal oxide, a lanthanide metal oxide and a group VIB metal oxide, more preferably the metal oxide is selected from Al₂O₃、MgO、TiO₂、ZrO₂、CeO₂And MoO₃At least one of (1).

In some embodiments, the method of preparing the supported cobalt-based catalyst comprises preparing a precursor, and optionally reducing the precursor to obtain the supported cobalt-based catalyst;

and/or the reduction temperature is 100-400 ℃, preferably 200-350 ℃;

and/or the reduction time is 1-6 h, preferably 1-3 h.

In some embodiments, the precursor is prepared by a method comprising co-precipitating a cobalt source and a support precursor to prepare a precipitate, and optionally calcining the precipitate to obtain the precursor;

preferably, the cobalt source comprises at least one of a salt, an ester, and a complex containing cobalt element, more preferably the cobalt source is selected from cobalt chloride;

and/or, the support precursor comprises at least one of a salt of a group IIIA metal, a salt of a group IIA metal, a salt of a group IVB metal, a salt of a lanthanide metal, and a salt of a group VIB metal;

and/or the calcining temperature is 350-450 ℃.

In some embodiments, the precursor is prepared by obtaining a support, then loading the support with a cobalt source by an equal volume impregnation method, an excess impregnation method or a precipitation deposition method, and finally optionally calcining;

and/or the calcining temperature is 350-450 ℃.

From the above description, the cobalt-based catalyst provided by the present disclosure is applied to the hydrogenolysis reaction of biomass and derivatives thereof, wherein the biomass or derivatives thereof are used as a reaction substrate, and the reaction substrate and a hydrogen source are subjected to the hydrogenolysis reaction under the catalysis of the cobalt-based catalyst; the cobalt-based catalyst has high catalytic activity, can realize hydrogenolysis of biomass and derivatives thereof at low temperature in a short time to obtain products with high purity, and the obtained products can be used as production raw materials of biomass fuel, degradable plastics, medicines, pesticides and the like and have high added value; secondly, the cobalt-based catalyst has magnetism, is convenient for separation and recycling of the catalyst, and has good industrial application prospect; the cobalt-based catalyst is low in cost, and the industrial cost can be effectively reduced.

Drawings

In order to more clearly illustrate the technical solutions in the present disclosure or related technologies, the drawings needed to be used in the description of the embodiments or related technologies are briefly introduced below, and it is obvious that the drawings in the following description are only embodiments of the present disclosure, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is a TEM image of the active phase of a core-shell Co @ CoO catalyst provided in an embodiment of the present disclosure;

FIG. 2 is an XRD pattern of a core-shell Co @ CoO catalyst provided in embodiments of the present disclosure;

FIG. 3 is a graph illustrating the cycle stability of core-shell Co @ CoO catalysts provided in accordance with an embodiment of the present disclosure.

Detailed Description

For the purpose of promoting a better understanding of the objects, aspects and advantages of the present disclosure, reference is made to the following detailed description taken in conjunction with the accompanying drawings.

It is to be noted that technical terms or scientific terms used in the embodiments of the present disclosure should have a general meaning as understood by those having ordinary skill in the art to which the present disclosure belongs, unless otherwise defined.

The current problems of energy shortage and environmental pollution are increasingly highlighted, and the development of renewable resources capable of replacing fossil energy is urgent.

The reserves of biomass resources on earth are very abundant, accounting for 68% of global renewable energy, mainly existing in the form of carbohydrates, but only less than 4% of the biomass energy is utilized by human beings. More importantly, chemical products obtained by utilizing the biomass energy are discharged into the atmosphere in the form of carbon dioxide after being used, and plants convert the carbon dioxide into the biomass energy through photosynthesis, so that carbon cycle in the nature is realized. A conversion strategy of preparing a series of platform compounds from raw biomass and preparing fine chemicals and biofuel by means of upgrading and upgrading is widely concerned.

Currently, hydrogenolysis of biomass and derivatives thereof is the most widely studied utilization strategy, but the hydrogenolysis reaction of biomass and derivatives thereof faces the problem of low catalyst activity, and in order to achieve high yield of target products, longer reaction time or higher reaction temperature is required; in addition, the catalyst and the product are difficult to separate and recycle, and the method has no industrial potential, thereby influencing the industrial process.

In order to solve the problems, the disclosure provides an application of a cobalt-based catalyst in a hydrogenolysis reaction of biomass and derivatives thereof, which includes that the biomass or derivatives thereof are used as reaction substrates, and the reaction substrates and a hydrogen source are subjected to the hydrogenolysis reaction under the catalysis of the cobalt-based catalyst.

In some possible embodiments, the biomass or derivative thereof may include at least one of furans, higher fatty acids, and lignin.

In the present disclosure, the furan-based compound refers to a compound having a furan group in a molecular structure, and the present disclosure does not have any limitation on the number of carbon atoms, substituents and specific structures contained in the furan group in the furan-based compound. The higher fatty acid refers to a compound having a carboxylic acid group and an aliphatic hydrocarbon group in a molecular structure, and the higher fatty acid may include a saturated higher fatty acid and an unsaturated higher fatty acid, and the present disclosure does not have any limitation on the number of carbon atoms, substituents, and specific structure contained in the aliphatic hydrocarbon group of the higher fatty acid.

In some possible embodiments, the furanic compounds may include at least one of 5-hydroxymethylfurfural, furfural, and furfuryl alcohol.

In some possible embodiments, the higher fatty acid may include at least one of palmitic acid, stearic acid, oleic acid, arachidic acid, and ligninic acid.

In some possible embodiments, the lignin may include at least one of hardwood lignin, softwood lignin, and herbaceous lignin. Preferably, the hardwood lignin may include at least one of birch lignin, poplar lignin, willow lignin, beech lignin and oak lignin, the softwood lignin may include at least one of pine lignin, cedar lignin and cedar lignin, and the herbaceous lignin may include at least one of corn stover lignin, wheat straw lignin and rice straw lignin.

In some possible embodiments, the hydrogen source may include at least one of hydrogen gas and an organic hydrogen source.

