CN113731469B - Solid catalyst for catalytic oxidation esterification reaction, and preparation method and application thereof - Google Patents

Solid catalyst for catalytic oxidation esterification reaction, and preparation method and application thereof Download PDF

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CN113731469B
CN113731469B CN202111068249.2A CN202111068249A CN113731469B CN 113731469 B CN113731469 B CN 113731469B CN 202111068249 A CN202111068249 A CN 202111068249A CN 113731469 B CN113731469 B CN 113731469B
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catalyst
solid catalyst
histidine
esterification reaction
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CN113731469A (en
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冷炎
黄宁
张萍波
蒋平平
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Jiangnan University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
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Abstract

The invention discloses a solid catalyst for catalytic oxidation esterification reaction, and a preparation method and application thereof, and belongs to the technical field of catalysis and fine organic chemical industry. The invention takes histidine as a precursor, introduces a sulfur-containing compound, and then calcinates the histidine-containing compound and transition metal cobalt copper to obtain the encapsulated nano metal catalyst. The catalyst has the advantages of simple preparation method, low cost and mass production, and the obtained catalyst has higher specific surface area and good metal particle dispersibility, can obtain ester yield higher than 90% and selectivity higher than 96% by catalyzing the oxidation esterification reaction of alcohol, has mild reaction conditions, can be recycled, has good application prospect, and is expected to provide technical support for the formation of a new catalytic process of ester compounds.

