CN113501798B - Method for preparing alkyl furoate by oxidizing and esterifying furfural - Google Patents

Method for preparing alkyl furoate by oxidizing and esterifying furfural Download PDF

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CN113501798B
CN113501798B CN202110807171.5A CN202110807171A CN113501798B CN 113501798 B CN113501798 B CN 113501798B CN 202110807171 A CN202110807171 A CN 202110807171A CN 113501798 B CN113501798 B CN 113501798B
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furfural
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furoate
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刘海龙
陈静
童进
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Lanzhou Institute of Chemical Physics LICP of CAS
CITIC National Chemical Co Ltd
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CITIC National Chemical Co Ltd
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Abstract

The invention relates to a method for preparing alkyl furoate by oxidizing and esterifying furfural, which is characterized by comprising the following steps of: the method comprises the steps of adding a furfural-alkyl alcohol solution and a supported Au-based catalyst into a high-pressure reaction kettle, and reacting for 2-20 hours under the conditions that the reaction temperature is 50-150 ℃ and the initial pressure is 0.1-5 MPa in an oxygen or air atmosphere to obtain the alkyl furoate. The catalytic system for preparing the alkyl furoate by oxidizing and esterifying the furfural does not need to additionally add an alkali assistant, and the product separation and catalyst circulation process is simpler and more economic.

