CN110586069A - Bimetallic oxide catalyst and preparation method and application thereof - Google Patents

Bimetallic oxide catalyst and preparation method and application thereof Download PDF

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CN110586069A
CN110586069A CN201910861949.3A CN201910861949A CN110586069A CN 110586069 A CN110586069 A CN 110586069A CN 201910861949 A CN201910861949 A CN 201910861949A CN 110586069 A CN110586069 A CN 110586069A
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catalyst
kettle
product
heating
reaction
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CN110586069B (en
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纪娜
李婷婷
刁新勇
王振娇
刘庆岭
宋春风
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Tianjin University
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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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a bimetallic oxide catalyst and a preparation method and application thereof; the catalyst structure is xSnO2‑yMoO3X is more than or equal to 1 and less than or equal to 6, and y is more than or equal to 1 and less than or equal to 6; synthesizing bimetallic oxide catalysts with different proportions by adding an alcoholic solution heating treatment method, adjusting the pH value of a soluble salt solution containing an active component Sn precursor by using ammonia water, adding a soluble salt containing a metal Mo precursor, fully stirring and uniformly mixing, adding hydrochloric acid, heating, washing, filtering, and drying in vacuum to obtain a white product, roasting the white product to obtain dark green, grinding the dark green into powder, and heating the alcoholic solution to obtain alcohol-heated xSnO2‑yMoO3A catalyst. The catalyst effectively increases active sites on the surface of the catalyst, further optimizes the catalytic performance, and provides a brand new method for the efficient conversion and utilization of ligninThe method is carried out. The catalyst has the characteristics of cheap raw materials, green and environment-friendly reaction process, simple and easy preparation and the like.

Description

Bimetallic oxide catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method and application of a bimetallic oxide catalyst subjected to alcohol heating treatment; in particular to a preparation method of a brand-new bimetallic oxide catalyst and application thereof in a lignin model compound.
Background
Energy is the foundation of the survival and development of the current society and is also an important index for measuring the comprehensive national power and the living standard of people. With the development of economy and the increase of world population, the demand of human beings for energy is increasing, and in recent years, the burning of traditional fossil fuels causes not only the continuous exhaustion of non-renewable resources, but also serious environmental pollution. Therefore, the development of clean renewable energy becomes the research center of the majority of researchers, and among the renewable energy, biomass is considered as one of the fossil fuel substitutes which hopefully relieve the energy crisis, and has the characteristics of being renewable, low in cost, carbon neutral, high in productivity and the like.
The biomass is composed of cellulose, hemicellulose and lignin. The lignin accounts for about 15-30% of the biomass by weight and 40% by energy, is a three-dimensional amorphous polymer consisting of methoxy phenylpropane structures, is a compound which is formed by connecting a plurality of units with different benzene ring structures through C-C bonds and C-O bonds and has a three-dimensional high molecular structure, has a stable chemical structure, is easy to be polymerized into a macromolecular compound again in a degradation process, and is not widely used for industrial production due to the characteristics of complex structure and difficulty in being decomposed into small molecular structures.
In previous reports, lignin can be converted to phenolic compounds by hydrogenation, oxidation, hydrolysis, thermal, photochemical and electrochemical conversion, among others. Among them, Hydrodeoxygenation (HDO) is a fast, efficient, green method for catalytic conversion of lignin derivatives.
At present, catalysts applied to hydrogenation and deoxidation of lignin model compounds are various, and can be divided into homogeneous catalysts and heterogeneous catalysts according to phase states of a reaction system, and the homogeneous catalysts are difficult to separate and regenerate, but the homogeneous catalysts are very important to a large-scale production process, so that a great deal of research is mainly focused on catalytic conversion of the heterogeneous catalysts on lignin. The catalyst can be classified into an acid catalyst, a basic catalyst, a metal catalyst and the like according to the property of the catalyst, and the metal catalyst can be classified into a traditional metal catalyst, a novel noble metal catalyst and a transition metal catalyst. The conventional sulfide, phosphide and nitride metal catalysts are easy to deactivate due to loss of active components, carbon deposit, water poisoning and the like, which is an important reason that they cannot be widely used in industrial production, and although the single metal oxide catalysts have stable properties and simple preparation processes, the catalytic effect and single selectivity of the products are not high.
At present, numerous researches show that an alloy catalytic system of noble metals Ru, Rh, Pd, Pt and Re and non-noble metals Cu, Ni, Fe and Mo has high-efficiency application in catalytic conversion of a lignin model compound, but harsh conditions such as high temperature and high pressure are required, excessive hydrogenation of benzene rings can be caused, aromatic compounds with high purity are difficult to obtain, but the aromatic compounds have irreplaceable important function in the chemical industry, so that the search for a catalyst which is high in efficiency, stable and low in price and can not cause excessive hydrogenation of reaction products becomes a research hotspot of lignin conversion in recent years. MoO3The catalyst is a catalyst with high attraction and rich content on the earth surface, can be widely applied to hydrodeoxygenation of lignin derivatives, and has simple preparation process and easy operation. From the research results of the current literatures, the conversion rate of the traditional single-metal MoO3 catalyst on lignin model compounds and the single selectivity of the product are not high, the products mainly comprise benzene and phenol, the contents of the two products are relatively close, the requirement on the reaction temperature is high, and the requirement on the reaction temperature is mainly concentrated above 320-350 ℃. There is currently little interest in SnO2And MoO3The synergistic research of the bimetallic oxide in the catalytic conversion of lignin model compounds and the mode of using alcoholic solution for heating treatment to change the surface active center of the catalyst so as to further improveAnd (4) researching the catalytic performance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention adds a second metal oxide SnO2Improving the MoO of the traditional metal oxide3The catalytic performance, the method of adding corresponding alcohol solution for treatment and the like obviously reduce the reaction condition, improve the conversion rate of reactants and the single selectivity of target products, which is the innovation of the invention, thereby solving the problems that the metal catalyst in the prior art is easy to inactivate, the reaction condition is high, the process is complex, the conversion rate of the reactants is low, the selectivity of the target products is not high and the like.
