CN111153801B - Preparation method of aromatic carboxylic ester compound - Google Patents

Preparation method of aromatic carboxylic ester compound Download PDF

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CN111153801B
CN111153801B CN201811318964.5A CN201811318964A CN111153801B CN 111153801 B CN111153801 B CN 111153801B CN 201811318964 A CN201811318964 A CN 201811318964A CN 111153801 B CN111153801 B CN 111153801B
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carbonate
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metal oxide
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CN111153801A (en
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李�灿
刘海龙
李泽龙
王集杰
卢胜梅
王蒙蒙
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/27—Preparation of carboxylic acid esters from ortho-esters
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
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    • 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
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    • 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
    • B01J23/20—Vanadium, niobium or tantalum

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Abstract

The application discloses a preparation method of aromatic carboxylic ester compounds, wherein in the presence of a catalyst, aromatic hydrocarbon compounds and carbonate compounds react to obtain aromatic carboxylic ester compounds; the catalyst is selected from at least one of acylation reaction catalysts. In the method, the catalyst has high catalytic efficiency, the product yield is obviously improved, the Delta G of the reaction is less than-20 kJ/mol, the aromatic hydrocarbon carboxylation reaction can be realized under high thermodynamic equilibrium conversion rate, the reaction equilibrium yield is greatly improved, the aromatic carboxylic ester product is easy to separate and purify, and the high-efficiency carbon dioxide indirect resource utilization can be realized to prepare high value-added chemicals.

Description

Preparation method of aromatic carboxylic ester compound
Technical Field
The application relates to a preparation method of an aromatic carboxylic ester compound, belonging to the fields of chemical synthesis and catalytic reaction.
Background
Aromatic carboxylic acids and their derivatives are very important basic chemicals, widely used as raw materials for various types of products, such as: benzoic acid and its sodium salt are very common food preservatives; terephthalic acid is an important raw material for the production of polyesters and is of great interest to the polymer industry; methyl benzoic acid is a synthetic precursor of various drugs; 2, 6-naphthalene diacid is mainly used for manufacturing high-strength polyester fibers and insulating materials, and is an important monomer of various types of high-performance synthetic resins. At present, the method for preparing aromatic carboxylic acid by using methyl-substituted aromatic hydrocarbon oxide is mainly used industrially, and the process is complex in process, high in energy consumption, low in reaction efficiency and easy to cause serious environmental pollution.
As shown in the formula III, the carboxylation coupling reaction of the aromatic hydrocarbon and the carbonic ester provides an efficient and reliable path for efficiently preparing aromatic carboxylic esters with high added values, and CO can be realized2Indirect resource utilization, wherein the substituent R, R1、R2、R3、R4Is hydrogen, aryl or alkyl.
Figure GDA0002953454090000011
Based on CO2Reports of preparing aromatic carboxylic acid and derivatives thereof by resource utilization mainly comprise three types (shown as a formula 2), which are respectively: first, Lewis acid activated CO2C — C bond coupling via electrophilic attack on the aromatic ring to produce carboxylic acid (j.am. chem. soc.2002,124, 11379; j.mater. sci. chem. en. 2015,3, 103.); the second category, the C-X bond activation in the aromatic ring is catalyzed by the transition metal complex under the auxiliary action of a reducing agent, CO2An insertion reaction occurs to effect carboxylation (chem.commun.2014,50,14360.); class III, CO with the assistance of strong bases2Carboxylation of the insert (Nature 2016,531,215.). The three reactions need to consume equivalent Lewis acid, alkali or reducing agent, excessive acid needs to be added to purify the product after the reaction is finished, the reaction efficiency is low, and CO is restricted2The popularization and the application of preparing aromatic carboxylic acid and derivatives thereof by carboxylation.
Figure GDA0002953454090000021
In addition, CO is limited by thermodynamic equilibrium2Δ G coupling reaction with direct carboxylation of aromatic hydrocarbons>55kJ/mol, the product yield is very low.
Disclosure of Invention
According to one aspect of the application, the preparation method of the aromatic carboxylic ester compound is provided, the catalyst in the method is high in catalytic efficiency, the product yield is remarkably improved, the delta G of the reaction is-20 kJ/mol, the aromatic hydrocarbon carboxylation reaction can be realized under high thermodynamic equilibrium conversion rate, the reaction equilibrium yield is greatly improved, the aromatic carboxylic ester product is easy to separate and purify, and efficient carbon dioxide indirect resource utilization can be realized to prepare high value-added chemicals.
The carbonate ester of the process described herein acts as an acylating agent and its specific structure allows the product of the reaction to be a carboxylic ester, which is an important chemical feedstock, rather than a conventional ketone compound, which provides an alternative strategy for the preparation of aryl carboxylic acids.
The method described in the application obtains aryl carboxylic ester by acylation reaction of aromatic hydrocarbon and carbonic ester and derivatives thereof in the presence of a catalyst. The catalyst refers to various homogeneous or heterogeneous catalysts for acylation reaction, the aromatic hydrocarbon refers to substituted or unsubstituted aromatic hydrocarbon, and the carbonate and derivatives thereof refer to chain or cyclic carbonate and amine carbonate.