In the present disclosure, the organic hydrogen source refers to an organic compound capable of providing hydrogen element, and the number of carbon atoms, substituents and specific structure contained in the organic hydrogen source are not limited in the present disclosure. Preferably, the organic hydrogen source may include at least one of methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerol, formic acid, acetic acid and cyclohexane, more preferably isopropanol.

In some possible embodiments, the mass ratio of the reaction substrate to the cobalt-based catalyst may be 1: (0.01-2).

The reaction substrate in this disclosure includes biomass or a biomass derivative; the "mass ratio of the reaction substrate to the cobalt-based catalyst" refers to a ratio of the mass of the reaction substrate to the mass of the cobalt-based catalyst, which may be 1: (0.01-2) may be, for example, 1:0.01, 1:0.05, 1:0.1, 1:0.5, 1:0.7, 1:1, 1:1.3, 1:1.5, 1:2, etc., and is not particularly limited.

In some possible embodiments, the reaction temperature may be 100 to 300 ℃, preferably 130 to 210 ℃.

The reaction temperature in the present disclosure refers to a temperature required for the hydrogenolysis reaction of the biomass or the derivative thereof, and the temperature may be 100 to 300 ℃, preferably 130 to 210 ℃, for example, 100 ℃, 130 ℃, 150 ℃, 170 ℃, 210 ℃, 250 ℃, or 300 ℃, and is not particularly limited. The cobalt-based catalyst provided by the disclosure has high catalytic activity, can catalyze the biomass or biomass derivative to carry out hydrogenolysis reaction at low temperature, saves energy and improves the synthesis efficiency.

In some possible embodiments, the reaction time may be 0.5 to 20 hours, preferably 2 to 16 hours.

The reaction time in the present disclosure refers to the time required for the hydrogenolysis reaction of the biomass or the derivative thereof, and the time may be 0.5 to 20 hours, preferably 2 to 16 hours, for example, 0.5 hour, 2 hours, 5 hours, 10 hours, 16 hours, or 20 hours, and is not particularly limited. The cobalt-based catalyst provided by the disclosure has high catalytic activity, can catalyze and finish hydrogenolysis reaction of biomass or biomass derivatives in a short time, shortens the reaction time and improves the synthesis efficiency.

In some possible embodiments, the pressure of the hydrogen gas may be 0.5 to 5MPa, preferably 0.5 to 2 MPa.

When hydrogen is used as a hydrogen source in the present disclosure, the pressure of hydrogen may be 0.5 to 5MPa, preferably 0.5 to 2 MPa; for example, the pressure may be 0.5MPa, 1MPa, 1.5MPa, 2MPa, 3MPa or 5MPa, and the like, and is not particularly limited.

In one possible embodiment, the mass ratio of the reaction substrate to the organic hydrogen source can be 1 (0.5-20), and preferably 1 (1-5).

When the organic hydrogen source is taken as the hydrogen source in the present disclosure, the mass ratio of the reaction substrate to the organic hydrogen source may be 1 (0.5-20), preferably 1 (1-5); for example, the ratio may be 1:0.5, 1:1, 1:3, 1:5, 1:8, 1:10, 1:15, or 1:20, and the like, and is not particularly limited.

In some possible embodiments, the hydrogenolysis reaction can be carried out in a reaction medium, wherein the mass ratio of the reaction substrate to the reaction medium can be 1 (1-20), and preferably 1 (1-5).

The "mass ratio of the reaction substrate to the reaction medium" in the present disclosure refers to a ratio of the mass of the reaction substrate to the mass of the reaction medium, and the ratio may be 1 (1 to 20), preferably 1 (1 to 5), and may be, for example, 1:1, 1:5, 1:10, 1:15, or 1:20, and is not particularly limited.

In some possible embodiments, the reaction medium comprises at least one of water, an ionic liquid, and an organic solvent.

In some possible embodiments, the organic solvent may include at least one of dioxane, tetrahydrofuran, cyclohexane, dodecane, methanol, and ethanol.

In some possible embodiments, the hydrogenolysis of biomass or its derivatives may be carried out using a batch reaction process using reactors that may include batch kettles, fluidized beds, and slurry beds, or a continuous reaction process using reactors that may include fixed and moving beds.

The process for the hydrogenolysis reaction of biomass or derivatives thereof provided in the present disclosure may be: preparing a prescription amount of biomass or biomass derivatives, a cobalt-based catalyst and a reaction medium, adding the biomass or biomass derivatives, the cobalt-based catalyst and the reaction medium into an intermittent reaction kettle, and reacting for 0.5-5 h under the conditions that the pressure of hydrogen is 0.5-1Mpa and the reaction temperature is 50-180 ℃.

The present disclosure also provides a method for determining the conversion rate and yield of the hydrogenolysis reaction of biomass or biomass derivatives, which may be: performing qualitative analysis and quantitative analysis on the reaction product by gas chromatography-mass spectrometry (GC-MS Agilent 7890A-5975C) and gas chromatography (GC Agilent 7890A), wherein an HP-5 chromatographic column is adopted, and the temperature programming conditions of the chromatographic column are as follows: the temperature is maintained at 50 ℃ for 10mins, the temperature is increased to 250 ℃ at the heating rate of 10 ℃/min, and the temperature is maintained at 250 ℃ for 5 mins.

In some possible embodiments, the cobalt-based catalyst comprises a core-shell Co @ CoO catalyst having a core of cobalt and an outer shell of cobaltous oxide containing oxygen vacancies.

Fig. 1 is a TEM image of the active phase of the core-shell Co @ CoO catalyst provided in the present disclosure, and the morphology information of the core-shell Co @ CoO catalyst was obtained by transmission electron microscopy. The core-shell structure of the core-shell Co @ CoO catalyst can be clearly seen in the figure, and the outer layer is the lattice stripe of CoO and the inner layer is the lattice stripe of metal Co through measurement, which shows that the core-shell Co @ CoO catalyst prepared by the method is the core-shell structure with the outer layer of CoO and the inner layer of Co.