The technical scheme of the invention is as follows:
a bimetallic oxide catalyst with the structural formula of xSnO2-yMoO3Wherein x is more than or equal to 1 and less than or equal to 6, and y is more than or equal to 1 and less than or equal to 6.
The method comprises the steps of synthesizing bimetallic oxide catalysts with different proportions by introducing an alcohol solution heating treatment method, adjusting the pH of a soluble salt solution containing an active component Sn precursor by using ammonia water, adding a soluble salt containing a metal Mo precursor, fully and uniformly stirring, adding hydrochloric acid, heating, washing, filtering and drying in vacuum to obtain a white product, roasting the white product to obtain dark green, grinding the dark green product to powder, and heating the alcohol solution to obtain alcohol-heated xSnO2-yMoO3A catalyst.
The invention relates to a bimetallic oxide catalyst, a preparation method and application thereof
The preparation method of the bimetallic oxide catalyst comprises the following steps:
a) preparing a soluble salt solution with the concentration of 0.033-0.200 mol/L and containing an active component Sn precursor, and adjusting the pH to 6-10 by using 25-28% by mass of ammonia water;
b) adding soluble salt with a corresponding concentration range of 0.033-0.200 mol/L of metal Mo precursor into the solution a) according to the proportion of 1/6-6/1 Sn/Mo, fully and uniformly mixing, adding hydrochloric acid, heating, washing, filtering and vacuum drying to obtain a white product;
c) roasting the white product obtained in the step b) in a muffle furnace, wherein the roasted white product is blackish green, and grinding the blackish green white product to be in a powder state;
d) heating the powder-state dark green product in the step c) in an alcohol solution to obtain alcohol-heated xSnO2-yMoO3A catalyst.
The mass fraction of the hydrochloric acid in the b) is 36.0-38.0 percent, the molar concentration of the hydrochloric acid is about 12mol/L through conversion, and the molar amount of the hydrochloric acid added is 0.5-2 times (Sn + Mo); the heating condition is that the mixture is heated and treated for 0.5 to 2 hours in an oven at the temperature of between 30 and 100 ℃, and then dried and treated for 4 to 12 hours under the condition of vacuum at the temperature of between 40 and 120 ℃;
the roasting condition in c) is roasting for 2 to 10 hours at the temperature of between 100 and 500 ℃, and then roasting for 5 to 10 hours at the temperature of between 300 and 800 ℃, wherein the heating rate is 5 ℃/min;
the alcohol solution selected in the step d) is one of methanol, absolute ethyl alcohol, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol, or a mixed solution of a plurality of alcohols, the mass ratio of the catalyst to the alcohol solution is 1: 20-1: 60g/mL, and the roasted and ground dark green powder product is heated in the alcohol solution at the temperature of 60-120 ℃ for 4-12 hours.
The alcohol heat treatment of the invention is carried out on the bimetallic oxide xSnO2-yMoO3Use of hydrodeoxygenation in lignin model compounds:
the hydrogenation reaction of the lignin model compound is carried out in an intermittent high-pressure reaction kettle, a reaction internal standard substance is a thermostable organic substance n-dodecane, and a reaction solvent can dissolve a substrate, a reaction product and the like. The method comprises the following specific steps:
a) fully mixing a lignin model compound, a catalyst, an internal standard substance and a reaction solvent, adding the mixture into a reaction kettle, replacing gas in the kettle with gas for three times before the reaction starts, and filling the pressure in the kettle to a target pressure of 2-7 MPa at normal temperature;
b) heating the reaction kettle to 250-300 ℃, wherein the stirring speed is 800-1200r/min, and the stirring time is 2-7 h;
c) after the reaction is finished, the temperature is reduced, the pressure is released, the kettle is opened, solid components in the kettle are filtered, and meanwhile, liquid products are obtained and used for gas chromatography analysis.
The reaction solvent in a) is one of n-pentane, n-hexane, n-heptane, decalin and methylcyclohexane, or the solvents are mixed in any proportion, the internal standard substance is n-dodecane, and the used gas is hydrogen;
the concentration of the lignin model compound in the a) in the reaction solvent is 0.042-0.375 mol/L; the mass ratio of the lignin to the catalyst is (1:1) - (10: 1);
the temperature rise rate in the step b) is 5 ℃/min.
Predecessors about monometallic oxide MoO3The hydrodeoxygenation result in the lignin model compound shows that the conversion rate is mostly concentrated at 70-80% when guaiacol is used as a reaction substrate, the main products are benzene and phenol, the yield of the benzene and the phenol is close to each other and is about 30%, and a pure-phase dominant product is difficult to obtain by improving the reaction conditions, so that the method is not favorable for large-scale production and application, the reaction temperature is required to be above 320-350 ℃, the reaction time is long, and the energy consumption is large. However, the results of this study show that the addition of a second metal oxide SnO2After the alcohol solution is heated, the conditions required by the reaction are reduced, and the conversion rate of the guaiacol and the yield of the phenol respectively reach 100.0 percent and 92.8 percent under the optimal reaction conditions, compared with the traditional single metal oxide MoO3The conversion rate of the substrate and the selectivity of a single product are greatly improved in the hydrodeoxygenation of the lignin model compound.