Description

Solid catalyst for catalytic oxidation esterification reaction and preparation method and application thereof
Technical Field
The invention relates to a solid catalyst for catalytic oxidation esterification reaction, a preparation method and application thereof, belonging to the technical field of catalysis and fine organic chemical industry.
Background
Ester compounds are important fine chemical raw materials and are widely applied to the fields of food, biology, medicine, chemical industry, materials and the like. The traditional synthetic ester compounds are mainly esterified with H through acid catalysis of alcohol and organic acid 2 SO 4 、HF、H 3 PO 4 And the inorganic liquid acid is used as a catalyst, so that the catalyst is difficult to separate and reuse, and has the problems of equipment corrosion, environmental pollution and the like. In recent years, with the continuous progress of oxidation reaction technology, the direct synthesis of ester compounds from alcohol compounds by oxidative esterification has received more and more attention. Among the numerous catalysts studied, non-noble metal catalysts are clearly in favour, especially supported non-metal catalysts, which are increasingly the focus of research due to their low cost, their recyclability and their reusability.
Transition nano-metals cobalt and copper are considered as effective catalysts for catalyzing oxidation esterification reactions, and in order to obtain a recyclable transition metal catalyst, the transition metal catalyst is immobilized on the surface of a porous carrier, but the obtained catalyst has the problems that active components are easy to dissolve and are difficult to reuse and the like. The encapsulated nano metal catalyst can effectively avoid the dissolution of metal particles, and the porous encapsulated carrier can also accelerate mass transfer. In view of this, there are various preparation strategies for the packaged catalysts, such as in-situ reduction/deposition, organic ligand blending calcination, metal-organic framework calcination, etc., however, most of these methods are complex and time-consuming to prepare, require the use of organic solvents, and the organic precursors used are usually expensive, so that it is of great importance to develop more simple and effective packaged transition metal oxidative esterification catalysts.
Disclosure of Invention
[ problem ] to
Aiming at the oxidation esterification reaction, the reaction conditions of the existing catalytic system are not green enough, the catalytic efficiency is low, and the catalyst is difficult to recover and reuse.
[ solution ]
In order to solve the problems, the invention provides a solid catalyst for oxidation esterification and a preparation method thereof. The preparation method of the catalyst is not reported at present, and the catalyst is not reported to be used in catalytic oxidation esterification reaction.
The catalyst prepared in the invention adopts histidine as an organic precursor, a porous carbon carrier with rich pore passages and higher specific surface area can be formed by roasting, the mass transfer rate can be effectively improved, in addition, the histidine contains rich nitrogen elements, the histidine and the metal form stronger metal-nitrogen interaction in the roasting process, the electronic conduction therebetween can effectively improve the catalytic efficiency of the metal, and the sulfur-containing organic matter is introduced for co-roasting, so that the catalytic activity of the metal can be further regulated.
The invention provides a method for preparing a solid catalyst for catalytic oxidation esterification reaction, which comprises the steps of carrying out ball milling on histidine, a sulfur source and a metal source on a three-dimensional oscillation ball mill, and then roasting in an inert atmosphere to obtain the solid catalyst M @ CNS.
In one embodiment of the present invention, the sulfur source is one or more of cysteine, bromamine acid, and thiourea.
In one embodiment of the invention, the metal source is a cobalt salt and/or a copper salt.
In one embodiment of the present invention, the cobalt salt is selected from one or more of cobalt chloride, cobalt nitrate and cobalt sulfate.
In one embodiment of the present invention, the copper salt is selected from one or more of copper chloride, copper nitrate and copper sulfate.
In one embodiment of the invention, the time of ball milling is 10-60min. Specifically, 30min can be selected.
In one embodiment of the invention, the inert atmosphere is nitrogen or argon.
In one embodiment of the invention, the temperature of roasting is 600-900 ℃; the specific choice is 800 ℃. The roasting time is 2-4h.
In one embodiment of the present invention, the mass ratio of histidine to sulfur source is 5: (1-5); preferably 5.
In one embodiment of the invention, the mass ratio of histidine to metal source is (4-10): 1; more preferably (5-8): 1. Specifically, 5.2.
In one embodiment of the invention, when the metal source is a cobalt salt and a copper salt, the molar ratio of cobalt to copper is (1-2): 1; specifically, the ratio is 1.65.
The invention provides a solid catalyst M @ CNS for oxidative esterification prepared by the method.
The invention provides an application of the solid catalyst in catalytic oxidation esterification reaction.
A process for catalytic oxidative esterification, comprising:
taking a benzyl alcohol compound shown in a formula (I) and an alkyl alcohol compound shown in a formula (II) as reaction substrates, and reacting under the catalytic action of the solid catalyst M @ CNS to obtain an ester compound shown in a formula (III);
Figure BDA0003259400120000021
wherein R is 1 Is a mono-substituted to tri-substituted substituent independently selected from H, C1-8 alkyl, C1-8 alkoxy, halogen (F, cl, br), cyano, ester group; r is 2 Is a C1-8 alkyl group.
In one embodiment of the invention, the solid catalyst M @ CNS is 2wt% -8 wt% of the total mass of the two alcohol substrates.
In one embodiment of the present invention, the molar ratio of the benzyl alcohol to the alkyl alcohol is 1. The specific optional 1.
In one embodiment of the present invention, the benzyl alcohol may be any one of benzyl alcohol and a derivative thereof.
In one embodiment of the present invention, the alkyl alcohol may be specifically any one of methanol, ethanol, n-propanol, and n-butanol.
In one embodiment of the invention, the temperature of the oxidative esterification reaction is 60-120 ℃; further preferably 60 to 80 ℃. The reaction time is 4-24 h; further preferably 10-24 hours.
[ advantageous effects ]
(1) The invention prepares the encapsulated solid catalyst by the method of ball milling and roasting the organic precursor and the metal source, and the method has simple process and simple and convenient operation and can be produced in large batch.
(2) The catalyst prepared by taking histidine as a precursor has higher specific surface area and rich pore structure, so that the catalyst can obtain higher ester yield of more than 90% in the oxidation esterification reaction.
(3) The invention introduces the sulfur-containing compound, so that the metal nanoparticles are partially reduced to form the nanoparticles with the core-shell structure in the roasting process of the catalyst, thereby improving the catalytic activity of the catalyst, and more importantly, the reaction condition is mild, and the reaction can be realized at the reaction temperature of 60-120 ℃.