Fig. 2 is an XRD pattern of the core-shell Co @ CoO catalyst provided by the present disclosure, and information on the crystalline phase of the core-shell Co @ CoO catalyst was obtained by an XRD diffractometer. The diffraction peaks for metallic Co are clearly discernible in the figure, and the diffraction peaks for CoO are also found in figure 1, indicating that the core-shell Co @ CoO catalyst prepared by the present disclosure contains both metallic Co and CoO phases.

The active phase of the core-shell Co @ CoO catalyst described in this disclosure is cobaltous oxide. It has been found that dissociation of hydrogen or organic hydrogen sources is an important step in the hydrogenolysis reaction. H produced by cracking of hydrogen^-The activity of the species is much higher than that of the H radical species. In the conventional catalyst used in the related art, in the course of catalyzing the hydrogenolysis reaction of biomass or a biomass derivative, the catalytic active site is a metal center where hydrogen gas generates H radicals by cracking. Since the activity of H radical is low, resulting in poor reactivity, higher reaction temperature and longer reaction time are required to obtain high yield of target product.

The disclosure introduces cobaltous oxide active sites containing rich oxygen vacancies in a cobalt-based catalyst, where hydrogen or an organic hydrogen source generates H by cleavage^-Species, H^-The species further participate in the hydrogenolysis process of biomass and biomass derivatives. Due to H^-The activity of the species is far higher than that of H free radicals, the catalytic activity of the reaction is obviously improved, and the high yield of the target product is realized under the conditions of low temperature and short time.

In some possible embodiments, the preparation method of the core-shell Co @ CoO catalyst comprises preparing a cobalt source and a precipitant by a precipitation method to obtain a precipitate, optionally calcining the precipitate to obtain the precursor, and optionally reducing the precursor to obtain the core-shell Co @ CoO catalyst.

The precipitation method in the present disclosure has a conventional meaning in the art, and may be performed according to the existing precipitation method in the art, as long as the cobalt source and the precipitant can be co-precipitated to obtain a precipitate, and will not be described herein again.

Preferably, the cobalt source is used in an amount such that the amount of active component in the resulting core-shell Co @ CoO catalyst satisfies the desired corresponding amount.

Preferably, the present disclosure is not limited to a specific kind of the cobalt source as long as the core-shell type Co @ CoO catalyst can be prepared by the above-mentioned method; more preferably, the cobalt source may include at least one of a salt, an ester and a complex containing cobalt element, the salt may include at least one of a nitrate, an acetate and a chloride salt, and the complex may be any one of existing complexes containing cobalt element, which will not be described herein again; further preferably, the cobalt source may be selected from at least one of cobalt nitrate, cobalt acetate, cobalt carbonyl, and cobalt chloride.

Preferably, the present disclosure is not limited to a specific kind of the precipitant as long as it can be coprecipitated with the cobalt source; more preferably, the precipitant may include at least one of an amide, a base, and a salt capable of coprecipitation with the cobalt source; further preferably, the precipitant may be at least one selected from the group consisting of ammonium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, ammonium bicarbonate, urea, sodium hydroxide, and potassium hydroxide.

Preferably, the calcination temperature may be 400 to 450 ℃; for example, the temperature may be 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, or 450 ℃, and the like, and is not particularly limited.

Preferably, the volume fraction of hydrogen in the reducing gas may be 5 to 30%, preferably 5 to 15%.

In the present disclosure, the reducing gas is a gas for reducing the precursor, the reducing gas is a mixed gas of hydrogen and argon, and the volume fraction of the hydrogen is a volume percentage of the hydrogen in the mixed gas, and the volume percentage may be 5 to 30%, preferably 5 to 15%, for example, 5%, 8%, 10%, 15%, 18%, 20%, 25%, or 30%, and the like, and is not particularly limited.

Preferably, the flow rate of the reducing gas can be 10-100 ml/min, and more preferably 10-40 ml/min; for example, the concentration may be 10ml/min, 20ml/min, 30ml/min, 40ml/min, 50ml/min, 60ml/min, 80ml/min, or 100ml/min, and the like, and is not particularly limited.

Preferably, the reduction temperature may be 100 to 400 ℃, more preferably 200 to 350 ℃.

In the present disclosure, the reduction temperature refers to a temperature at which the precursor is reduced by using a reduction gas, and the temperature may be 100 to 400 ℃, preferably 200 to 350 ℃, and may be, for example, 100 ℃, 150 ℃, 200 ℃, 225 ℃, 250 ℃, 275 ℃, 300 ℃, 350 ℃, or 400 ℃, and is not particularly limited.

Preferably, the reduction time can be 1-6 h, and more preferably 1-3 h.

In the present disclosure, the reduction time refers to a time for reducing the precursor with the reducing gas, and the time may be 1 to 6 hours, preferably 1 to 3 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, or 6 hours, and the like, and is not particularly limited.

The method for preparing the core-shell type Co @ CoO catalyst by adopting the precipitation method provided by the disclosure can comprise the following steps: co-precipitating a cobalt source and a precipitator by a precipitation method to obtain a precipitate, calcining the precipitate at 400-450 ℃ to obtain a precursor, and reducing the precursor in a reducing gas with the flow rate of 10-100 ml/min and the volume fraction of hydrogen of 5-30% for 1-6 h to obtain the core-shell Co @ CoO catalyst.

In some possible embodiments, the preparation method of the core-shell Co @ CoO catalyst may include preparing the precursor by a high temperature pyrolysis method, and then optionally reducing the precursor to obtain the core-shell Co @ CoO catalyst.

The pyrolysis method described in the present disclosure has a general meaning in the art, and can be performed according to the existing pyrolysis method in the art, as long as the precursor can be prepared, and will not be described herein again.

Preferably, the present disclosure is not limited to a specific kind of the cobalt source as long as the core-shell type Co @ CoO catalyst can be prepared by the above-mentioned method; more preferably, the cobalt source may include at least one of a salt, an ester and a complex containing cobalt element, the salt may include at least one of a nitrate, an acetate and a chloride salt, and the complex may be any one of existing complexes containing cobalt element, which will not be described herein again; further preferably, the cobalt source may be selected from at least one of cobalt nitrate and cobalt acetate.