Description

Method for preparing alkyl furoate by oxidizing and esterifying furfural
Technical Field
The invention relates to the technical field of energy and chemical engineering, in particular to a method for preparing alkyl furoate through furfural oxidative esterification.
Background
Alkyl furoate is an important fine chemical, and on one hand, as a synthetic spice, the alkyl furoate has wide application in the industries of food, tobacco, cosmetics and the like; on the other hand, the furoic acid alkyl ester is an important chemical raw material and an intermediate, can be used as a gasoline antiknock agent to improve the quality of gasoline, is a synthetic intermediate of medicines, and can also be used as a raw material for producing furan products. Therefore, the development of a simple, efficient and clean method for synthesizing the alkyl furoate has very important application value and sustainable development significance.
At present, alkyl furoate is mainly prepared by first oxidizing furfural into furoic acid and then carrying out esterification reaction with alkyl alcohol by a two-step method. Compared with the prior technical route, the method has more competitive power for obtaining the furoic acid alkyl ester by oxidizing and esterifying the furfural and the alkyl alcohol in one step. However, the preparation of alkyl furoate by one-step oxidative esterification of furfural with alkyl alcohol has been reported to be less, and a large amount of alkali promoter has been reported to improve the conversion rate of furfural and the yield of alkyl furoate. For example, tararing et al reported supported Au/TiO 2 The catalyst is sodium methoxide is taken as an auxiliary agent, so that the preparation of the furoic acid methyl ester (methyl ester) (is prepared by oxidizing and esterifying the furfural)ChemSusChem, 2008, 1, 75- 78) (ii) a Tong et al reported thatAu-Fe loaded with hydroxyapatite x O y As a catalyst, K 2 CO 3 The furfural conversion rate and the methyl furoate selectivity can respectively reach 93 percent and 99 percent as an auxiliary agent, and the furfural conversion rate and the methyl furoate selectivity can only respectively reach 54 percent and 11 percent in the absence of an alkaline auxiliary agent (Chem. Commun., 2015, 51, 3674) (ii) a Deng et al Co x O y -N @ C is catalyst and K 2 CO 3 When the furfural is used as an auxiliary agent, the conversion rate of furfural is close to 100 percent, and the selectivity of methyl furoate is high>95%（ChemSusChem, 2014, 7, 3334) (ii) a Patent applicationCN 109824634AA method for preparing methyl furoate by directly oxidizing and esterifying furfural is reported, wherein under the condition of using an alkaline assistant, supported nano cobalt particles are used as a catalyst, and the methyl furoate is obtained by efficiently catalyzing the oxidizing and esterifying furfural. Although these catalytic systems can realize the one-step oxidation esterification of furfural to prepare alkyl furoate, the addition of a large amount of homogeneous alkali makes it difficult to separate and recycle the furfural, so that the subsequent process needs to introduce acid to neutralize the system, which increases the production cost and generates a large amount of solid waste. Patent applicationCN 108148024AReports an efficient oxidation esterification system of furfural without adding homogeneous alkali auxiliary agent, and the technology adopts carbon-coated CoO x the-N/MgO is used as a catalyst, the conversion rate of furfural and the selectivity of methyl furoate can respectively reach 98 percent and 99 percent at most, but the catalyst needs to be added with expensive organic nitrogen-containing ligand in the preparation process, and the large-scale industrial preparation is difficult to realize. Therefore, it is very important to develop a catalytic system capable of efficiently catalyzing furfural to perform oxidative esterification to prepare alkyl furoate without using an alkaline auxiliary agent.
Disclosure of Invention
The invention aims to provide a simple, efficient and economical method for preparing alkyl furoate through furfural oxidative esterification without an alkali assistant.
In order to solve the problems, the invention provides a method for preparing alkyl furoate by oxidizing and esterifying furfural, which is characterized by comprising the following steps: adding a furfural-alkyl alcohol solution and a supported Au-based catalyst into a high-pressure reaction kettle, and reacting for 2 to 20 hours under the conditions that the reaction temperature is 50 to 150 ℃ and the initial pressure is 0.1 to 5 MPa in an oxygen or air atmosphere to obtain alkyl furoate; wherein: the mass part of the furfural in the furfural-alkyl alcohol solution is 1 to 50 wt%; the mass ratio of the supported Au-based catalyst to the furfural is 0.05 to 2.
The alkyl alcohol in the furfural-alkyl alcohol solution is at least one of methanol, ethanol, propanol, isopropanol and n-butanol.
The content of metal Au in the supported Au-based catalyst is 1 to 10 wt%.
The content of the metal oxide in the supported Au-based catalyst is 1 to 50 wt%.
The metal oxide in the supported Au-based catalyst is Fe 2 O 3 、Co 3 O 4 、NiO、CuO、La 2 O 3 、CeO 2 、MoO x One kind of (1).
