CN108671960B - High hydrothermal stability MOFs catalyst, preparation method thereof and method for preparing chemicals by using MOFs catalyst for cellulose conversion - Google Patents

High hydrothermal stability MOFs catalyst, preparation method thereof and method for preparing chemicals by using MOFs catalyst for cellulose conversion Download PDF

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CN108671960B
CN108671960B CN201810407709.1A CN201810407709A CN108671960B CN 108671960 B CN108671960 B CN 108671960B CN 201810407709 A CN201810407709 A CN 201810407709A CN 108671960 B CN108671960 B CN 108671960B
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陈宇
王恺丰
纪红兵
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Sun Yat Sen University
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J35/617—
    • B01J35/633—
    • B01J35/643—
    • 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
    • B01J37/0201—Impregnation
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C07D307/48—Furfural
    • C07D307/50—Preparation from natural products

Abstract

The invention discloses a high hydrothermal stability MOFs catalyst, a preparation method thereof and a method for preparing chemicals by cellulose conversion. The catalyst is obtained by using a metal organic framework compound as a carrier, modifying the metal organic framework compound UiO-66 by using a metal oxide, and modifying by using one or more transition metals through an isometric impregnation method. The invention also discloses a process for preparing chemicals by catalyzing cellulose hydrothermal conversion by one or more modified catalysts, which comprises the step of placing the catalyst introduced with the modified metal organic framework compound into a reaction kettle, and preparing functional chemicals by catalyzing cellulose hydrothermal conversion. After the catalytic product is separated and purified, the obtained product mainly takes functional chemicals such as furfural, cinnamaldehyde, lactic acid, levulinic acid and the like as main materials.