Preferably, the conditions of the high temperature thermal decomposition method include: the calcination temperature can be 300-600 ℃, and more preferably 400-550 ℃; for example, the temperature may be 300 ℃, 350 ℃, 400 ℃, 430 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃, and the like, and is not particularly limited.

Preferably, the volume fraction of hydrogen in the reducing gas can be 5-30%, more preferably 5-15%; for example, the concentration may be 5%, 8%, 10%, 12%, 15%, 20%, 25%, or 30%, and the like, and is not particularly limited.

Preferably, the flow rate of the reducing gas can be 10-100 ml/min, and more preferably 10-40 ml/min; for example, the concentration may be 10ml/min, 30ml/min, 40ml/min, 50ml/min, 60ml/min, 80ml/min, or 100ml/min, without limitation

Preferably, the reduction temperature can be 100-400 ℃, and more preferably 200-350 ℃; for example, the temperature may be 100 ℃, 150 ℃, 200 ℃, 225 ℃, 250 ℃, 275 ℃, 300 ℃, 350 ℃, 375 ℃, or 400 ℃ and the like, and the temperature is not particularly limited.

Preferably, the reduction time can be 1-6 h, and more preferably 1-3 h; for example, the reaction time may be 1h, 2h, 3h, 4h, 5h, or 6h, and the like, and is not particularly limited.

The method for preparing the core-shell Co @ CoO catalyst by adopting the high-temperature thermal decomposition method provided by the disclosure can comprise the following steps: calcining a cobalt source at 300-600 ℃ to obtain a precursor, and reducing the precursor in a reducing gas with the flow rate of 10-100 ml/min and the volume fraction of hydrogen of 5-30% for 1-6 h to obtain the core-shell Co @ CoO catalyst.

In some possible embodiments, the cobalt-based catalyst may comprise a supported cobalt-based catalyst; the present disclosure is not limited to a specific kind of carrier as long as it can carry a cobalt source; preferably, the carrier of the supported cobalt-based catalyst may include metal oxide, SiO₂And activated carbon.

The present disclosure is not limited to a specific kind of metal oxide as long as it can support a cobalt source; preferably, the metal oxide may comprise at least one of a group IIIA metal oxide, a group IIA metal oxide, a group IVB metal oxide, a lanthanide metal oxide and a group VIB metal oxide, more preferably the metal oxide is selected from Al₂O₃、MgO、TiO₂、ZrO₂、CeO₂And MoO₃At least one of (1).

In some possible embodiments, the preparation method of the supported cobalt-based catalyst may include coprecipitating a cobalt source and a support precursor to prepare a precipitate, then optionally calcining the precipitate to obtain the precursor, and finally optionally reducing the precursor to obtain the supported cobalt-based catalyst.

The co-precipitation described in the present disclosure has a conventional meaning in the art, and may be performed according to the existing co-precipitation method in the art, as long as the cobalt source can be introduced into the support, and is not described herein again.

Preferably, the cobalt source is used in an amount such that the content of active component in the resulting supported cobalt-based catalyst meets the desired corresponding content.

The present disclosure is not limited to a specific kind of the cobalt source as long as the supported cobalt-based catalyst can be prepared by the above-mentioned method; preferably, the cobalt source may include at least one of a salt, an ester and a complex containing cobalt element, the salt may include at least one of a nitrate, an acetate and a chloride salt, and the complex may be any one of existing complexes containing cobalt element, which is not described herein again; more preferably, the cobalt source may be selected from cobalt chloride.

Preferably, the support precursor comprises at least one of a salt of a group IIIA metal, a salt of a group IIA metal, a salt of a group IVB metal, a salt of a lanthanide metal, and a salt of a group VIB metal.

The present disclosure is not limited with respect to the specific type of support precursor, as long as the supported cobalt source of the support can be made; preferably, the support precursor can include at least one of a group IIIA metal salt, a group IIA metal salt, a group IVB metal salt, a lanthanide metal salt, and a group VIB metal salt, which can be at least one of a nitrate, phosphate, sulfate, carbonate, and the like; more preferably, the support precursor is selected from magnesium nitrate, aluminium nitrate or cerium nitrate.

Preferably, the calcination temperature can be 350-450 ℃; for example, the temperature may be 350 ℃, 380 ℃, 400 ℃, 420 ℃ or 450 ℃, and the like, and is not particularly limited.

Preferably, the volume fraction of hydrogen in the reducing gas can be 5-30%, preferably 5-15%; for example, the concentration may be 5%, 10%, 15%, 20%, 25%, 30%, etc., and is not particularly limited.

Preferably, the flow rate of the reducing gas can be 10-100 ml/min, preferably 10-40 ml/min; for example, the concentration may be 10ml/min, 20ml/min, 40ml/min, 60ml/min, or 80ml/min, and the like, and is not particularly limited.

Preferably, the reduction temperature can be 100-400 ℃, and preferably 200-350 ℃; for example, the temperature may be 100 ℃, 200 ℃, 250 ℃, 275 ℃, 300 ℃, 350 ℃ or 400 ℃, and the like, and is not particularly limited.

Preferably, the reduction time can be 1-6 h, preferably 1-3 h; for example, the reaction time may be 1h, 2h, 3h, 4h, 5h, or 6h, and the like, and is not particularly limited.

In some possible embodiments, the preparation method of the supported cobalt-based catalyst may include preparing a support, then loading a cobalt source on the support by an equal volume impregnation method, an excess impregnation method or a precipitation deposition method, and optionally calcining to obtain a precursor, and finally optionally reducing the precursor to obtain the supported cobalt-based catalyst.

The isovolumetric impregnation method, the excess impregnation method or the precipitation deposition method in the present disclosure have conventional explanations in the art, and may be performed according to the existing isovolumetric impregnation method, the excess impregnation method or the precipitation deposition method in the art, as long as the cobalt source and the support can be impregnated, and thus, the details are not repeated herein.

The present disclosure has no limitation on the kind of the cobalt source as long as the supported cobalt-based catalyst can be obtained by the above-mentioned method; preferably, the cobalt source may include at least one of a salt, an ester, and a complex containing cobalt element, and more preferably, the cobalt source may be selected from cobalt chloride.