In the preparation method of the aromatic carboxylic ester compound, in the presence of a catalyst, an aromatic hydrocarbon compound and a carbonate compound react to obtain an aromatic carboxylic ester compound;
optionally, the catalyst is selected from at least one of the acylation reaction catalysts.
The catalyst is selected from at least one of acylation reaction catalysts.
Optionally, the catalyst is selected from at least one of homogeneous catalysts, heterogeneous catalysts.
Optionally, the homogeneous catalyst is selected from at least one of organic acids, lewis acids.
Optionally, the organic acid comprises at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic anhydride, trifluoroacetic anhydride.
Optionally, the lewis acid comprises at least one of aluminum trichloride, ferric trichloride, and zinc chloride.
The heterogeneous catalyst is a metal oxide catalyst.
Optionally, the catalyst is a heterogeneous catalyst.
Optionally, the metal oxide catalyst comprises a single metal oxide and/or a composite metal oxide thereof;
the metal element in the metal oxide catalyst is selected from at least one of IIA group, IIIA group, IVA group, VA group, VB group, VIB group, VIIB group and VIIIB group;
the composite metal oxide includes at least two of the single metal oxides.
Optionally, the ratio of each metal element of the composite metal oxide is 1: 10-10: 1 in terms of molar content.
Alternatively, the lower limit of the ratio of each metal element of the composite metal oxide may be independently selected from 1:10, 1:5, 3:10, 2:5, 1:2, 3:5, 7:10, 4:5, 9:10, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, and any of the ranges consisting of any two of the above.
Alternatively, the upper limit of the ratio of each metal element of the composite metal oxide may be independently selected from 1.5:10, 1:5, 3:10, 2:5, 1:2, 3:5, 7:10, 4:5, 9:10, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, and any of the ranges consisting of any two of the above.
Optionally, the metal element In the metal oxide is selected from at least one of Mg, Al, La, Zn, Ce, Ti, Zr, In, Ga, Y, Sn, Sb, W, Mo, Cr, Mn, Fe, Nb.
Optionally, the single metal oxide comprises MgO, Al2O3、La2O3、ZnO、CeO2、TiO2、ZrO2、In2O3、Ga2O3、Y2O3、SnO2、Sb2O5、WO3、MoO3、CrO3、MnO2、Fe2O3、Nb2O5One kind of (1).
As an embodiment, single metal oxides and compositesMetal oxides, respectively denoted as MaOxAnd M1 b-M2 cOyWherein M isaOxAre respectively MgO and Al2O3、La2O3、ZnO、CeO2、TiO2、ZrO2、In2O3、Ga2O3、Y2O3、SnO2、Sb2O5、WO3、MoO3、CrO3、MnO2、Fe2O3Or Nb2O5(ii) a Composite metal oxide M1 b-M2 cOyComprises a mixture of any two or more of the above oxides, wherein M is 1/10-M1/M2≤10/1。
Optionally, the metal oxide catalyst is prepared by a precipitation method, and the metal oxide catalyst is obtained by precipitating a solution containing metal salt and/or mixed metal salt and a precipitating agent in an aqueous solution, drying and roasting.
As an embodiment, the method for preparing the metal oxide catalyst is characterized in that: prepared by precipitation from a metal salt of M or M1、M2Precipitating the metal salt mixed solution and a precipitator in an aqueous solution, and washing, filtering, drying and roasting to obtain the catalyst.
Optionally, the metal salt is selected from at least one of nitrate, acetate, halide, sulfate, oxalate, ammonium salt and organic salt of metal element.
Optionally, when the metal element is Ti, the salt thereof is at least one selected from titanyl sulfate, titanium isopropoxide, and butyl titanate.
Alternatively, when the metal element is Zr, the salt thereof is selected from at least one of zirconyl nitrate and zirconium isopropoxide.
Optionally, the precipitant is selected from at least one of ammonia water, ammonium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, and potassium hydroxide.
Optionally, the firing comprises static firing and/or flowing atmosphere firing;
the roasting atmosphere is at least one of air, oxygen and nitrogen, and the roasting temperature is between room temperature and 1000 ℃.
As an embodiment, the preparation method of the metal oxide catalyst adopts a precipitation method, and comprises the following steps: preparing a certain concentration of M salt solution or M1、M2And (3) preparing a precipitator aqueous solution with a certain concentration from the salt mixed solution, and precipitating the precipitator aqueous solution and the precipitator aqueous solution in the aqueous solution to ensure that the end-point pH of a supernatant after precipitation is 3-12. The precipitation mode comprises the steps of dripping a precipitator aqueous solution into a metal salt solution, dripping the metal salt solution into the precipitator aqueous solution and co-current and co-precipitation of the precipitator aqueous solution and the metal salt solution. Filtering, washing, drying and roasting the obtained precipitate at the room temperature to 1000 ℃ to obtain the metal oxide catalyst MaOxOr M1 b-M2 cOy。
As an embodiment, the preparation method of the single metal oxide catalyst adopts a precipitation method, and comprises the following steps:
a) preparing a metal salt solution and a precipitator solution;
b) dropwise adding the precipitant solution into the metal salt solution under stirring until the metal elements are completely precipitated, wherein the final pH value of the precipitation mother solution is 3-12;
c) and (3) aging, filtering, washing, drying and roasting the filter cake to obtain the single metal oxide catalyst.