Description

High hydrothermal stability MOFs catalyst, preparation method thereof and method for preparing chemicals by using MOFs catalyst for cellulose conversion
Technical Field
The invention relates to the field of renewable biomass energy, in particular to a high hydrothermal stability MOFs catalyst, a preparation method thereof and a method for preparing chemicals by cellulose conversion.
Background
Energy is the material basis on which humans rely for survival. At present, people still rely on fossil fuels such as coal, petroleum and natural gas for energy demand. However, this presents two problems: on one hand, fossil resources are increasingly exhausted, and on the other hand, serious environmental problems are brought. The new energy nuclear energy, wind energy, solar energy and the like cannot be applied in a large scale due to the reasons of imperfect technology and the like. Therefore, the method has great significance for establishing a sustainable energy system, promoting national economic development and environmental protection by changing energy production and consumption modes and developing and utilizing renewable clean energy resources. The search and development of new energy sources become one of the main tasks of current academic research and are expected techniques in the industry. Among a plurality of renewable energy sources, biomass is the only resource form which can be converted into liquid fuel, and is expected to become a substitute of fossil resources, so that the biomass has been widely concerned by researchers.
The biomass energy is energy accumulated in the biomass, is energy stored in the biomass by converting solar energy into chemical energy through chlorophyll by green plants, and belongs to renewable energy sources. Biomass energy is the energy that is second only to coal, oil and gas and is the fourth of the world's total energy consumption. The biomass is derived from carbon dioxide, and is converted into carbon dioxide after being utilized, and the carbon emission in the whole carbon circulation process is zero, so that the content of carbon dioxide in the air can be effectively reduced, and the environmental problems such as greenhouse effect and the like are reduced. Based on this, biomass resources are also considered as a new clean energy source that is renewable and environmentally friendly.
Biomass generally includes several aspects: firstly, wood and forest industrial wastes; secondly, agricultural wastes; thirdly, aquatic plants; fourthly, oil plants; fifthly, urban and industrial organic waste; sixthly, animal excrement. Briefly, the major components of biomass consist of cellulose, hemicellulose and lignin.
Cellulose is one of three major components of biomass, is a biomass resource with the highest content in nature, and has a total cellulose amount of about 7200 million tons statistically, wherein about 400 million tons of new cellulose resources are generated annually. However, only less than 2 million tons of non-edible cellulose is used as a raw material in the paper and packaging industries, and most of the cellulose is not utilized.
Cellulose is a linear high polymer formed by connecting D-glucopyranose (AGU) through beta-1, 4-glycosidic bonds, each glucose ring in a macromolecule has 3 alcoholic hydroxyl groups, and cellulose has strong hydrogen bonding action among molecules and in molecules. Cellulose can be divided into two parts according to the length of chains and the difference of hydrogen bond energy: a crystalline portion and an amorphous portion. The crystalline cellulose has the characteristics of high crystallinity, stable physical and chemical properties and higher glass transition temperature, and the extremely strong hydrogen bonds and dense and ordered array structures also make the crystalline cellulose difficult to dissolve in hot water and common organic solvents and further difficult to be directly utilized.
At present, the utilization methods of cellulose include conventional combustion, thermochemical conversion, and biological conversion. Thermochemical conversion is a widely studied process by researchers, where pyrolysis is a very promising thermochemical conversion technology. Pyrolysis is to directly convert cellulose into liquid fuel and other chemical substances under high temperature conditions, but the product components directly generated by pyrolysis have the defects of high oxygen content, instability, low calorific value, strong acidity, high corrosivity, poor selectivity and the like, and the liquid fuel generated under the conditions is difficult to apply, consumes a large amount of energy in the process and is not a green chemical procedure. In order to solve these problems, researchers have proposed a method of catalytic hydrothermal conversion to improve the liquid fuel and the reaction process and to increase the selectivity of functional chemicals having high added values.
The hydrothermal conversion of cellulose is a reaction carried out at relatively high temperature (200-400 ℃) and pressure (5-40MPa) with water as a solvent. The high-temperature and high-pressure water is used as an ideal solvent, can replace an organic solvent, and has remarkable advantages. For example: the dielectric constant of the high-temperature water is reduced, the hydrogen bonds among molecules are weakened, and the isothermal compressibility is improved. When pure water changes from neutral to acidic (pH 5.0) at 200 ℃, cellulose can be broken down into oligosaccharides, monosaccharides, or other chemicals, accompanied by high temperature and pressure conditions. However, the prior art has the defects of incomplete biomass conversion (less than 70 percent), non-directional decomposition in water, difficulty in preparing and separating high value-added chemicals and the like, so that the introduction of a proper catalyst can be an effective way for solving the problems.
In recent years, the emergence of metal organic framework Materials (MOFs) as novel multifunctional materials has attracted considerable attention in both the industrial and academic sectors. The material is a porous crystal material with a periodic multidimensional net structure generated by hybridization of metal ions and organic ligands through a self-assembly process, unsaturated coordination sites of the metal ions can be used as active centers of catalytic reaction, and a plurality of ligands with catalytic performance can be introduced to a framework of the material; the size of the MOFs framework pore can be adjusted between micro-pore and meso-pore, and the large specific surface area can also load highly dispersed nano metal active components, so that the MOFs material has unique structural characteristics different from other catalyst materials. However, compared with the traditional porous material, the physical and chemical stability of the MOFs is relatively low, so that the development of a novel MOFs material with good hydrothermal stability has a very good application prospect.