Preferably, the calcination temperature may be 350 to 450 ℃, for example, 350 ℃, 380 ℃, 400 ℃, 410 ℃, 420 ℃ or 450 ℃, and the like, and is not particularly limited.

Preferably, the volume fraction of hydrogen in the reducing gas can be 5-30%, preferably 5-15%; for example, the concentration may be 5%, 10%, 15%, 20%, 27%, 30%, etc., and is not particularly limited.

Preferably, the flow rate of the reducing gas can be 10-100 ml/min, preferably 10-40 ml/min; for example, the concentration may be 10ml/min, 20ml/min, 30ml/min, 40ml/min, 60ml/min, or 100ml/min, and the like, and is not particularly limited.

Preferably, the reduction temperature can be 100-400 ℃, and preferably 200-350 ℃; for example, the temperature may be 100 ℃, 200 ℃, 225 ℃, 250 ℃, 275 ℃, 300 ℃, 350 ℃, or 400 ℃ and the like, and is not particularly limited.

The application of the cobalt-based catalyst in the hydrogenolysis reaction of biomass and derivatives thereof provided by the disclosure is characterized in that the biomass or the derivatives thereof are used as reaction substrates, and the reaction substrates and a hydrogen source are subjected to hydrogenolysis reaction under the catalysis of the cobalt-based catalyst; the cobalt-based catalyst has high catalytic activity, can realize hydrogenolysis of biomass and derivatives thereof at low temperature in a short time to obtain products with high purity, and the obtained products can be used as production raw materials of biomass fuel, degradable plastics, medicines, pesticides and the like and have high added value; in addition, the cobalt-based catalyst has magnetism, is convenient for separation and recycling of the catalyst, and has good industrial application prospect; the cobalt-based catalyst is low in cost, and the industrial cost can be effectively reduced.

The present disclosure will be described in detail below by way of examples.

In the following examples, the hydrogenolysis process performed by a cobalt-based catalyst using a batch reactor includes: adding a reaction substrate, a cobalt-based catalyst and a reaction medium into a 25mL batch reactor, and reacting for 0.5-5 hours under the conditions that the hydrogen partial pressure is 0.5-1Mpa and the temperature is 50-180 ℃. Performing qualitative analysis and quantitative analysis on the reaction product by gas chromatography-mass spectrometry (GC-MS Agilent 7890A-5975C) and gas chromatography (GC Agilent 7890A), wherein an HP-5 chromatographic column is adopted, and the temperature programming conditions of the chromatographic column are as follows: the temperature is maintained at 50 ℃ for 10mins, the temperature is increased to 250 ℃ at the heating rate of 10 ℃/min, and the temperature is maintained at 250 ℃ for 5 mins.

In the following examples, the preparation of core-shell Co @ CoO catalyst by precipitation comprises: dissolving 60mmol of cobalt source in 200ml of deionized water to obtain a solution A; 69mmol of precipitant were dissolved in 200ml of deionized water as solution B. In a water bath at 65 ℃, the solution B was slowly dropped into the solution a while vigorously stirring until the pH of the mixed solution was 9, and the dropping of the solution B was stopped. Stirring was continued in the water bath at 65 ℃ for 1h and then allowed to stand at room temperature for 12 h. Filtering, washing with deionized water for several times, drying in an oven at 100 deg.C overnight, grinding,calcining the mixture for 4 hours in a muffle furnace at the temperature of 450 ℃ to obtain a precursor Co₃O₄(ii) a Then the precursor Co₃O₄At a temperature of 225-400 ℃, adopting H₂Reducing gas with volume fraction of 5-10% and flow rate of 10-40 ml/mim for 1-3 h to obtain the catalyst.

Examples 1 to 7

In examples 1-7, the precipitation method was used to prepare the core-shell Co @ CoO catalyst: the cobalt source was cobalt nitrate, the precipitant was sodium carbonate, the calcination temperature was 450 ℃ and the reduction temperature was 300 ℃, and examples 1 to 7 were different in the volume fraction of hydrogen in the reducing gas used, the flow rate of the reducing gas, and the reduction time.

In examples 1 to 7, the hydrogenolysis reaction was catalyzed with a cobalt-based catalyst: the reaction substrate is 0.15g of 5-Hydroxymethylfurfural (HMF), the catalyst is 0.03g of core-shell Co @ CoO catalyst, the reaction medium is 5ml of tetrahydrofuran, the hydrogen partial pressure is 1MPa, the reaction temperature is 130 ℃, the reaction time is 2 hours, and a batch reaction kettle is adopted to obtain a reaction product, namely 2, 5-Dimethylfuran (DMF). The conversion of the reaction substrate and the yield of the reaction product in each example were measured, and the results are shown in Table 1.

TABLE 1

Examples 8 to 13

In the preparation of core-shell Co @ CoO catalysts by precipitation in examples 8-13: the cobalt source is cobalt nitrate, the precipitator is sodium carbonate, the calcination temperature is 450 ℃, the volume fraction of hydrogen in the reducing gas is 10%, the flow rate of the reducing gas is 30ml/min, the reduction time is 2h, and the difference of examples 8-13 lies in that the adopted reduction temperatures are different, specifically, the reduction temperatures of examples 8-13 are 225 ℃, 250 ℃, 275 ℃, 300 ℃, 350 ℃ and 400 ℃, and the obtained core-shell type Co @ CoO catalysts are Co @ CoO-P-225, Co @ CoO-P-250, Co @ CoO-P-275, Co @ CoO-P-300, Co @ CoO-P-350 and Co CoO-P-400 respectively.

In examples 8-13, the hydrogenolysis reaction was catalyzed with a cobalt-based catalyst: the reaction substrate is 0.15g of 5-hydroxymethylfurfural, the catalyst is 0.03g of core-shell Co @ CoO catalyst, the reaction medium is 5ml of tetrahydrofuran, the hydrogen partial pressure is 1MPa, the reaction temperature is 130 ℃, the reaction time is 2 hours, and a batch reactor is adopted to obtain the reaction product 2, 5-dimethylfuran. The conversion of the reaction substrate and the yield of the reaction product in each example were measured, and the results are shown in Table 2.