The catalyst is prepared from non-noble metal salt raw materials, and has the advantages of low cost, simple preparation process, and less time and material consumption.
The preparation of the catalyst of the invention not only introduces the second metal oxide SnO2The hydrodeoxygenation effect of the catalyst is improved, and a brand new technical method, namely an alcoholic solution is used for heating the roasted catalyst, so that the performance of the prepared catalyst is further optimized. And the conventional metal oxide MoO in the literature3Compared with the hydrodeoxygenation effect in the lignin model compound, the catalyst prepared by the method has the advantages of conversion rate of the lignin model compound and aromatic compoundsThe single selectivity of the method is improved to a large extent, and meanwhile, the reaction conditions are reduced, and the energy is saved.
The reaction solvent in the invention is a conventional organic solvent, and is environment-friendly and pollution-free.
The mass of the catalyst used in the invention is smaller than the proportion of the reaction substrate, the using amount of the catalyst is less, and the activity of the prepared catalyst is higher.
The catalyst system has good cyclicity and water resistance, and can be repeatedly used.
Drawings
FIG. 1 shows n-butanol treatment 1SnO in example 13 of the present invention2-1MoO3The catalyst takes normal hexane as a solvent to analyze the result of GC-MS spectrum analysis in guaiacol conversion.
FIG. 2 shows Anhydrous ethanol treatment 1SnO in example 14 of the present invention2-1MoO3The catalyst takes normal hexane as a solvent to analyze the result of GC-MS spectrum analysis in guaiacol conversion.
FIG. 3 shows the treatment of 1SnO with anhydrous ethanol in example 15 of the present invention2-2MoO3The catalyst takes normal hexane as a solvent to analyze the result of GC-MS spectrum analysis in guaiacol conversion.
FIG. 4 shows Anhydrous ethanol treatment of 1SnO in example 17 of the present invention2-2MoO3The catalyst takes n-pentane as a solvent to analyze the result of GC-MS spectrum analysis in guaiacol conversion.
Detailed Description
The invention will be described in more detail with reference to the following figures and embodiments, but the scope of the invention is not limited thereto.
Example 1
Methanol treatment of 6SnO2-1MoO3Preparation of the catalyst:
a) SnCl with the mass of 7.012g4.5H2Completely dissolving O in 100mL of deionized water, wherein the concentration is 0.2mol/L, and adding ammonia water with the mass fraction of 25-28% to adjust the pH value to 10;
b) then 0.589g of (NH) is added4)6Mo7O24.4H2O is dissolved in the solution a) aboveIn liquid, (NH)4)6Mo7O24.4H2The concentration of O is 0.033mol/L, the mixture is fully stirred and uniformly mixed, and 0.047mol of hydrochloric acid is added, wherein the molar weight of the hydrochloric acid is 2 times that of the metal (Sn + Mo);
c) fully stirring the white turbid solution obtained in the step b), reacting in a 60 ℃ oven for 1h, washing, filtering, vacuum-drying at 40 ℃ for 12h, roasting the obtained white product in a muffle furnace at 100 ℃ for 10h, roasting at 300 ℃ for 5h to obtain a dark green product, cooling to room temperature, and grinding into powder;
d) taking the dark green powder product obtained in the step c) and a methanol solution to react for 4 hours in a 120 ℃ oven according to the ratio of 1:20g/mL to obtain the methanol-treated 6SnO2-1MoO3A catalyst.
Example 2
Isopropanol treatment of 5SnO2-1MoO3Preparation of the catalyst:
a) SnCl with the mass of 7.012g4.5H2Completely dissolving O in 100mL of deionized water, wherein the concentration is 0.2mol/L, and adding ammonia water with the mass fraction of 25-28% to adjust the pH value to 8;
b) then, 0.706g of (NH) was added4)6Mo7O24.4H2O is dissolved in the solution of a), (NH)4)6Mo7O24.4H2The O concentration is 0.04mol/L, the mixture is fully stirred and evenly mixed, 0.036mol of concentrated hydrochloric acid is added, and the molar weight of the hydrochloric acid is 1.5 times that of metal (Sn + Mo);
c) fully stirring the white turbid solution obtained in the step b), reacting in a 60 ℃ oven for 1h, washing, filtering, carrying out vacuum drying at 60 ℃ for 10h, roasting the obtained white product in a muffle furnace at 200 ℃ for 8h, roasting at 400 ℃ for 5h to obtain a dark green product, cooling to room temperature, and grinding into powder;
d) taking the dark green powder product obtained in the step c) and isopropanol solution to react for 4 hours in a 100 ℃ oven according to the proportion of 1:30g/mL to obtain 5SnO treated by isopropanol2-1MoO3A catalyst.