UiO-66 is a MOFs material with ultra-high stability, and the stability comes from a highly symmetrical inorganic metal unit Zr6O4(OH)4And the Zr6The interaction of the octahedral nucleus and carboxyl oxygen in the ligand makes the ligand MOFs have good water resistance and acid resistance. The material can be used as a Lewis acid catalyst in the hydrothermal conversion process of cellulose, and the catalytic performance of the material is improved by introducing a form of transition metal oxide.
Disclosure of Invention
The invention aims to provide a preparation method of an MOFs catalyst with high hydrothermal stability, high activity and good shape-selective catalytic performance and a method for preparing fine chemicals by catalyzing cellulose through hydrothermal conversion by using the MOFs catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
a MOFs catalyst with high hydrothermal stability is obtained by modifying a metal organic framework compound UiO-66 with a metal oxide (a metal organic framework compound N-UiO-66 catalyst).
In the above MOFs catalyst with high hydrothermal stability, the metal oxide is CeO2、Ga2O3、Co2O3、Fe2O3、Er2O3One or more of ZnO and NiO.
The preparation method of the MOFs catalyst with high hydrothermal stability comprises the following steps:
(1) fully dissolving transition metal salt in deionized water, carrying out ultrasonic treatment at room temperature, weighing a metal organic framework compound UiO-66 according to an isometric immersion method, and adding the metal organic framework compound UiO-66 into the transition metal salt solution;
(2) the resulting mixture was dried at 105 ℃;
(3) and calcining the dried product at 240 ℃ to obtain the MOFs catalyst (metal organic framework compound N-UiO-66 catalyst) with high hydrothermal stability.
The specific surface area of the MOFs catalyst (metal organic framework compound N-UiO-66 catalyst) is 800-1200 m2/g。
In the preparation method of the MOFs catalyst with high hydrothermal stability, the transition metal salt is one or a mixture of more of cerium nitrate, gallium nitrate, cobalt nitrate, ferric nitrate, erbium nitrate, zinc nitrate and nickel nitrate.
The method for preparing the functional chemical by catalyzing the hydrothermal conversion of the cellulose by using the high hydrothermal stability MOFs catalyst comprises the following steps:
(1) adding MOFs catalyst and cellulose into a reaction kettle, heating and raising the temperature, and carrying out catalytic hydrothermal conversion under the condition of changing different catalytic time;
(2) and after the reaction is finished, filtering, extracting and evaporating the solvent to obtain the functional chemical product.
In the method for preparing the functional chemical, the adding amount of the MOFs catalyst is 1-10% of the dry weight of cellulose.
In the above method for preparing functional chemicals, the reaction conditions of the catalytic hydrothermal conversion are as follows: the catalytic temperature is 180-300 ℃; the reaction time is 0.5-6 h.
In the above method for preparing functional chemicals, the liquid products obtained by catalytic hydrothermal conversion of cellulose are mainly furfural, cinnamaldehyde, lactic acid, levulinic acid, and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention uses cellulose as raw material to carry out in-situ catalytic hydrothermal conversion products, can relieve the problems of energy and environment, and the existence of the catalyst can improve the defects of non-directional decomposition, difficult preparation and separation of high value-added chemicals and the like of the catalytic conversion products. The hydrothermal conversion uses high-temperature and high-pressure water as a solvent to replace an organic solvent, thereby reducing the production cost.
(2) The catalyst has high hydrothermal stability, high activity and good shape-selective catalytic performance, meets the reaction conditions required by the hydrothermal conversion of cellulose, is suitable for obtaining fine chemicals by the catalytic hydrothermal conversion of the cellulose, has high hydrothermal stability, and has high activity and good shape-selective catalytic performance, and is simple in process and easy to obtain raw materials.
(3) The whole process is simple, convenient to operate and low in cost, and has an industrial application prospect.
(4) The catalytic hydrothermal conversion process improves the conversion rate of cellulose, and the obtained catalytic conversion product mainly comprises compounds such as furfural, cinnamaldehyde, lactic acid, levulinic acid and the like, so that a new direction is provided for the subsequent utilization of renewable resources and the preparation of functional chemicals.
Detailed Description
Loading 10 wt% of metal ions on a metal organic framework compound catalyst UiO-66 by an isometric impregnation method, weighing a certain amount of transition metal salt according to the loading amount, respectively placing the transition metal salt in beakers, respectively adding 5mL of deionized water, performing ultrasonic treatment at room temperature for 30min, then adding 10g of UiO-66, and standing for 6h to obtain a product C; and transferring the product C into a forced air drying oven, drying at 105 ℃ for 8h to obtain a catalyst D, putting the catalyst D into a muffle furnace, and calcining at 240 ℃ for 4h to obtain the catalyst N-UiO-66 for the experiment.
The catalytic hydrothermal conversion experiment was as follows: firstly, granulating and sieving a catalyst, respectively taking 40 meshes as catalysts used for reaction, and then weighing a cellulose sample, a metal organic framework compound catalyst and water according to a certain feed-liquid ratio and respectively adding the cellulose sample, the metal organic framework compound catalyst and the water into a reaction kettle. The addition of the catalyst is 1-10 wt% of the dry weight of the cellulose, the reaction kettle is transferred into the reaction kettle after being sealed, and then the reaction is carried out under the proper reaction conditions: the hydrothermal conversion temperature is 180 ℃ and 300 ℃; the reaction time is 0.5-6 h. After the reaction was completed, the heating was stopped. Taking out the solid-liquid mixture in the reaction kettle, filtering to obtain a water-soluble product and a solid-phase product, adding dichloromethane into the solid-phase product for extraction, filtering and separating to obtain a solid-phase product and an organic-phase product, drying and weighing the solid-phase product, calculating the coke yield, distilling the organic-phase product under the reduced pressure distillation condition to recover the organic solvent to obtain a fine chemical mixture, weighing, and calculating the yield.