TABLE 2

P represents the cobalt-based catalyst prepared by precipitation.

Examples 14 to 16

In the preparation of core-shell Co @ CoO catalysts by precipitation in examples 14-16: the precipitant was sodium carbonate, the calcination temperature was 450 ℃, the reduction temperature was 300 ℃, the volume fraction of hydrogen in the reducing gas was 10%, the flow rate of the reducing gas was 30ml/min, and the reduction time was 2 hours, and examples 14 to 16 were different in the cobalt source used, specifically, the cobalt sources used in examples 14 to 16 were cobalt acetate, cobalt chloride, and cobalt carbonyl, respectively.

In examples 14-16, the hydrogenolysis reaction was catalyzed with a cobalt-based catalyst: the reaction substrate is 0.15g of 5-hydroxymethylfurfural, the catalyst is 0.03g of core-shell Co @ CoO catalyst, the reaction medium is 5ml of tetrahydrofuran, the hydrogen partial pressure is 1MPa, the reaction temperature is 130 ℃, the reaction time is 2 hours, and a batch reactor is adopted to obtain the reaction product 2, 5-dimethylfuran. The conversion of the reaction substrate and the yield of the reaction product in each example were measured, and the results are shown in Table 3.

TABLE 3

The results in table 3 show that cobalt-based catalysts prepared using various cobalt sources all have catalytic activity.

Examples 17 to 23

In the preparation of core-shell Co @ CoO catalysts by precipitation in examples 17-23: the cobalt source is cobalt nitrate, the calcination temperature is 450 ℃, the reduction temperature is 300 ℃, the volume fraction of hydrogen in the reduction gas is 10%, the flow rate of the reduction gas is 30ml/min, and the reduction time is 2h, and examples 17 to 23 are different in the adopted precipitating agents, specifically, the precipitating agents of examples 17 to 23 are ammonium carbonate, potassium carbonate, sodium bicarbonate, ammonium bicarbonate, urea, sodium hydroxide, and potassium hydroxide, respectively.

In examples 17-23, the hydrogenolysis reaction was catalyzed with a cobalt-based catalyst: the reaction substrate is 0.15g of 5-hydroxymethylfurfural, the catalyst is 0.03g of core-shell Co @ CoO catalyst, the reaction medium is 5ml of tetrahydrofuran, the hydrogen partial pressure is 1MPa, the reaction temperature is 130 ℃, the reaction time is 2 hours, and a batch reactor is adopted to obtain the reaction product 2, 5-dimethylfuran. The conversion of the reaction substrate and the yield of the reaction product in each example were measured, and the results are shown in Table 4.

TABLE 4

The results in table 4 show that cobalt-based catalysts prepared with various precipitants all have catalytic activity.

Examples 24 to 31

In preparing supported cobalt-based catalysts in examples 24-31: soaking cobalt chloride solution on a carrier by an equal-volume soaking method, wherein the loading is 5%, the cobalt accounts for 5% of the total weight of the supported cobalt-based catalyst, drying the cobalt-based catalyst in a 100 ℃ oven for 12h, and then placing a catalyst precursor in a nitrogen atmosphere for high-temperature treatment, wherein the specific process comprises the following steps: 1g of the precursor is heated to 450 ℃ from room temperature for 2h in a quartz tube, kept for 4h and automatically cooled; the cooled catalyst was then taken up in H₂Volume fraction of 10% of H₂The reduction is carried out under the Ar atmosphere, and the specific process is as follows: 1g of the precursor was raised from room temperature for 1h to 300 ℃ in a quartz tube and held for 2 h; examples 24 to 31 differ in the carrier used, specifically, Al is used as the carrier in examples 27 to 35, respectively₂O₃、MgO、TiO₂、ZrO₂、CeO₂、MoO₃、SiO₂And active carbon.

In examples 24-31, the hydrogenolysis reaction was catalyzed with a cobalt-based catalyst: the reaction substrate is 0.15g of 5-hydroxymethylfurfural, the catalyst is 0.03g of supported Co @ CoO catalyst, the reaction medium is 5ml of tetrahydrofuran, the hydrogen partial pressure is 1MPa, the reaction temperature is 130 ℃, the reaction time is 2 hours, and a batch reactor is adopted to obtain the reaction product 2, 5-dimethylfuran. The conversion of the reaction substrate and the yield of the reaction product in each example were measured, and the results are shown in Table 5.

TABLE 5

The results in table 5 show that the supported cobalt-based catalysts prepared with various supports all have catalytic activity.

Examples 32 to 35

When preparing core-shell Co @ CoO catalysts in examples 32-35: the cobalt source is cobalt nitrate, the precipitator is sodium carbonate, the calcining temperature is 450 ℃, the reducing temperature is 300 ℃, the volume fraction of hydrogen in the reducing gas is 10%, the flow rate of the reducing gas is 30ml/min, and the reducing time is 2 h.

In examples 32 to 35, the hydrogenolysis reaction was catalyzed with a cobalt-based catalyst: the reaction substrate is 0.15g of 5-hydroxymethylfurfural, the catalyst is 0.03g of Co @ CoO-P-300, the reaction medium is 5ml of tetrahydrofuran, the reaction temperature is 130 ℃, the reaction time is 2 hours, and a batch reactor is adopted to obtain a reaction product 2, 5-dimethylfuran; examples 32-35 differ in the source of hydrogen, specifically, 0.15g of methanol, ethanol, isopropanol, formic acid, respectively, for examples 32-35. The conversion of the reaction substrate and the yield of the reaction product in each example were measured, and the results are shown in Table 6.

TABLE 6

The results in table 6 show that cobalt-based catalysts are capable of catalyzing hydrogenolysis reactions using a variety of species as hydrogen sources.

Examples 36 to 54

In the preparation of core-shell Co @ CoO catalysts in examples 36-54: the cobalt source is cobalt nitrate, the precipitator is sodium carbonate, the calcining temperature is 450 ℃, the reducing temperature is 300 ℃, the volume fraction of hydrogen in the reducing gas is 10%, the flow rate of the reducing gas is 30ml/min, and the reducing time is 2 h.