As an embodiment, the preparation method of the composite metal oxide catalyst is prepared by a precipitation method, and comprises the following steps:
a) preparing a solution of mixed metal salt and a precipitant solution according to a proportion;
b) dropwise adding the precipitant solution into the mixed metal salt solution under stirring until the mixed metal elements are completely precipitated, wherein the final pH of the precipitation mother solution is 3-12;
c) and (3) aging, filtering, washing, drying and roasting the filter cake to obtain the composite metal oxide catalyst.
Optionally, the end point pH of the precipitation mother liquor is 5-9.
Optionally, the end point pH of the precipitation mother liquor is neutral.
Preferably, the aromatic hydrocarbon compound is selected from at least one of a compound having a chemical formula shown in formula I-1 and a compound having a chemical formula shown in formula I-2:
Figure GDA0002953454090000051
wherein R is11Independently selected from hydrogen, C1～C5Alkyl groups of (a); n is 0,1, 2, 3, 4 or 5;
Figure GDA0002953454090000052
wherein R is12Independently selected from hydrogen, C1～C5Alkyl groups of (a); m is 0,1, 2, 3, 4,5, 6 or 7.
Preferably, n in said formula I-1 is 0 or 1.
Preferably, m in said formula I-2 is 0 or 1.
Preferably, the aromatic hydrocarbon compound comprises at least one of benzene, toluene, ethylbenzene and naphthalene.
Preferably, the carbonate compound is selected from at least one of a compound having a chemical formula shown in formula II-1 and a compound having a chemical formula shown in formula II-2:
Figure GDA0002953454090000061
wherein R is211And R212Each independently selected from hydrogen and C1～C5Alkyl groups of (a);
Figure GDA0002953454090000062
wherein R is2211And R222Each independently selected from hydrogen, alkyl, aryl; x and Y are each independently selected from C, O or N, and X and Y are not both C.
Preferably, the carbonate compound is CO2A derivative carbonate compound.
Preferably, the carbonate compound comprises at least one of dimethyl carbonate, propylene carbonate, styrene carbonate and 2-oxazolidinone.
Taking an aromatic hydrocarbon compound with a chemical formula shown as a formula I-1 and a carbonate compound with a chemical formula shown as a formula II-1 as examples, the reaction formula of the aromatic carboxylate compound is as follows:
Figure GDA0002953454090000063
optionally, the reaction conditions of the reaction include: the reaction temperature is 0-600 ℃, the initial reaction pressure is 0-20 MPa, the reaction atmosphere is at least one selected from nitrogen, carbon dioxide, helium, argon and hydrogen, and the molar concentration ratio of reactants in the reaction liquid is n (carbonate compound): n (aromatic hydrocarbon compound) is 1:9 to 9: 1.
Optionally, the reaction conditions of the reaction include: the reaction temperature is 100-500 ℃, the initial reaction pressure is 1-5 MPa, the reaction atmosphere is at least one selected from nitrogen, carbon dioxide and argon, and the molar concentration ratio of reactants in the reaction liquid is n (carbonate compound): n (aromatic hydrocarbon compound) is 1:9 to 1: 1.
Alternatively, the reaction conditions of the carboxylated coupling reaction include: the reaction temperature is 100-600 ℃, the initial reaction pressure is 0-20 MPa, the reaction atmosphere is at least one selected from nitrogen, carbon dioxide, helium, argon and hydrogen, and the molar concentration ratio of reactants in the reaction liquid is n (carbonate compound): n (aromatic hydrocarbon compound) is 1:9 to 9: 1.
Optionally, the lower reaction temperature limit of the carboxylation coupling reaction is independently selected from 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, and any point in a range consisting of any two of the above points.
Optionally, the upper reaction temperature limit of the carboxylation coupling reaction is independently selected from 110 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, and any point in a range consisting of any two of the above points.
Alternatively, the lower limit of the initial pressure of the carboxylation coupling reaction is independently selected from 0MPa, 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa, 15MPa, 16MPa, 17MPa, 18MPa, 19MPa, 20MPa, and any point in the range consisting of any two of the above.
Alternatively, the upper limit of the initial pressure of the carboxylation coupling reaction is independently selected from 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa, 15MPa, 16MPa, 17MPa, 18MPa, 19MPa, 20MPa, and any of the ranges consisting of any two of the above.
Optionally, the molar concentration ratio of the reactants in the reaction solution of the carboxylation coupling reaction is n (carbonate compound): the lower limit of n (aromatic hydrocarbon) is independently selected from 1:9, 2:9, 1:3, 4:9, 5:9, 2:3, 7:9, 8:9, 1:1, 9:8, 9:7, 3:2, 9:5, 9:4, 3:1, 9:2, 9:1, and any point in the range consisting of any two of the foregoing.