Comparative example:
weighing 5g of a cellulose sample, 0.125g of a catalyst and 50mL of deionized water according to a feed-liquid ratio of 10:1, adding the cellulose sample, the catalyst and the deionized water into a reaction kettle, wherein the addition amount of the catalyst is 2.5% of that of cellulose, the metal organic framework compound catalyst is UiO-66, and the hydrothermal conversion temperature is 240 ℃; the reaction time was 6h and the cellulose conversion was 69.7%. The relative content of organic phase products such as furfural and cinnamaldehyde in the catalytic conversion product is 32.18%, and the relative content of acid compounds such as lactic acid and levulinic acid in the water-soluble product is 74.09%.
Example 1:
weighing 5g of cellulose sample, 0.125g of catalyst and 50mL of deionized water according to the material-liquid ratio of 10:1, adding the mixture into a reaction kettle, wherein the addition amount of the catalyst is 2.5 percent of the cellulose, and the metal organic framework compound catalyst is CeO2-UiO-66, hydrothermal conversion temperature 240 ℃; the reaction time was 6h and the cellulose conversion was 77.08%. The relative content of organic phase products such as furfural and cinnamaldehyde in the catalytic conversion product is 41.75%, and the water-soluble productsThe relative content of acid compounds such as lactic acid, levulinic acid and the like is 88.66 percent.
Example 2:
weighing 5g of cellulose sample, 0.125g of catalyst and 50mL of deionized water according to the material-liquid ratio of 10:1, adding the mixture into a reaction kettle, wherein the addition amount of the catalyst is 2.5% of the cellulose, and Ga is selected as a metal organic framework compound catalyst2O3-UiO-66, hydrothermal conversion temperature 240 ℃; the reaction time was 6h and the cellulose conversion was 79.59%. The relative content of organic phase products such as furfural and cinnamaldehyde in the catalytic conversion product is 40.87%, and the relative content of acid compounds such as lactic acid and levulinic acid in the water-soluble product is 94.82%.
Example 3:
weighing 5g of cellulose sample, 0.125g of catalyst and 50mL of deionized water according to the feed-liquid ratio of 10:1, adding the mixture into a reaction kettle, wherein the addition amount of the catalyst is 2.5% of the cellulose, and the catalyst of a metal organic framework compound is Co2O3-UiO-66, hydrothermal conversion temperature 240 ℃; the reaction time was 6h and the cellulose conversion was 78.31%. The relative content of organic phase products such as furfural and cinnamaldehyde in the catalytic conversion product is 39.02%, and the relative content of acid compounds such as lactic acid and levulinic acid in the water-soluble product is 95.68%.
Example 4:
weighing 5g of cellulose sample, 0.125g of catalyst and 50mL of deionized water according to the feed-liquid ratio of 10:1, adding the mixture into a reaction kettle, wherein the addition amount of the catalyst is 2.5% of the cellulose, and the catalyst of a metal organic framework compound is Fe2O3-UiO-66, hydrothermal conversion temperature 240 ℃; the reaction time was 2h and the cellulose conversion was 68.85%. The relative content of organic phase products such as furfural and cinnamaldehyde in the catalytic conversion product is 48.65%, and the relative content of acid compounds such as lactic acid and levulinic acid in the water-soluble product is 82.46%.
Example 5:
weighing 5g of cellulose sample, 0.125g of catalyst and 50mL of deionized water according to the feed-liquid ratio of 10:1, adding the mixture into a reaction kettle, wherein the addition amount of the catalyst is 2.5 percent of the cellulose, and selecting metalThe organic framework compound catalyst is Er2O3-UiO-66, hydrothermal conversion temperature 240 ℃; the reaction time was 2h and the cellulose conversion was 70.06%. The relative content of organic phase products such as furfural and cinnamaldehyde in the catalytic conversion product is 45.15%, and the relative content of acid compounds such as lactic acid and levulinic acid in the water-soluble product is 85.41%.
Example 6:
weighing 5g of a cellulose sample, 0.125g of a catalyst and 50mL of deionized water according to a material-to-liquid ratio of 10:1, adding the cellulose sample, the catalyst and the deionized water into a reaction kettle, wherein the addition amount of the catalyst is 2.5% of that of cellulose, the metal organic framework compound catalyst is ZnO-UiO-66, and the hydrothermal conversion temperature is 240 ℃; the reaction time was 2h and the cellulose conversion was 69.47%. The relative content of organic phase products such as furfural and cinnamaldehyde in the catalytic conversion product is 46.32%, and the relative content of acid compounds such as lactic acid and levulinic acid in the water-soluble product is 87.83%.
Example 7:
weighing 5g of a cellulose sample, 0.125g of a catalyst and 50mL of deionized water according to a feed-liquid ratio of 10:1, adding the cellulose sample, the catalyst and 50mL of deionized water into a reaction kettle, wherein the addition amount of the catalyst is 2.5% of that of cellulose, the metal organic framework compound catalyst is NiO-UiO-66, and the hydrothermal conversion temperature is 240 ℃; the reaction time was 2h and the cellulose conversion was 69.47%. The relative content of organic phase products such as furfural and cinnamaldehyde in the catalytic conversion product is 47.66%, and the relative content of acid compounds such as lactic acid and levulinic acid in the water-soluble product is 84.22%.
The properties of the metal oxide-doped metal-organic framework compound UiO-66 (abbreviated as N-UiO-66) are compared with those of UiO-66 not doped with metal oxide in Table 1 below:
TABLE 1 UiO-66 and N-UiO-66 surface area and pore Properties
Figure GDA0002794936780000061
Table 1 compares the surface area and pore properties of the metal organic framework compounds UiO-66 and N-UiO-66. As can be seen from table 1, the impregnation method introduced the metal oxide to the metal organic framework compound UiO-66, and the pore size of the resulting metal organic framework compound was increased, while the specific surface area, the total pore volume and the micropore volume of the metal organic framework compound were all decreased, which indicates that the metal oxide was supported on the surface of the catalyst or entered into the pore channels, and the specific surface area of the catalyst was decreased to increase the pore size.