Example 3
N-butanol treatment of 4SnO2-1MoO3Preparation of the catalyst:
a) SnCl with the mass of 7.012g4.5H2Completely dissolving O in 100mL of deionized water, wherein the concentration is 0.2mol/L, and adding ammonia water with the mass fraction of 25-28% to adjust the pH to 9;
b) then, 0.883g of (NH) is added4)6Mo7O24.4H2O is dissolved in the solution of a), (NH)4)6Mo7O24.4H2The O concentration is 0.05mol/L, the mixture is fully stirred and evenly mixed, and 0.05mol of hydrochloric acid is added, wherein the molar weight of the hydrochloric acid is 2 times of that of the metal (Sn + Mo);
c) fully stirring the white turbid solution obtained in the step b), reacting in an oven at 30 ℃ for 2 hours, washing, filtering, carrying out vacuum drying at 60 ℃ for 8 hours, roasting the obtained white product in a muffle furnace at 250 ℃ for 8 hours, then roasting at 400 ℃ for 5 hours to obtain a dark green product, cooling to room temperature, and grinding into powder;
d) taking the dark green powder product obtained in the step c) and n-butyl alcohol solution to react for 6 hours in a 100 ℃ oven according to the proportion of 1:20g/mL to obtain n-butyl alcohol treated 4SnO2-1MoO3A catalyst.
Example 4
Methanol treatment of 3SnO2-1MoO3Preparation of the catalyst:
a) SnCl with the mass of 7.012g4.5H2Completely dissolving O in 100mL of deionized water, wherein the concentration is 0.2mol/L, and adding ammonia water with the mass fraction of 25-28% to adjust the pH value to 8;
b) then, 1.177g of (NH) was added4)6Mo7O24.4H2O is dissolved in the solution of a), (NH)4)6Mo7O24.4H2The O concentration is 0.067mol/L, the mixture is fully stirred and uniformly mixed, and 0.027mol of hydrochloric acid is added, wherein the molar weight of the hydrochloric acid is 1 time of that of the metal (Sn + Mo);
c) fully stirring the white turbid solution obtained in the step b), reacting in an oven at 40 ℃ for 1.5h, washing, filtering, drying in vacuum at 80 ℃ for 8h, roasting the obtained white product in a muffle furnace at 400 ℃ for 5h, roasting at 700 ℃ for 5h to obtain a dark green product, cooling to room temperature, and grinding into powder;
d) taking the dark green powder product obtained in the step c) and a methanol solution to react for 12 hours in a 60 ℃ oven according to the proportion of 1:50g/mL to obtain the 3SnO treated by the methanol2-1MoO3A catalyst.
Example 5
2SnO treated by absolute ethyl alcohol2-1MoO3Preparation of the catalyst:
a) SnCl with the mass of 7.012g4.5H2Completely dissolving O in 100mL of deionized water, wherein the concentration is 0.2mol/L, and adding ammonia water with the mass fraction of 25-28% to adjust the pH value to 7;
b) then (NH) with the mass of 1.766g is added4)6Mo7O24.4H2O is dissolved in the solution of a), (NH)4)6Mo7O24.4H2The O concentration is 0.1mol/L, the mixture is fully stirred and evenly mixed, and 0.015mol of hydrochloric acid is added, wherein the molar weight of the hydrochloric acid is 0.5 time of that of the metal (Sn + Mo);
c) fully stirring the white turbid solution obtained in the step b), reacting in a 70 ℃ oven for 1h, washing, filtering, vacuum-drying at 100 ℃ for 6h, roasting the obtained white product in a muffle furnace at 300 ℃ for 5h, roasting at 500 ℃ for 8h to obtain a dark green product, cooling to room temperature, and grinding into powder;
d) taking the dark green powder product obtained in the step c) and absolute ethyl alcohol solution to react for 4 hours in a 100 ℃ oven according to the proportion of 1:40g/mL to obtain absolute ethyl alcohol treated 2SnO2-1MoO3A catalyst.
Example 6
N-butanol treatment of 1SnO2-1MoO3Preparation of the catalyst:
a) SnCl with the mass of 7.012g4.5H2Completely dissolving O in 100mL of deionized water, wherein the concentration is 0.2mol/L, and adding ammonia water with the mass fraction of 25-28% to adjust the pH value to 8;
b) then 3.531g of (NH) were added4)6Mo7O24.4H2O is dissolved in the solution of a), (NH)4)6Mo7O24.4H2The O concentration is 0.2mol/L, the mixture is fully stirred and evenly mixed, and 0.04mol of hydrochloric acid is added, wherein the molar weight of the hydrochloric acid is 1 time of that of the metal (Sn + Mo);
c) fully stirring the white turbid solution obtained in the step b), reacting in an oven at 100 ℃ for 0.5h, washing, filtering, carrying out vacuum drying at 120 ℃ for 4h, roasting the obtained white product in a muffle furnace at 500 ℃ for 2h, roasting at 800 ℃ for 10h to obtain a dark green product, cooling to room temperature, and grinding into powder;
d) taking the dark green powder product obtained in the step c) and n-butyl alcohol solution to react for 8 hours in a 120 ℃ oven according to the proportion of 1:40g/mL to obtain n-butyl alcohol treated 1SnO2-1MoO3A catalyst.
Example 7
Treatment of 1SnO with absolute ethanol2-1MoO3Preparation of the catalyst:
a) SnCl with the mass of 7.012g4.5H2Completely dissolving O in 100mL of deionized water, wherein the concentration is 0.2mol/L, and adding ammonia water with the mass fraction of 25-28% to adjust the pH value to 7;
b) then 3.531g of (NH) were added4)6Mo7O24.4H2O is dissolved in the solution of a), (NH)4)6Mo7O24.4H2The O concentration is 0.2mol/L, the mixture is fully stirred and evenly mixed, and 0.04mol of hydrochloric acid is added, wherein the molar weight of the hydrochloric acid is 1 time of that of the metal (Sn + Mo);
c) fully stirring the white turbid solution obtained in the step b), reacting in a 60 ℃ oven for 1h, washing, filtering, vacuum-drying at 60 ℃ for 8h, roasting the obtained white product in a muffle furnace at 300 ℃ for 5h, roasting at 500 ℃ for 8h to obtain a dark green product, cooling to room temperature, and grinding into powder;
d) taking the green powder product of the ink in the step c) and absolute ethyl alcohol solution to react for 8 hours in an oven at 100 ℃ according to the proportion of 1:40g/mLTo obtain absolute ethanol treated 1SnO2-1MoO3A catalyst.