In examples 36-54, hydrogenolysis was catalyzed using a cobalt-based catalyst: the method comprises the following steps of (1) taking 0.15g of 5-hydroxymethylfurfural as a reaction substrate, 0.03g of Co @ CoO-P-300 as a catalyst, taking 5ml of tetrahydrofuran as a reaction medium, taking hydrogen pressure of 0.5-3 MPa, taking the reaction temperature of 50-200 ℃, taking the reaction time of 0.5-4 h, and obtaining a reaction product 2, 5-dimethylfuran by adopting an intermittent reaction kettle; examples 36 to 54 differ in the reaction medium, the hydrogen partial pressure, the reaction temperature and the reaction time. The conversion of the reaction substrate and the yield of the reaction product in each example were measured, and the results are shown in Table 7.

TABLE 7

The results in table 7 show that the cobalt-based catalyst of the present disclosure can catalyze hydrogenolysis of reaction substrates at lower temperatures, in shorter time, in a variety of reaction media, and at lower hydrogen partial pressures.

Examples 55 to 76

Examples 55-76 differ in that a cobalt-based catalyst was prepared using a different method.

In examples 55 to 76, the hydrogenolysis reaction was catalyzed by using a cobalt-based catalyst: the reaction substrate is 5-hydroxymethylfurfural, the reaction medium is tetrahydrofuran, and the feeding airspeed of HMF is 25h^-1The catalyst amount was 0.5g, the hydrogen flow rate was 30mL/h, the hydrogen partial pressure was 1MPa, the temperature was 130 ℃ and a continuous fixed bed was used. Measurement of each implementationThe conversion of the reaction substrates and the yield of the reaction products in the examples are shown in Table 8.

TABLE 8

The results in Table 8 show that cobalt-based catalysts prepared by different methods can catalyze the hydrogenolysis reaction of furan compounds.

Examples 77 to 100

Examples 77-100 differ in that a cobalt-based catalyst was prepared using a different process.

In examples 77 to 100, the hydrogenolysis reaction was catalyzed with a cobalt-based catalyst: 0.2g of palmitic acid serving as a reaction substrate, 0.05g of catalyst, 2MPa of hydrogen partial pressure, 5ml of cyclohexane serving as a solvent, 170 ℃ of temperature and 12 hours of reaction time, and a batch reactor is adopted to obtain a reaction product, namely the palmitol. The conversion of the reaction substrate and the yield of the reaction product in each example were measured, and the results are shown in Table 9.

TABLE 9

The results in Table 9 show that cobalt-based catalysts prepared by different methods can catalyze hydrogenolysis reaction of higher fatty acid.

Example 101-

When preparing the core-shell Co @ CoO catalyst in example 101-104: the cobalt source is cobalt nitrate, the precipitator is sodium carbonate, the calcining temperature is 450 ℃, the reducing temperature is 300 ℃, the volume fraction of hydrogen in the reducing gas is 10%, the flow rate of the reducing gas is 30ml/min, and the reducing time is 2 h.

Example 101-104 catalytic hydrogenolysis reaction using a cobalt-based catalyst: the catalyst is 0.05g of Co @ CoO-P-300, the reaction medium is 5ml of cyclohexane, the hydrogen pressure is 2MPa, the reaction temperature is 170 ℃, the reaction time is 12 hours, and an intermittent reaction kettle is adopted; example 101-104 differs in that the reaction substrate is a different higher fatty acid and the reaction product is the corresponding higher fatty alcohol. The conversion of the reaction substrate and the yield of the reaction product in each example were measured, and the results are shown in Table 10.

Watch 10

The results in table 10 show that the cobalt-based catalyst disclosed by the disclosure can catalyze the hydrogenolysis reaction of higher fatty acid to obtain higher fatty alcohol, and the applicable substrate range is wide.

Example 105-

Example 105-128 differs in that a cobalt-based catalyst was prepared using a different method.

Example 105-128 catalytic hydrogenolysis reactions using a cobalt-based catalyst: the reaction substrate is 0.1g of birch lignin, the catalyst amount is 0.2g, the hydrogen partial pressure is 1MPa, the solvent is 5ml of dioxane, the temperature is 210 ℃, the reaction time is 16 hours, and an intermittent reaction kettle is adopted. The selectivity and yield of the reaction product in each example were measured, and the results are shown in Table 11.

TABLE 11

The results in Table 11 show that the cobalt-based catalysts prepared by the different methods all have catalytic activity.

Example 129-138

When preparing the core-shell Co @ CoO catalyst in example 129-138: the cobalt source is cobalt nitrate, the precipitator is sodium carbonate, the calcining temperature is 450 ℃, the reducing temperature is 300 ℃, the volume fraction of hydrogen in the reducing gas is 10%, the flow rate of the reducing gas is 30ml/min, and the reducing time is 2 h.

Example 129-138 catalytic hydrogenolysis reaction using a cobalt-based catalyst: the catalyst is 0.2g of Co @ CoO-P-300, the reaction medium is 5ml of dioxane, the hydrogen pressure is 1MPa, the reaction temperature is 210 ℃, the reaction time is 16h, and an intermittent reaction kettle is adopted; example 129-138 differs in that the reaction substrates are different lignins and the reaction product is the corresponding alkylcyclohexanols. The yield and selectivity of the reaction product in each example were measured, and the results are shown in Table 12.

The results in table 12 show that the cobalt-based catalyst of the present disclosure can catalyze the hydrogenolysis reaction of lignin to obtain alkylcyclohexanols, and the applicable substrate range is wide.

Example 139

And evaluating the stability of the cobalt-based catalyst in the HMF hydrogenolysis reaction.

In example 139, a cobalt-based catalyst was used to catalyze the hydrogenolysis reaction: the dosage of the catalyst Co @ CoO-P-300 is 0.5g, the reaction substrate is HMF, the reaction medium is tetrahydrofuran, and the feeding airspeed of the HMF is 26.6h^-1The hydrogen flow rate is 30mL/h, the hydrogen partial pressure is 1MPa, the reaction temperature is 130 ℃, and a continuous fixed bed is adopted. The conversion of the reaction substrate and the yield of the reaction product were measured in the reaction time of 0 to 100 hours in example 139, and the results are shown in FIG. 3.