(4) The catalyst prepared by the invention can be recycled and reused, and the catalyst prepared by the invention can be reused for 4 times without reducing the catalytic activity. Is expected to become an oxidation esterification solid catalyst with great market competitiveness.
Drawings
Fig. 1 is a TEM image of the catalyst prepared in example 1.
Fig. 2 is an XRD pattern of the catalyst prepared in example 1.
FIG. 3 is N of the catalyst prepared in example 1 2 The attached drawing is sucked and removed.
Detailed Description
The invention will now be further illustrated by reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
[ example 1 ]
1.25g of histidine, 0.75g of cysteine and 0.24g of cobalt chloride are added into a ball mill tank, ball milling is carried out for 30mim, and the obtained mixture is calcined for 2h in a nitrogen atmosphere at 800 ℃ to obtain a solid catalyst Co @ CNS.
N2 adsorption and desorption tests, XRD and TEM characterization are carried out on the solid catalyst Co @ CNS prepared in the embodiment, and FIG. 1 is a TEM image of the Co @ CNS, so that the nano particles are uniformly dispersed on the carrier and show an obvious core-shell structure. The XRD pattern (figure 2) shows obvious characteristic diffraction peaks (36.5, 42.4 and 61.5) of nano cobalt (44.1 and 51.2) and oxide, and the metal cobalt oxide is formed on the surface of the nano cobalt. N is a radical of 2 The absorption-desorption attached figure (figure 3) shows that the catalyst has rich pore channel structure and the specific surface area is 463m 2 /g。
[ example 2 ] A method for producing a polycarbonate
1.25g of histidine, 0.75g of cysteine, 0.15g of cobalt chloride and 0.07g of copper chloride were added to a ball mill pot, ball-milled for 30 mm, and the resulting mixture was calcined at 800 ℃ for 2 hours in a nitrogen atmosphere to obtain a solid catalyst CoCu @ CNS.
[ example 3 ]
1mmol of benzyl alcohol, 3mmol of methanol and 80mg of Co @ CNS catalyst prepared in example 1 were charged in a round-bottomed flask and stirred at 60 ℃ under atmospheric air for 10 hours to obtain a mixture containing methyl benzoate.
The yield and selectivity of the product were calculated from the gas chromatography detection chart using area normalization. The yield of methyl benzoate in this example was 96% and the selectivity was 99% by gas chromatography.
[ example 4 ] A method for producing a polycarbonate
1mmol of benzyl alcohol, 3mmol of butanol, and 80mg of Co @ CNS catalyst prepared in example 1 were charged in a round-bottomed flask, and stirred at 80 ℃ under atmospheric air for 12 hours to obtain a mixture containing butyl benzoate.
The yield and selectivity of the product were calculated from the gas chromatography profile using area normalization. The yield of butyl benzoate in this example was 81% and the selectivity was 96% by gas chromatography.
[ example 5 ]
1mmol of terephthalyl alcohol, 3mmol of methanol, and 80mg of Co @ CNS catalyst prepared in example 1 were charged in a round bottom flask and stirred at 60 ℃ under atmospheric air for 24 hours to obtain a mixture containing methyl terephthalate.
The yield and selectivity of the product were calculated from the gas chromatography detection chart using area normalization. The yield of methyl terephthalate in this example was 87% and the selectivity was 91% as determined by gas chromatography.
[ example 6 ]
1mmol of benzyl alcohol, 3mmol of methanol and 80mg of the catalyst CoCu @ CNS prepared in example 2 were charged in a round-bottomed flask, and the reaction was stirred at 60 ℃ under atmospheric air conditions for 12 hours to obtain a mixture containing methyl benzoate.
The yield and selectivity of the product were calculated from the gas chromatography detection chart using area normalization. The yield of methyl benzoate in this example was 90% and the selectivity was 99% by gas chromatography.
[ example 7 ]
In example 1, after the reaction, the catalyst was separated by filtration and reused under the same reaction conditions for 3 times, and the obtained methyl benzoate had yields of 96%, 93% and 94% in this order, and had a selectivity of 99% and no other by-products.
Comparative example 1
During the preparation of the catalyst, no cysteine is added: adding 2g of histidine and 0.24g of cobalt chloride into a ball milling tank, carrying out ball milling for 30min, and calcining the obtained mixture for 2h at 800 ℃ in a nitrogen atmosphere to obtain a sulfur-element-free solid catalyst Co @ CN. The catalyst was used in the oxidative esterification of benzyl alcohol and methanol according to the procedure of example 3, and the obtained benzyl alcohol had a conversion of only 46% and a selectivity of 58%.
Comparative example 2
During the preparation of the catalyst, cobalt chloride is changed into nickel chloride: adding 1.25g of histidine, 0.75g of cysteine and 0.24g of nickel chloride into a ball milling tank, carrying out ball milling for 30min, and calcining the obtained mixture for 2h at 800 ℃ in a nitrogen atmosphere to obtain a solid catalyst Ni @ CNS. The catalyst was used in the oxidative esterification of benzyl alcohol and methanol according to the procedure of example 3, and the obtained benzyl alcohol had a conversion of only 25% and a selectivity of 67%.
Comparative example 3
In the process of preparing the catalyst, histidine is replaced by conventional organic precursor chitosan: 1.25g of chitosan, 0.75g of cysteine and 0.24g of cobalt chloride are put into a ball mill pot, ball milling is carried out for 30min, and the obtained mixture is calcined for 2h in a nitrogen atmosphere at 800 ℃ to obtain the solid catalyst. The specific surface area of the catalyst was less than 100m according to the procedure of example 3 2 Is used for the oxidative esterification reaction of benzyl alcohol and methanol, and the obtained benzyl alcohol has the conversion rate of 77 percent and the selectivity of 96 percent.
Comparative example 4
During the preparation of the catalyst, histidine is replaced by glycine: 1.25g of glycine, 0.75g of cysteine and 0.24g of cobalt chloride were added to a ball mill pot, ball milling was carried out for 30min, and the resulting mixture was calcined at 800 ℃ for 2h in a nitrogen atmosphere to obtain a solid catalyst. The catalyst was used to catalyze the oxidative esterification of benzyl alcohol with methanol according to the procedure of example 3, resulting in a benzyl alcohol conversion of 81% and a selectivity of 94%.
Comparative example 5
1.25g of histidine, 0.75g of ammonium sulfate as a sulfur-containing reagent, and 0.24g of cobalt chloride were charged into a ball mill pot, ball-milled for 30 mm, and the resulting mixture was calcined at 800 ℃ for 2 hours in a nitrogen atmosphere to obtain a solid catalyst. The catalyst was used in the oxidative esterification of benzyl alcohol and methanol according to the procedure of example 3, and the obtained benzyl alcohol had a conversion of 75% and a selectivity of 84%.
[ COMPARATIVE EXAMPLE 6 ]
Referring to example 1, the amount of cysteine was changed from 0.75g to 0.5g and 1g, respectively, to obtain the corresponding solid catalyst.
The catalyst was used in oxidative esterification of benzyl alcohol and methanol according to the procedure of example 3, and the conversion and selectivity results of the obtained benzyl alcohol are shown in table 1.
TABLE 1
The amount of cysteine Mass ratio of histidine to sulfur source Conversion of benzyl alcohol Selectivity of reaction
0.75g (example 1) 5:3 96％ 99％
0.5g 5:2 88％ 92％
1g 5:4 63％ 70％
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (7)