Example 8
Treatment of 1SnO with absolute ethanol2-2MoO3Preparation of the catalyst:
a) SnCl with the mass of 3.506g4.5H2Completely dissolving O in 100mL of deionized water, wherein the concentration is 0.1mol/L, and adding ammonia water with the mass fraction of 25-28% to adjust the pH value to 7;
b) then 3.531g of (NH) were added4)6Mo7O24.4H2O is dissolved in the solution of a), (NH)4)6Mo7O24.4H2The O concentration is 0.2mol/L, the mixture is fully stirred and evenly mixed, and 0.03mol of hydrochloric acid is added, wherein the molar weight of the hydrochloric acid is 1 time of that of the metal (Sn + Mo);
c) fully stirring the white turbid solution obtained in the step b), reacting in a 60 ℃ oven for 1h, washing, filtering, vacuum-drying at 60 ℃ for 8h, roasting the obtained white product in a muffle furnace at 300 ℃ for 5h, roasting at 500 ℃ for 8h to obtain a dark green product, cooling to room temperature, and grinding into powder;
d) taking the ink green powder product in the step c) and absolute ethyl alcohol solution to react for 8 hours in a 100 ℃ oven according to the proportion of 1:40g/mL to obtain absolute ethyl alcohol treated 1SnO2-2MoO3A catalyst.
Example 9
Methanol treatment of 1SnO2-3MoO3Preparation of the catalyst:
a) SnCl with the mass of 2.337g4.5H2Completely dissolving O in 100mL of deionized water, wherein the concentration is 0.067mol/L, and adding ammonia water with the mass fraction of 25-28% to adjust the pH to 7;
b) then 3.531g of (NH) were added4)6Mo7O24.4H2O is dissolved in the solution of a), (NH)4)6Mo7O24.4H2The O concentration is 0.2mol/L, the mixture is fully stirred and evenly mixed, 0.013mol of hydrochloric acid is added, and the molar weight of the hydrochloric acid is 0.5 time of that of the metal (Sn + Mo);
c) fully stirring the white turbid solution obtained in the step b), reacting in a 50 ℃ oven for 1.5h, washing, filtering, carrying out vacuum drying at 70 ℃ for 10h, roasting the obtained white product in a muffle furnace at 300 ℃ for 6h, roasting at 550 ℃ for 5h, cooling to room temperature to obtain a dark green product, and grinding into powder;
d) taking the dark green powder product obtained in the step c) and a methanol solution to react for 10 hours in an oven at 80 ℃ according to the proportion of 1:60g/mL to obtain the methanol-treated 1SnO2-3MoO3A catalyst.
Example 10
Isopropanol treatment of 1SnO2-4MoO3Preparation of the catalyst:
a) SnCl with the mass of 1.753g4.5H2Completely dissolving O in 100mL of deionized water, wherein the concentration is 0.05mol/L, and adding ammonia water with the mass fraction of 25-28% to adjust the pH value to 8;
b) then 3.531g of (NH) were added4)6Mo7O24.4H2O is dissolved in the solution of a), (NH)4)6Mo7O24.4H2The O concentration is 0.2mol/L, the mixture is fully stirred and evenly mixed, and 0.025mol of hydrochloric acid is added, wherein the molar weight of the hydrochloric acid is 1 time of that of the metal (Sn + Mo);
c) fully stirring the white turbid solution obtained in the step b), reacting in an oven at 80 ℃ for 1h, washing, filtering, carrying out vacuum drying at 80 ℃ for 12h, roasting the obtained white product in a muffle furnace at 300 ℃ for 4h, roasting at 500 ℃ for 6h, cooling to room temperature to obtain a dark green product, and grinding into powder;
d) taking the ink green powder product in the step c) and isopropanol solution to react for 10 hours in an oven at 80 ℃ according to the proportion of 1:60g/mL to obtain isopropanol-treated 1SnO2-4MoO3A catalyst.
Example 11
Treatment of 1SnO with absolute ethanol2-5MoO3Preparation of the catalyst:
a) SnCl with the mass of 1.402g4.5H2O was completely dissolved in 100mL of deionized waterAdding ammonia water with the mass fraction of 25-28% into water with the concentration of 0.04mol/L to adjust the pH to 9;
b) then 3.531g of (NH) were added4)6Mo7O24.4H2O is dissolved in the solution of a), (NH)4)6Mo7O24.4H2The O concentration is 0.2mol/L, the mixture is fully stirred and evenly mixed, 0.036mol of hydrochloric acid is added, and the molar weight of the hydrochloric acid is 1.5 times that of the metal (Sn + Mo);
c) fully stirring the white turbid solution obtained in the step b), reacting in a 60 ℃ oven for 1h, washing, filtering, vacuum-drying at 80 ℃ for 8h, roasting the obtained white product in a muffle furnace at 300 ℃ for 5h, roasting at 500 ℃ for 8h, cooling to room temperature to obtain a dark green product, and grinding into powder;
d) taking the ink green powder product in the step c) and absolute ethyl alcohol solution to react for 8 hours in an oven at 80 ℃ according to the proportion of 1:50g/mL, and obtaining the absolute ethyl alcohol treated 1SnO2-5MoO3 catalyst.