Optionally, the molar concentration ratio of the reactants in the reaction solution of the carboxylation coupling reaction is n (carbonate compound): the upper limit of n (aromatic hydrocarbon) is independently selected from 1:9, 2:9, 1:3, 4:9, 5:9, 2:3, 7:9, 8:9, 1:1, 9:8, 9:7, 3:2, 9:5, 9:4, 3:1, 9:2, 9:1, and any point in the range consisting of any two of the foregoing.
Alternatively, the carboxylation coupling reaction is carried out in an autoclave batch reactor.
In one embodiment, the activity evaluation of the reaction of the metal oxide to catalyze the coupling of the aromatic hydrocarbon compound and the carbonate compound to produce the aromatic carboxylic acid ester is carried out in an autoclave type batch reactor. Before reaction, a certain amount of metal oxide catalyst and reaction initial materials are added into a reaction kettle, and after the reaction atmosphere is replaced for three times, the temperature is raised to the set temperature to start the reaction. The coupling reaction conditions of the aromatic hydrocarbon compound and the carbonate compound are as follows: the reaction temperature is 100-600 ℃, the reaction atmosphere is one or more than two of high-purity nitrogen, carbon dioxide, helium, argon or hydrogen, the initial pressure is 0-20 MPa, and the concentration of the reaction liquid is n (carbonate compounds): n (aromatic hydrocarbon compound) is 1:9 to 9:1 (mol%). And (3) after the reaction is finished, introducing cooling water to quickly cool the reaction kettle to room temperature, and taking a small amount of supernatant for quantitative analysis after the kettle is disassembled.
In the present application, the carbonate-based compound is preferably CO2Derived carbonate compounds, said "CO2The derivative carbonate compound refers to carbonate and derivatives thereof which are directly synthesized by taking renewable resource carbon dioxide as a raw material source.
As used herein, the term "hydrocarbyl" refers to a group formed by the loss of any hydrogen atom from a hydrocarbon molecule; the "aryl" is a group formed by losing any one hydrogen atom on an aromatic ring on the molecule of the aromatic compound.
Benefits that can be produced by the present application include, but are not limited to:
1) the metal oxide catalyst provided by the application is used for catalyzing aromatic hydrocarbon compounds and CO2When the aromatic carboxylic ester is prepared by the carboxylation coupling reaction of the derived carbonate compound, the catalytic efficiency is high, the product yield is obviously improved, the selectivity of the aromatic carboxylic ester under the catalysis of the metal oxide catalyst can reach 70 percent under the optimized operation and reaction conditions, and simultaneously, 30 percent of dimethylbenzene and a small amount of CO and CO can be produced2And by-products such as methanol and water.
2) According to the preparation method of the aromatic carboxylic ester compound, the reacted delta G < -20kJ/mol can realize the carboxylation reaction of the aromatic compound under high thermodynamic equilibrium conversion rate, so that the reaction equilibrium yield is greatly improved, and the aromatic carboxylic ester product which is easy to separate and purify is obtained.
3) The preparation method of the aromatic carboxylic ester compound provided by the application comprises the step of reacting CO2The derived carbonate compound is used as a reaction initiator, and the high-added-value chemicals can be prepared by efficient indirect resource utilization of carbon dioxide.
Drawings
FIG. 1 shows a sample of a metal oxide catalyst C1 in the examples of the present application#～C14#And XRD spectra of the comparative example.
FIG. 2 shows a sample of a metal oxide catalyst C15 in the examples of the present application#、C16#And C17#～C30#XRD spectrum of (1).
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The analysis method in the examples of the present application is as follows:
in the examples, the structure of a sample of a metal oxide catalyst was characterized by X-ray powder diffraction using a Rigaku PW1050/81 powder diffractometer using a Cu Ka radiation source
Figure GDA0002953454090000091
In the examples, the concentrations of the reactants and products were analyzed by high performance liquid chromatography, which was performed by using a model 7890B-5977A liquid chromatography-mass spectrometer from Agilent.
The conversion, selectivity, in the examples of the present application were calculated as follows:
in the examples of the present application, both the reactant conversion and the product selectivity were calculated on a carbon mole basis: wherein the yield of the aromatic carboxylic ester compound is calculated according to the carbon mole number of the carbonate compound in the raw materials.
EXAMPLE 1 preparation of a Mono-Metal oxide catalyst
#Preparation of C1 catalyst samples
Weighing 10.0mmol Mg (NO)3)2·6H2O is preparedPreparing an aqueous solution with the metal ion concentration of 1mol/L, placing the aqueous solution into a 500mL beaker, measuring 50mL of ammonia water (the mass fraction is 28 wt%) to dilute the aqueous solution with a certain proportion to prepare an aqueous solution with the concentration of 10 wt%, dripping the prepared aqueous solution of ammonia into a metal salt solution at 30 ℃, the dripping speed is about 5mL/min, the stirring speed is 600r/min, stopping dripping after the metal ions in the solution are completely precipitated, aging the obtained precipitated mother solution at 30 ℃, performing suction filtration, washing with deionized water until the filtrate is neutral, drying the obtained filter cake overnight in a vacuum oven, performing temperature programming in static air to the roasting temperature of 300 ℃ and keeping the roasting temperature for 3 hours to obtain an oxide catalyst, wherein the catalyst is marked as C1#A sample of the catalyst.