The results in FIG. 3 show that the DMF yield is always maintained at about 75% in 100h of continuous reaction, indicating that the cobalt-based catalyst has excellent stability in hydrogenolysis reaction.

Comparative examples 1 to 6

The catalysts used in comparative examples 1 to 6 were copper-based catalysts, and the methods for preparing the copper-based catalysts in comparative examples 1 to 6 were the same as those for preparing the cobalt-based catalysts in examples 8 to 13, respectively. The process for catalyzing the hydrogenolysis reaction using the copper-based catalyst in comparative examples 1-6 was the same as that for the hydrogenolysis reaction using the cobalt-based catalyst in examples 8-13. The conversion rates of the reaction substrates and the yields of the reaction products in comparative examples 1 to 6 were measured, and the results are shown in Table 13.

Watch 13

As can be seen from comparative examples 8 to 13 and comparative examples 1 to 6, the cobalt-based catalyst has higher catalytic activity, selectivity and stability.

Comparative examples 7 to 8

Comparative examples 7 to 8 and examples 8 to 13 differ only in the reduction temperature, and the reduction temperature of comparative example 7 was 80 ℃ and the reduction temperature of comparative example 8 was 420 ℃. The conversion rates of the reaction substrates and the yields of the reaction products in comparative examples 7 to 8 were measured, and the results are shown in Table 14.

TABLE 14

As can be seen from comparison of examples 8-13 and comparative examples 7-8, the reduction temperature used in the preparation of the cobalt-based catalyst is 100-400 ℃, and the prepared cobalt-based catalyst has higher catalytic activity.

Comparative examples 9 to 10

Comparative examples 9 to 10 differ from example 2 only in the reaction temperature, comparative example 9 having a reaction temperature of 45 ℃ and comparative example 10 having a reaction temperature of 310 ℃. The conversion rates of the reaction substrates and the yields of the reaction products in comparative examples 9 to 10 were measured, and the results are shown in Table 15.

Watch 15

As can be seen from the comparison of example 2 and comparative examples 9 to 10, when the cobalt-based catalyst is used to catalyze the hydrogenolysis reaction, the catalytic effect is not good when the reaction temperature is lower than 50 ℃ or higher than 300 ℃.

Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the present disclosure, also technical features in the above embodiments or in different embodiments may be combined, steps may be implemented in any order, and there are many other variations of the different aspects of the embodiments of the present disclosure as described above, which are not provided in detail for the sake of brevity.

The disclosed embodiments are intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalents, improvements, and the like that may be made within the spirit and principles of the embodiments of the disclosure are intended to be included within the scope of the disclosure.

Claims

1. The application of the cobalt-based catalyst in the hydrogenolysis reaction of biomass and derivatives thereof is characterized by comprising the step of taking the biomass or the derivatives thereof as a reaction substrate, wherein the reaction substrate and a hydrogen source are subjected to the hydrogenolysis reaction under the catalysis of the cobalt-based catalyst.

2. The use of claim 1, wherein the biomass or derivative thereof comprises at least one of furans, higher fatty acids and lignin;

3. Use according to claim 2, wherein the furanic compounds comprise at least one of 5-hydroxymethylfurfural, furfural, and furfuryl alcohol;

4. The use according to claim 2, wherein the mass ratio of the reaction substrate to the cobalt-based catalyst is 1: (0.01-2);

and/or the reaction temperature is 50-300 ℃, preferably 130-210 ℃;

and/or the reaction time is 0.5-20 h, preferably 2-16 h;

and/or the pressure of the hydrogen is 0.5-5 MPa, preferably 0.5-2 MPa;

5. The use according to claim 1, wherein the hydrogenolysis reaction is carried out in a reaction medium, wherein the mass ratio of the reaction substrate to the reaction medium is 1 (1-20), preferably 1 (1-5); the reaction medium comprises at least one of water, an ionic liquid, and an organic solvent;

6. The use of claim 1, wherein said cobalt-based catalyst comprises a core-shell Co @ CoO catalyst having a core of cobalt and an outer shell of cobaltous oxide containing oxygen vacancies.

7. The use of claim 6, wherein the preparation method of the core-shell Co @ CoO catalyst comprises preparing a precursor, and optionally reducing the precursor to obtain the core-shell Co @ CoO catalyst;

and/or the reduction temperature is 100-400 ℃, preferably 200-350 ℃;

and/or the reduction time is 1-6 h, preferably 1-3 h.

8. The use according to claim 7, wherein the precursor is prepared by a method comprising preparing a precipitate from a cobalt source and a precipitant by precipitation, and optionally calcining the precipitate to obtain the precursor;

and/or the calcining temperature is 400-450 ℃.

9. The application of claim 7, wherein the preparation method of the precursor comprises preparing a cobalt source by a high-temperature thermal decomposition method to obtain the precursor;

10. The use of claim 1, wherein the cobalt-based catalyst comprises a supported cobalt-based catalyst, the support of which comprises a metal oxide, SiO₂And activated carbon;

11. The use according to claim 10, wherein the supported cobalt-based catalyst is prepared by a method comprising preparing a precursor, and optionally reducing the precursor to obtain the supported cobalt-based catalyst;

and/or the reduction temperature is 100-400 ℃, preferably 200-350 ℃;

and/or the reduction time is 1-6 h, preferably 1-3 h.

12. Use according to claim 11, wherein the precursor is prepared by a process comprising co-precipitating a cobalt source and a support precursor to prepare a precipitate, and optionally calcining the precipitate to obtain the precursor;

and/or the calcining temperature is 350-450 ℃.

13. The use according to claim 11, characterized in that the precursor is prepared by obtaining a support, then loading a cobalt source on the support by an isovolumetric impregnation method, an excess impregnation method or a precipitation deposition method, and finally optionally calcining;

and/or the calcining temperature is 350-450 ℃.