Example 12
Isopropanol treatment of 1SnO2-6MoO3Preparation of the catalyst:
a) SnCl with the mass of 1.169g4.5H2Completely dissolving O in 100mL of deionized water, wherein the concentration is 0.033mol/L, and adding ammonia water with the mass fraction of 25-28% to adjust the pH value to 6;
b) then 3.531g of (NH) were added4)6Mo7O24.4H2O is dissolved in the solution of a), (NH)4)6Mo7O24.4H2The concentration of O is 0.2mol/L, the mixture is fully stirred and evenly mixed, 0.046mol of hydrochloric acid is added, and the molar weight of the hydrochloric acid is 2 times of that of the metal (Sn + Mo);
c) fully stirring the white turbid solution obtained in the step b), reacting in a 30 ℃ oven for 2 hours, washing, filtering, carrying out vacuum drying at 60 ℃ for 8 hours, roasting the obtained white product in a muffle furnace at 500 ℃ for 2 hours, then roasting at 800 ℃ for 10 hours, cooling to room temperature to obtain a dark green product, and grinding into powder;
d) taking the ink in c)The green powder product and isopropanol solution react for 12 hours in a 60 ℃ oven according to the proportion of 1:40g/mL to obtain isopropanol-treated 1SnO2-6MoO3A catalyst.
Example 13
a) 0.0325g of the n-butanol obtained in example 6 was treated with 1SnO2-1MoO3Adding a catalyst and 10mL of n-hexane solution containing 0.125mol/L guaiacol and 0.125mol/L n-dodecane into a 50mL high-pressure reaction kettle;
b) replacing air in the kettle with hydrogen for three times, then filling the hydrogen until the initial pressure in the kettle is 4MPa, heating to 300 ℃, stirring at the speed of 1000r/min, and reacting for 4 h;
c) and after the reaction is finished, stopping stirring and cooling to room temperature, separating reactants and the catalyst, taking out a liquid product, and performing qualitative and quantitative analysis on the liquid product by GC-MS to obtain the conversion rate of the guaiacol serving as a substrate and the selectivity of the phenol serving as a product.
The analytical profile of the product is shown in FIG. 1, and the guaiacol conversion and phenol yield are shown in Table 1.
TABLE 1 treatment of 1SnO with guaiacol in n-butanol2-1MoO3Conversion in catalyst and phenol yield
Example 14
a) 0.0325g of the absolute ethanol obtained in example 7 was treated with 1SnO2-1MoO3Adding a catalyst and 10mL of n-hexane solution containing 0.125mol/L guaiacol and 0.125mol/L n-dodecane into a 50mL high-pressure reaction kettle;
b) replacing air in the kettle with hydrogen for three times, then filling the hydrogen until the initial pressure in the kettle is 4MPa, heating to 300 ℃, stirring at the speed of 1000r/min, and reacting for 4 h;
c) and after the reaction is finished, stopping stirring and cooling to room temperature, separating reactants and the catalyst, taking out a liquid product, and performing qualitative and quantitative analysis on the liquid product by GC-MS to obtain the conversion rate of the guaiacol serving as a substrate and the selectivity of the phenol serving as a product.
The analytical profile of the product is shown in FIG. 2, and the guaiacol conversion and phenol yield are shown in Table 2.
TABLE 2 treatment of 1SnO with guaiacol in Anhydrous ethanol2-1MoO3Conversion in catalyst and phenol yield
Example 15
a) 0.0325g of the absolute ethanol obtained in example 8 was treated with 1SnO2-2MoO3Adding a catalyst and 10mL of n-hexane solution containing 0.125mol/L guaiacol and 0.125mol/L n-dodecane into a 50mL high-pressure reaction kettle;
b) replacing air in the kettle with hydrogen for three times, then filling the hydrogen until the initial pressure in the kettle is 4MPa, heating to 300 ℃, stirring at the speed of 1000r/min, and reacting for 4 h;
c) and after the reaction is finished, stopping stirring and cooling to room temperature, separating reactants and the catalyst, taking out a liquid product, and performing qualitative and quantitative analysis on the liquid product by GC-MS to obtain the conversion rate of the guaiacol serving as a substrate and the selectivity of the phenol serving as a product.
The analytical profile of the product is shown in FIG. 3, and the guaiacol conversion and phenol yield are shown in Table 3.
TABLE 3 treatment of 1SnO with guaiacol in Anhydrous ethanol2-2MoO3Conversion in catalyst and phenol yield
Example 16
a) 0.065g of the absolute ethanol obtained in example 8 was treated with 1SnO2-2MoO3Adding a catalyst and 10mL of n-hexane solution containing 0.125mol/L guaiacol and 0.125mol/L n-dodecane into a 50mL high-pressure reaction kettle;
b) replacing air in the kettle with hydrogen for three times, then filling the hydrogen until the initial pressure in the kettle is 4MPa, heating to 280 ℃, stirring at the speed of 1000r/min, and reacting for 4 h;
c) and after the reaction is finished, stopping stirring and cooling to room temperature, separating reactants and the catalyst, taking out a liquid product, and performing qualitative and quantitative analysis on the liquid product by GC-MS to obtain the conversion rate of the guaiacol serving as a substrate and the selectivity of the phenol serving as a product.
The guaiacol conversion and phenol yield are shown in table 4.