#Preparation of C2 catalyst samples
C2#The metal salt used for the catalyst preparation is 10.0mmol of Al (NO)3)3·6H2And O. The other preparation steps were the same as in example 1.
#Preparation of C3 catalyst samples
C3#The metal salt used for the catalyst preparation is 10.0mmol of La (NO)3)3·9H2And O. The other preparation steps were the same as in example 1.
#Preparation of C4 catalyst samples
C4#The metal salt used for the catalyst preparation is 10.0mmol of Zn (NO)3)3·6H2And O. The other preparation steps were the same as in example 1.
#Preparation of C5 catalyst samples
C5#The metal salt used for preparing the catalyst is 10.0mmol of Ce (NO)3)3·6H2And O. The other preparation steps were the same as in example 1.
#Preparation of C6 catalyst samples
C6#The metal salt used for preparing the catalyst is 10.0mmol of TiOSO4. The other preparation steps were the same as in example 1.
#Preparation of C7 catalyst samples
C7#The metal salt used for the catalyst preparation is 10.0mmol of Zr (NO)3)4·5H2And O. The other preparation steps were the same as in example 1.
#Preparation of C8 catalyst samples
C8#The metal salt used for preparing the catalyst is NbCl with the concentration of 10.0mmol5. The other preparation steps were the same as in example 1.
Example 2 preparation of composite Metal oxide catalyst
#Preparation of C9 catalyst samples
C9#The metal salt used for the catalyst preparation is 10.0mmol of Zn (NO)3)3·6H2O, 10.0mmol of Ce (NO)3)3·6H2O was formulated into an aqueous solution having a metal ion concentration of 1mol/L and placed in a 1000mL beaker. The other preparation steps were the same as in example 1.
#Preparation of C10 catalyst samples
C10#The metal salt used for the catalyst preparation is 10.0mmol of Zn (NO)3)3·6H2O, 10.0mmol of TiOSO4An aqueous solution having a metal ion concentration of 1mol/L was prepared and placed in a 1000mL beaker. The other preparation steps were the same as in example 1.
#Preparation of C11 catalyst samples
C11#The metal salt used for the catalyst preparation is 10.0mmol of Zn (NO)3)3·6H2O, 10.0mmol of Zr (NO)3)4·5H2O was formulated into an aqueous solution having a metal ion concentration of 1mol/L and placed in a 1000mL beaker. The other preparation steps were the same as in example 1.
#Preparation of C12 catalyst samples
C12#The metal salt used for preparing the catalyst is 10.0mmol Ce (NO)3)3·6H2O、10.0mmolTiOSO4An aqueous solution having a metal ion concentration of 1mol/L was prepared and placed in a 1000mL beaker. The other preparation steps were the same as in example 1.
#Preparation of C13 catalyst samples
C13#The metal salt used for the catalyst preparation is 10.0mmol of Zr (NO)3)4·5H2O、10.0mmol Ce(NO3)3·6H2O an aqueous solution having a specific metal ion concentration of 1mol/L was prepared and placed in a 1000mL beaker. The other preparation steps were the same as in example 1.
#Preparation of C14 catalyst samples
The metal salt used for the catalyst preparation is 10.0mmol of Zr (NO)3)4·5H2O、10.0mmol TiOSO4An aqueous solution having a metal ion concentration of 1mol/L was prepared and placed in a 1000mL beaker. The other preparation steps were the same as in example 1.
#Preparation of C15 catalyst samples
The metal salt used for the catalyst preparation is 10.0mmol of Zr (NO)3)4·5H2O、30.0mmol TiOSO4An aqueous solution having a metal ion concentration of 1mol/L was prepared and placed in a 1000mL beaker. The other preparation steps were the same as in example 1.
#Preparation of C16 catalyst samples
The metal salt used for the catalyst preparation is 30.0mmol of Zr (NO)3)4·5H2O、10.0mmol TiOSO4An aqueous solution having a metal ion concentration of 1mol/L was prepared and placed in a 1000mL beaker. The other preparation steps were the same as in example 1.
# #Preparation of C17-C30 catalyst samples
C17#～C30#Preparation of catalyst samples and C14#The same, the difference lies in:
C17#precipitation ofThe end point was a supernatant pH of 5.
C18#The end point was that the supernatant had a pH of 9.
C19#The calcination temperature of (2) was 250 ℃.
C20#The calcination temperature of (2) was 300 ℃.
C21#The calcination temperature of (A) was 350 ℃.
C22#The calcination temperature of (2) was 400 ℃.
C23#The calcination temperature of (A) was 450 ℃.
C24#The calcination temperature of (2) was 500 ℃.
C25#The calcination temperature of (3) was 550 ℃.
C26#The calcination temperature of (2) was 600 ℃.
C27#The calcination temperature of (2) was 650 ℃.
C28#The calcination temperature of (2) was 700 ℃.
C29#The calcination temperature of (3) was 750 ℃.
C30#The calcination temperature of (2) was 800 ℃.