Claims (5)

1. A MOFs catalyst with high hydrothermal stability is characterized by being obtained by modifying a metal organic framework compound UiO-66 with a metal oxide;
the metal oxide is CeO2、Ga2O3、Co2O3、Fe2O3、Er2O3One or more of ZnO and NiO;
the preparation method comprises the following steps:
(1) fully dissolving transition metal salt in deionized water, carrying out ultrasonic treatment at room temperature, weighing a metal organic framework compound UiO-66 according to an isometric immersion method, and adding the metal organic framework compound UiO-66 into the transition metal salt solution;
(2) the resulting mixture was dried at 105 ℃;
(3) and calcining the dried product at 240 ℃ to obtain the MOFs catalyst with high hydrothermal stability.
2. The MOFs catalyst with high hydrothermal stability according to claim 1, wherein said transition metal salt is one or a mixture of several selected from the group consisting of cerium nitrate, gallium nitrate, cobalt nitrate, ferric nitrate, erbium nitrate, zinc nitrate and nickel nitrate.
3. A method for preparing functional chemicals by catalyzing hydrothermal conversion of cellulose by using the high hydrothermal stability MOFs catalyst of claim 1, wherein the method comprises the following steps:
(1) adding MOFs catalyst and cellulose into a reaction kettle, heating and raising the temperature, and carrying out catalytic hydrothermal conversion under the condition of changing different catalytic time;
(2) and after the reaction is finished, filtering, extracting and evaporating the solvent to obtain the functional chemical product.
4. The process according to claim 3, characterized in that the MOFs catalyst is added in an amount of 1-10% by dry weight of the cellulose.
5. The method according to claim 3, characterized in that the reaction conditions of the catalytic hydrothermal conversion are: the catalytic temperature is 180-300 ℃; the reaction time is 0.5-6 h.
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MOF catalysts in biomass upgrading towards value-added fine chemicals;Annika Herbst等;《CrystEngComm》;20160905;第19卷;第4092-4117页 *

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