TABLE 4 treatment of 1SnO with guaiacol in Anhydrous ethanol2-2MoO3Conversion in catalyst and phenol yield
Example 17
a) 0.0325g of absolute ethanol obtained in example 8 was treated with 1SnO2-2MoO3Adding a catalyst and 10mL of n-pentane solution containing 0.125mol/L guaiacol and 0.125mol/L n-dodecane into a 50mL high-pressure reaction kettle;
b) replacing air in the kettle with hydrogen for three times, then filling the hydrogen until the initial pressure in the kettle is 4MPa, heating to 300 ℃, stirring at the speed of 1000r/min, and reacting for 4 h;
c) and after the reaction is finished, stopping stirring and cooling to room temperature, separating reactants and the catalyst, taking out a liquid product, and performing qualitative and quantitative analysis on the liquid product by GC-MS to obtain the conversion rate of the guaiacol serving as a substrate and the selectivity of the phenol serving as a product.
The analytical profile of the product is shown in FIG. 4, and the guaiacol conversion and phenol yield are shown in Table 5.
TABLE 5 treatment of 1SnO with guaiacol in Anhydrous ethanol2-2MoO3Conversion in catalyst and phenol yield
Example 18
a) 0.0325g of the absolute ethanol obtained in example 8 was treated with 1SnO22MoO catalyst, 10mL guaiac catalyst containing 0.125mol/LAdding the n-heptane solution of the lignan and 0.125mol/L n-dodecane into a 50mL high-pressure reaction kettle;
b) replacing air in the kettle with hydrogen for three times, then filling the hydrogen until the initial pressure in the kettle is 4MPa, heating to 300 ℃, stirring at the speed of 1000r/min, and reacting for 4 h;
c) and after the reaction is finished, stopping stirring and cooling to room temperature, separating reactants and the catalyst, taking out a liquid product, and performing qualitative and quantitative analysis on the liquid product by GC-MS to obtain the conversion rate of the guaiacol serving as a substrate and the selectivity of the phenol serving as a product.
The guaiacol conversion and phenol yield are shown in table 6.
TABLE 6 treatment of 1SnO with guaiacol in Anhydrous ethanol2-2MoO3Conversion in catalyst and phenol yield
Example 19
a) 0.0325g of the absolute ethanol obtained in example 8 was treated with 1SnO2-2MoO3Adding a catalyst and 10mL of decalin solution containing 0.125mol/L guaiacol and 0.125mol/L n-dodecane into a 50mL high-pressure reaction kettle;
b) replacing air in the kettle with hydrogen for three times, then filling the hydrogen until the initial pressure in the kettle is 4MPa, heating to 300 ℃, stirring at the speed of 1000r/min, and reacting for 4 h;
c) and after the reaction is finished, stopping stirring and cooling to room temperature, separating reactants and the catalyst, taking out a liquid product, and performing qualitative and quantitative analysis on the liquid product by GC-MS to obtain the conversion rate of the guaiacol serving as a substrate and the selectivity of the phenol serving as a product.
The guaiacol conversion and phenol yield are shown in table 7.
TABLE 7 treatment of 1SnO with guaiacol in Anhydrous ethanol2-2MoO3Conversion in catalyst and phenol yield
Example 20
a) 0.0325g of the absolute ethanol obtained in example 8 was treated with 1SnO2-2MoO3Adding a catalyst and 10mL of methylcyclohexane solution containing 0.125mol/L guaiacol and 0.125mol/L n-dodecane into a 50mL high-pressure reaction kettle;
b) replacing air in the kettle with hydrogen for three times, then filling the hydrogen until the initial pressure in the kettle is 4MPa, heating to 300 ℃, stirring at the speed of 1000r/min, and reacting for 4 h;
c) and after the reaction is finished, stopping stirring and cooling to room temperature, separating reactants and the catalyst, taking out a liquid product, and performing qualitative and quantitative analysis on the liquid product by GC-MS to obtain the conversion rate of the guaiacol serving as a substrate and the selectivity of the phenol serving as a product.
The guaiacol conversion and phenol yield are shown in table 8.
TABLE 8 treatment of 1SnO with guaiacol in Anhydrous ethanol2-2MoO3Conversion in catalyst and phenol yield
Example 21
a) 0.0325g of the absolute ethanol obtained in example 8 was treated with 1SnO2-2MoO3Adding a catalyst and 10mL of n-hexane solution containing 0.125mol/L anisole and 0.125mol/L n-dodecane into a 50mL high-pressure reaction kettle;
b) replacing air in the kettle with hydrogen for three times, then filling the hydrogen until the initial pressure in the kettle is 4MPa, heating to 300 ℃, stirring at the speed of 1000r/min, and reacting for 4 h;
c) and after the reaction is finished, stopping stirring, cooling to room temperature, separating reactants and the catalyst, taking out a liquid product, and performing qualitative and quantitative analysis on the liquid product by GC-MS to obtain the conversion rate of the substrate anisole and the selectivity of the product phenol.
The guaiacol conversion and phenol yield are shown in table 9.
TABLE 9 treatment of 1SnO with anisole in Anhydrous ethanol2-2MoO3Conversion in catalyst and phenol yield
Example 22
a) 0.010g of the methanol obtained in example 1 was treated with 6SnO2-1MoO3Adding a catalyst and 20mL of n-hexane solution containing 0.042mol/L guaiacol and 0.125mol/L n-dodecane into a 50mL high-pressure reaction kettle;
b) replacing air in the kettle with hydrogen for three times, then filling the hydrogen until the initial pressure in the kettle is 4MPa, heating to 250 ℃, stirring at the speed of 800r/min, and reacting for 4 h;
c) and after the reaction is finished, stopping stirring, cooling to room temperature, separating reactants and the catalyst, and taking out a liquid product to enter GC-MS for qualitative and quantitative analysis. The guaiacol conversion rate is lower than 30% and the phenol yield is lower than 10% due to the over-low reaction temperature.