# #Preparation of C31-C36 catalyst samples
C31#～C36#In the catalyst sample preparation process, the catalyst sample number, the corresponding metal salt type and mixing ratio, the precipitant type, and the calcination conditions are listed in table 1, and the other preparation steps are the same as those in example 1.
TABLE 1
Figure GDA0002953454090000131
EXAMPLE 3 evaluation of Metal oxide catalyst-preparation of methyl methylbenzoate by reaction of dimethyl carbonate with toluene
#Evaluation of C1 catalyst samples
Weigh 1.0g of C1#Metal oxide catalyst was mixed with 3.0g of dimethyl carbonate and 27.0g of tolueneFilling the mixed solution into a high-pressure reaction kettle, replacing the mixed solution with nitrogen for three times, filling the mixed solution to the set pressure of 2MPa, starting timing after the mixed solution is heated to 300 ℃, wherein the heating rate is 5 ℃/min, closing the heating after the mixed solution reacts for 10 hours, introducing cooling water to quickly cool the reaction kettle to the room temperature, and taking a small amount of supernatant for quantitative analysis after the reaction kettle is detached. The catalyst evaluation results are shown in Table 2.
# #Evaluation of C2-C16 catalyst samples
C2#～C16#Evaluation procedure of catalyst samples and C1#The catalyst samples were evaluated in the same manner. The catalyst evaluation results are shown in Table 2.
#Evaluation of C14 catalyst samples under different reaction conditions
1.0g of a composite metal oxide catalyst sample C14 was weighed#And putting the mixture together with 2.7-27.0 g of dimethyl carbonate and 26.0-2.8 g of toluene into a high-pressure reaction kettle (when the molar ratio of the dimethyl carbonate to the toluene is 1:9, namely the molar number of the dimethyl carbonate is 10%), replacing the mixture for three times by using a reaction atmosphere, filling the mixture to a set initial pressure, starting timing after heating to a set reaction temperature, wherein the heating rate is 5 ℃/min, closing the heating after reacting for 10 hours, introducing cooling water to quickly cool the reaction kettle to room temperature, and taking a small amount of supernatant for quantitative analysis after detaching the reaction kettle. The set reaction initial pressure, reaction temperature and reaction atmosphere are shown in Table 3, and the catalyst evaluation results are shown in Table 3.
TABLE 2C 2#～C16#Evaluation results of Metal catalyst samples
Figure GDA0002953454090000141
TABLE 3C 14#Evaluation results of composite metal catalyst samples under different reaction conditions
Figure GDA0002953454090000151
Example 4 evaluation of Metal oxide catalysts-different reaction raw materials
#Evaluation of C14 catalyst samples with different reaction materials
1.0g of a composite metal oxide catalyst sample C14 was weighed#Filling the carbonic ester and the aromatic hydrocarbon solution into a high-pressure reaction kettle, replacing the carbonic ester and the aromatic hydrocarbon solution by nitrogen for three times, filling the solution to 2.0MPa, starting timing after the temperature is increased to 300 ℃, wherein the temperature increase rate is 5 ℃/min, closing the heating after the reaction is carried out for 10 hours, introducing cooling water to quickly reduce the temperature of the reaction kettle to room temperature, and taking a small amount of supernatant for quantitative analysis after the kettle is removed. The types of the reaction raw materials and the molar ratios of the raw materials are shown in Table 4, and the catalyst evaluation results are shown in Table 4.
TABLE 4C 14#Evaluation results of composite metal catalyst samples under different reaction raw materials
Figure GDA0002953454090000152
N.d. indicates no other products were determined.
Example 5
At room temperature, to a mixed solution of toluene (90mmol) and dimethyl carbonate (10mmol), trifluoromethanesulfonic acid (2mmol) was slowly added dropwise at a rate of 0.5mL/min, and after completion of the dropwise addition, the mixture was heated to reflux (120 ℃ C.) to react for 10 hours, then cooled to room temperature, and a saturated aqueous solution of sodium hydrogencarbonate in ice was added, followed by extraction with ethyl acetate (3X 15mL), drying, removal of 1mL of the organic layer, addition of 1mL of ethyl acetate for dilution, and GC analysis. (conversion of dimethyl carbonate 80%, selectivity of methyl methylbenzoate 55%).
Example 6
Trifluoroacetic acid (2mmol) was slowly dropped into a mixed solution of toluene (90mmol) and dimethyl carbonate (10mmol) at a dropping rate of 0.5mL/min at room temperature, after completion of the dropping, the temperature was raised to a reflux state (120 ℃ C.) to react for 10 hours, then the reaction mixture was cooled to room temperature, a saturated ice-water solution of sodium bicarbonate was added, extraction was then carried out with ethyl acetate, after drying, 1mL of the organic layer was taken out, and then 1mL of ethyl acetate was added to dilute the organic layer, followed by GC analysis. (dimethyl carbonate conversion 60%, methyl benzoate selectivity 50%).