1. A method for preparing a solid catalyst for catalytic oxidation esterification reaction is characterized in that histidine, a sulfur source and a metal source are subjected to ball milling on a three-dimensional oscillation ball mill, and then are roasted in an inert atmosphere to obtain the solid catalyst; the metal source is cobalt salt and/or copper salt; the sulfur source is cysteine; the mass ratio of the histidine to the sulfur source is 5:2-3.
2. The method according to claim 1, wherein the mass ratio of histidine to metal source is 4-10.
3. The method as claimed in claim 1, wherein the roasting temperature is 600-900 ℃; the roasting time is 2-4h.
4. The method according to any one of claims 1 to 3, wherein the inert atmosphere is nitrogen or argon.
5. A solid catalyst for catalytic oxidative esterification prepared by the process of any one of claims 1 to 4.
6. A method for catalytic oxidation esterification reaction is characterized in that benzyl alcohol compounds shown in formula (I) and alkyl alcohol compounds shown in formula (II) are used as reaction substrates and react under the catalytic action of a solid catalyst in claim 5 to prepare ester compounds shown in formula (III);
Figure FDA0003820387680000011
wherein R is 1 Is a substituent of mono-to tri-substitution, and is independently selected from H, C1-8 alkyl, C1-8 alkoxy, halogen, cyano and ester group; r 2 Is a C1-8 alkyl group.
7. The method of claim 6, wherein the solid catalyst is added in an amount of 2wt% to 8wt% based on the total mass of the two alcohol substrates.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1922129A (en) * 2004-02-17 2007-02-28 埃克森美孚研究工程公司 Catalytic preparation of severely sterically hindered amino-ether alcohols using a metal loaded catalyst
CN106694007A (en) * 2016-12-19 2017-05-24 中国科学院山西煤炭化学研究所 Monodisperse metal atom/graphene composite catalyst and preparation method and application thereof

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EP2535971B1 (en) * 2010-02-10 2018-10-24 Showa Denko K.K. Process for producing fuel cell electrode catalyst, process for producing transition metal oxycarbonitride, fuel cell electrode catalyst, and uses thereof
CN103402633B (en) * 2011-01-20 2017-03-01 昭和电工株式会社 The manufacture method of catalyst carrier, the manufacture method of composite catalyst, composite catalyst and the fuel cell using this composite catalyst
CN107252702B (en) * 2017-07-24 2020-01-17 苏州大学 Co-N-C/SiO2Composite nano catalyst, preparation method and application thereof
CN111545239B (en) * 2020-05-29 2021-06-25 江南大学 Solid catalyst for glycerol oxidation and preparation method thereof
CN113042099B (en) * 2021-03-19 2022-06-07 江南大学 Solid acid catalyst for catalytic esterification synthesis of gallic acid ester

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1922129A (en) * 2004-02-17 2007-02-28 埃克森美孚研究工程公司 Catalytic preparation of severely sterically hindered amino-ether alcohols using a metal loaded catalyst
CN106694007A (en) * 2016-12-19 2017-05-24 中国科学院山西煤炭化学研究所 Monodisperse metal atom/graphene composite catalyst and preparation method and application thereof

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