Example 23
a) 0.047g of the absolute ethanol obtained in example 11 was treated with 1SnO2-5MoO3Adding a catalyst and 10mL of n-hexane solution containing 0.375mol/L guaiacol and 0.125mol/L n-dodecane into a 50mL high-pressure reaction kettle;
b) replacing air in the kettle with hydrogen for three times, then filling the hydrogen until the initial pressure in the kettle is 2MPa, heating to 270 ℃, stirring at the speed of 1200r/min, and reacting for 7 h;
c) and after the reaction is finished, stopping stirring, cooling to room temperature, separating reactants and the catalyst, and taking out a liquid product to enter GC-MS for qualitative and quantitative analysis. The conversion rate of guaiacol is lower than 50% and the yield of phenol is lower than 30% because of too low reaction pressure.
Example 24
a) 0.156g of the isopropanol obtained in example 12 was treated with 1SnO2-6MoO3Catalyst, 10mL contains 0.125mol/L YuAdding the n-hexane solution of the guaiacol and 0.125mol/L n-dodecane into a 50mL high-pressure reaction kettle;
b) replacing air in the kettle with hydrogen for three times, then filling the hydrogen until the initial pressure in the kettle is 7MPa, heating to 250 ℃, stirring at the speed of 1000r/min, and reacting for 2 h;
c) and after the reaction is finished, stopping stirring, cooling to room temperature, separating reactants and the catalyst, and taking out a liquid product to enter GC-MS for qualitative and quantitative analysis. The guaiacol conversion rate is lower than 10% and the phenol yield is lower than 5% due to the over-low reaction temperature.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A bimetallic oxide catalyst for alcohol heating treatment has a structural formula of xSnO2-yMoO3Wherein x is more than or equal to 1 and less than or equal to 6, and y is more than or equal to 1 and less than or equal to 6.
2. A method for preparing the alcohol heat-treated double metal oxide catalyst according to claim 1, wherein the alcohol heat treatment is adopted, comprising the steps of:
a) preparing a soluble salt solution with the concentration of 0.033-0.200 mol/L and containing an active component Sn precursor, and adjusting the pH to 6-10 by using 25-28% by mass of ammonia water;
b) adding soluble salt with a corresponding concentration range of 0.033-0.200 mol/L of metal Mo precursor into the solution a) according to the proportion of 1/6-6/1 Sn/Mo, fully and uniformly mixing, adding hydrochloric acid, heating, washing, filtering and vacuum drying to obtain a white product;
c) calcining the white product obtained in claim b) in a muffle furnace to turn the calcined white product into blackish green, and grinding the blackish green white product into powder;
d) heating the powder-state dark green product in the step c) in an alcohol solution to obtain alcohol-heated xSnO2-yMoO3CatalysisAnd (3) preparing.
3. The method as set forth in claim 2, wherein the mass fraction of hydrochloric acid in b) is 36.0-38.0%, and the molar amount of hydrochloric acid added is 0.5-2 times (Sn + Mo); the heating condition is that the mixture is heated in an oven at the temperature of 30-100 ℃ for 0.5-2 h and then dried under the vacuum condition of 40-120 ℃ for 4-12 h.
4. The method as set forth in claim 2, wherein the calcination in c) is carried out at 100 ℃ to 500 ℃ for 2 hours to 10 hours and then at 300 ℃ to 800 ℃ for 5 hours to 10 hours at a temperature rise rate of 5 ℃/min.
5. The method as set forth in claim 2, wherein the alcohol solution selected in d) is one of methanol, absolute ethanol, n-propanol, isopropanol, n-butanol, or a mixture of several alcohols.
6. The method of claim 2, wherein the ratio of the mass of the catalyst to the mass of the alcohol solution is 1:20 to 1:60 g/mL.
7. The method as set forth in claim 2, wherein the blackish green powder product ground after the calcination in d) is heated in an alcohol solution at 60 ℃ to 120 ℃ for 4 hours to 12 hours.
8. The bimetallic oxide, xSnO, of claim 12-yMoO3Application to hydrodeoxygenation in lignin model compounds.
9. The application of claim 8, which comprises the following steps:
a) fully mixing a lignin model compound, a catalyst, an internal standard substance and a reaction solvent, adding the mixture into a reaction kettle, replacing gas in the kettle with gas for three times before the reaction starts, and filling the pressure in the kettle to a target pressure of 2-7 MPa at normal temperature;
b) heating the reaction kettle to 250-300 ℃, wherein the stirring speed is 800-1200r/min, and the stirring time is 2-7 h;
c) after the reaction is finished, the temperature is reduced, the pressure is released, the kettle is opened, solid components in the kettle are filtered, and meanwhile, liquid products are obtained and used for gas chromatography analysis.
The reaction solvent in a) is one of n-pentane, n-hexane, n-heptane, decalin and methylcyclohexane, or the solvents are mixed in any proportion, the internal standard substance is n-dodecane, and the used gas is hydrogen.
10. The method as claimed in claim 8, wherein the concentration of the lignin model compound in the a) in the reaction solvent is 0.042-0.375 mol/L; the mass ratio of the lignin to the catalyst is 1: 1-10: 1.
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