Example 7
Trifluoroacetic anhydride (2mmol) is slowly dropped into a mixed solution of toluene (90mmol) and dimethyl carbonate (10mmol) at the dropping speed of 0.5mL/min at room temperature, after the dropping is finished, the temperature is raised to the reflux state (120 ℃) for reaction for 10 hours, then the reaction product is cooled to the room temperature, a saturated ice water solution of sodium bicarbonate is added, then the extraction is carried out by ethyl acetate, after the drying, 1mL of an organic layer is taken out, then 1mL of ethyl acetate is added for dilution, and the GC analysis is carried out. (conversion of dimethyl carbonate 65%, selectivity of methyl methylbenzoate 52%).
Example 8
At room temperature, aluminum trichloride (2mmol) was slowly dropped into a mixed solution of toluene (90mmol) and dimethyl carbonate (10mmol) at a dropping rate of 0.5mL/min, after completion of the dropping, the temperature was raised to a reflux state (120 ℃ C.) to react for 10 hours, the reaction mixture was cooled to room temperature, a saturated sodium bicarbonate ice water solution was added, extraction was then performed with ethyl acetate, after drying, 1mL of the organic layer was taken out, and then 1mL of ethyl acetate was added to dilute the organic layer, followed by GC analysis. (conversion of dimethyl carbonate 80%, selectivity of methyl methylbenzoate 65%).
Example 9
At room temperature, slowly dropwise adding ferric trichloride (3mmol) into a mixed solution of toluene (90mmol) and dimethyl carbonate (10mmol) at a dropping speed of 0.5mL/min, heating to a reflux state (120 ℃) after the dropwise adding is finished, reacting for 10 hours, cooling to room temperature, adding an ice water solution of saturated sodium bicarbonate, extracting with ethyl acetate, drying, taking out 1mL of an organic layer, adding 1mL of ethyl acetate for dilution, and carrying out GC analysis. (conversion of dimethyl carbonate 50%, selectivity of methyl methylbenzoate 60%).
Example 10
At room temperature, zinc dichloride (3mmol) is slowly dropped into a mixed solution of toluene (90mmol) and dimethyl carbonate (10mmol) at the dropping speed of 0.5mL/min, after the dropping is finished, the temperature is raised to a reflux state (120 ℃) for reaction for 10 hours, then the mixture is cooled to room temperature, a saturated ice water solution of sodium bicarbonate is added, then the mixture is extracted by ethyl acetate, after the drying, 1mL of an organic layer is taken out, then 1mL of ethyl acetate is added for dilution, and GC analysis is carried out. (conversion of dimethyl carbonate 40%, selectivity of methyl methylbenzoate 40%).
Comparative example 1
TiO prepared by mechanical mixing method2+ZrO2A composite metal oxide catalyst.
10.0mmol of TiOSO is taken4Preparing 1mol/L aqueous solution, placing the aqueous solution into a 500mL beaker, measuring 50mL of ammonia water (the mass fraction is 28wt percent) to dilute the aqueous solution until the concentration is 10wt percent, and dripping TiOSO into the prepared aqueous solution at the temperature of 30 DEG C4Dripping into the solution at a speed of about 5mL/min and a stirring speed of 600r/min, stopping dripping after metal ions in the solution are completely precipitated, aging the obtained precipitation mother liquor at 30 ℃, performing suction filtration, washing with deionized water until the filtrate is neutral, drying the obtained filter cake in a vacuum oven overnight, and heating to 300 ℃ in static air for 3 hours to obtain TiO2A catalyst.
Taking 10.0mmol of Zr (NO)3)4·5H2O, ZrO made by the above method2A catalyst.
Taking the above 2mmol of ZrO2With 2mmol TiO2Mechanically mixing, heating to 300 deg.C in static air, and maintaining for 3 hr to obtain TiO catalyst2+ZrO2。
The catalyst evaluation procedure was the same as in example 1, and the catalyst evaluation results are shown in Table 2.
Aromatic hydrocarbon and carbonic ester derived from carbon dioxide are subjected to carboxylation coupling to prepare aromatic carboxylic ester, so that efficient indirect resource utilization of carbon dioxide can be realized to prepare high-value-added chemicals. From C14#And C1#～C16#Comparison of the evaluation results of the comparative samples shows that Ti was prepared by precipitation in a molar ratio of 1:11-Zr1OxComplex metal oxide catalyst (sample C14)#) The yield advantage of the aromatic carboxylic ester is obvious; when the catalyst is prepared in static air and under optimized aging and roasting conditions, under optimized reaction conditions, the carboxylation coupling of various aromatic hydrocarbons and carbonic ester can be realized, and a new way for efficiently preparing aromatic carboxylic acid and derivatives thereof is provided.
EXAMPLE 11 XRD Structure characterization of the catalyst
Characterizing the structure of a sample of the metal oxide catalyst by X-ray powder diffraction, wherein the sample of the metal oxide catalyst is C1#～C14#And the XRD pattern of the comparative example is shown in FIG. 1, and the metal oxide catalyst sample C15#、C16#And C17#～C30#The XRD spectrum of the compound is shown in figure 2. The correspondence between each sample number and the sample name in fig. 1 and 2 is listed in correspondence with table 5.
As can be seen from fig. 1, the method can successfully prepare single metal and composite metal oxides, and the roasting process can completely convert hydroxide into oxide, and no obvious hydroxide residue is found.
As can be seen from FIG. 2, the composite metal oxides with different Ti and Zr ratios have amorphous structures under the preparation conditions; ti1-Zr1OxThe catalyst is also in an amorphous structure when prepared by adopting supernatant with different pH values; ti1-Zr1OxThe catalyst is in an amorphous structure at the roasting temperature of less than 600 ℃, and gradually crystallizes after the roasting temperature is higher than 650 ℃.
TABLE 5 correspondence of sample number to sample name in the drawing
Figure GDA0002953454090000181
Figure GDA0002953454090000191
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (14)

1. A preparation method of aromatic carboxylic ester compounds is characterized in that in the presence of a catalyst, aromatic hydrocarbon compounds and carbonate compounds react to obtain aromatic carboxylic ester compounds;
the catalyst is selected from at least one of homogeneous catalyst and heterogeneous catalyst;
the homogeneous catalyst is selected from at least one of organic acid, Lewis acid and trifluoroacetic anhydride;
the organic acid is at least one of trifluoromethanesulfonic acid and trifluoroacetic acid;
the Lewis acid is selected from at least one of aluminum trichloride, ferric trichloride and zinc dichloride;
the heterogeneous catalyst is a metal oxide catalyst;
the metal oxide catalyst comprises a single metal oxide and/or a composite metal oxide;
the single metal oxide comprises MgO and ZrO2One of (1);
the composite metal oxide is selected from Zn1-Ce1Ox、Zn1-Ti1Ox、Zn1-Zr1Ox、Ce1-Ti1Ox、Ce1-Zr1Ox、Ti1-Zr1Ox、Ti3-Zr1OxAny one of (a);
the aromatic hydrocarbon compound is selected from at least one of a compound with a chemical formula shown as a formula I-1 and a compound with a chemical formula shown as a formula I-2:
Figure FDA0003206934970000011
wherein R is11Independently selected from hydrogen, C1～C5Alkyl groups of (a); n is 0,1, 2, 3, 4 or 5;
Figure FDA0003206934970000012
wherein R is12Independently selected from hydrogen, C1～C5Alkyl groups of (a); m is 0,1, 2, 3, 4,5, 6 or 7.
2. The method of claim 1, wherein the metal oxide catalyst is prepared by a precipitation method, and the metal oxide catalyst is obtained by precipitating a solution containing a metal salt and/or a mixed metal salt and a precipitant in an aqueous solution, drying and calcining.
3. The method according to claim 2, wherein the metal salt is at least one selected from the group consisting of nitrates, halides, sulfates, ammonium salts, and organic salts of the metal element.
4. The method according to claim 3, wherein the organic salt is at least one selected from an acetate and an oxalate of the metal element.
5. The method according to claim 2, wherein the metal salt is selected from the group consisting of titanyl sulfate, titanium isopropoxide, butyl titanate.
6. The method of claim 2, wherein the metal salt is selected from the group consisting of zirconium oxychloride, zirconyl nitrate, zirconium isopropoxide.
7. The method of claim 2, wherein the precipitant is at least one selected from the group consisting of ammonia, ammonium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, and potassium hydroxide.
8. The method of claim 2, wherein the firing comprises static firing and/or flowing atmosphere firing;
the roasting atmosphere is at least one of air, oxygen and nitrogen, and the roasting temperature is between room temperature and 1000 ℃.
9. The method of claim 1, wherein the aromatic hydrocarbon compound comprises at least one of benzene, toluene, ethylbenzene, and naphthalene.
10. The method according to claim 1, wherein the carbonate compound is at least one selected from the group consisting of a compound having a chemical formula shown in formula II-1 and a compound having a chemical formula shown in formula II-2:
Figure FDA0003206934970000031
wherein R is211And R212Each independently selected from hydrogen and C1～C5And R is alkyl of211And R212Not hydrogen at the same time;
Figure FDA0003206934970000032
wherein R is221And R222Each independently selected from hydrogen, alkyl, aryl; x and Y are each independently selected from C, O, and X and Y are not both C.
11. The method of claim 1, wherein the carbonate compound comprises at least one of dimethyl carbonate, propylene carbonate, styrene carbonate, and 2-oxazolidinone.
12. The method of claim 1, wherein the reaction conditions of the reaction comprise: the reaction temperature is 0-600 ℃, the initial reaction pressure is 0-20 MPa, the reaction atmosphere is at least one selected from nitrogen, carbon dioxide, helium and argon, and the molar concentration ratio of reactants in the reaction liquid is n (carbonate compound): n (aromatic hydrocarbon compound) is 1:9 to 9: 1.
13. The method of claim 1, wherein the reaction conditions of the reaction comprise: the reaction temperature is 100-500 ℃, the initial reaction pressure is 1-5 MPa, the reaction atmosphere is at least one selected from nitrogen, carbon dioxide and argon, and the molar concentration ratio of reactants in the reaction liquid is n (carbonate compound): n (aromatic hydrocarbon compound) is 1:9 to 1: 1.
14. The process of claim 1, wherein the reaction is carried out in an autoclave batch reactor.
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