The supported Au-based catalyst is prepared by the following method: mixing the mixed solution of chloroauric acid and non-noble metal salt with carrier powder according to a ratio of 500 mL: uniformly mixing 4.0-9.4 g, dropwise adding an alkali solution with the concentration of 5-50 wt% under vigorous stirring until the pH of the solution is greater than 7, and aging at 30-100 ℃ for 1-20 h to obtain a solid; and filtering and washing the solid, drying the solid for 10 hours at 110 ℃, and roasting the solid for 1 to 20 hours at 200 to 600 ℃ in an air atmosphere to obtain the solid.
The carrier is MgO or SiO 2 、Al 2 O 3 、TiO 2 、ZrO 2 、ZnO、MnO 2 、Mg 3 AlO x 、Zn 3 AlO x And activated carbon.
The mixed solution of the chloroauric acid and the non-noble metal salt is prepared by mixing the chloroauric acid with the Au content of 0.5 wt% and the non-noble metal salt according to the weight ratio of 5 to 100:1, and dissolved in water to prepare 500 mL of an aqueous solution.
The non-noble metal salt is Fe (NO) 3 ) 3 ·9H 2 O、Co(NO 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O、La(NO 3 ) 3 ·6H 2 O、Ce(NO 3 ) 3 ·6H 2 O、Ammonium molybdate tetrahydrate.
The alkaline solution is Na 2 CO 3 、K 2 CO 3 、(NH 3 ) 2 CO 3 、NaOH、KOH、NaHCO 3 、KHCO 3 One of ammonium bicarbonate, urea and ammonia water solution.
The mass part of the furfural in the furfural-alkyl alcohol solution is preferably 10 to 20 wt%.
The mass ratio of the supported Au-based catalyst to the furfural is preferably 0.2 to 1.
The content of metal Au in the supported Au-based catalyst is preferably 1 to 5 wt%.
The content of the metal oxide in the supported Au-based catalyst is preferably 5 to 30 wt%.
The concentration of the alkali solution is preferably 10 to 25 wt%.
The aging temperature is preferably 40 to 80 ℃; the aging time is 4 to 10 hours.
The roasting temperature is preferably 300 to 500 ℃; the baking time is 4 to 10 hours.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, furfural is used as a substrate, supported Au modified by metal oxide is used as a catalyst, oxygen or air is used as an oxidant, and furfural is efficiently catalyzed, oxidized and esterified to synthesize the alkyl furoate under the mild condition without an alkaline auxiliary agent, so that the method has remarkable technical and economic effects and good application prospect.
2. The catalyst adopted by the invention has the advantages of simple preparation, high stability and relatively low cost.
3. The catalytic system adopted by the invention has mild reaction conditions, and the furfural conversion rate and the selectivity of the alkyl furoate can both exceed 98 percent.
4. The catalytic system for preparing the alkyl furoate by oxidizing and esterifying the furfural does not need to additionally add an alkali assistant, and the product separation and catalyst circulation process is simpler and more economic.
Detailed Description
A method for preparing alkyl furoate through oxidative esterification of furfural is characterized by adding a furfural-alkyl alcohol solution and a supported Au-based catalyst into a high-pressure reaction kettle, and reacting for 2 to 20 hours under the conditions that the reaction temperature is 50 to 150 ℃ and the initial pressure is 0.1 to 5 MPa in an oxygen or air atmosphere to obtain the alkyl furoate.
Wherein: the mass part of the furfural in the furfural-alkyl alcohol solution is 1 to 50 wt%, preferably 10 to 20 wt%; the mass ratio of the supported Au-based catalyst to the furfural is 0.05 to 2, preferably 0.2 to 1.
The alkyl alcohol in the furfural-alkyl alcohol solution is at least one of methanol, ethanol, propanol, isopropanol and n-butanol.
The content of metal Au in the supported Au-based catalyst is 1 to 10 wt%, preferably 1 to 5 wt%.
The content of the metal oxide in the supported Au-based catalyst is 1 to 50 wt%, preferably 5 to 30 wt%.
The metal oxide in the supported Au-based catalyst is Fe 2 O 3 、Co 3 O 4 、NiO、CuO、La 2 O 3 、CeO 2 、MoO x One kind of (1).
The supported Au-based catalyst is prepared by the following method: mixing a mixed solution of chloroauric acid and non-noble metal salt with carrier powder according to a ratio of 500 mL: uniformly mixing 4.0 to 9.4g, dropwise adding an alkali solution with the concentration of 5 to 50 wt% under vigorous stirring until the pH of the solution is more than 7, and aging at 30 to 100 ℃ for 1 to 20 hours to obtain a solid; and filtering and washing the solid, drying the solid for 10 hours at 110 ℃, and roasting the solid for 1 to 20 hours at 200 to 600 ℃ in an air atmosphere to obtain the catalyst.
The carrier is MgO or SiO 2 、Al 2 O 3 、TiO 2 、ZrO 2 、ZnO、MnO 2 、Mg 3 AlO x 、Zn 3 AlO x And activated carbon.
The mixed solution of the chloroauric acid and the non-noble metal salt is prepared by mixing the chloroauric acid with 0.5 wt% of Au and the non-noble metal salt according to the weight ratio of 5-100: 1, and dissolved in water to prepare 500 mL of an aqueous solution.
The non-noble metal salt is Fe (NO) 3 ) 3 ·9H 2 O、Co(NO 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O、La(NO 3 ) 3 ·6H 2 O、Ce(NO 3 ) 3 ·6H 2 O and ammonium molybdate tetrahydrate.
The alkaline solution is Na 2 CO 3 、K 2 CO 3 、(NH 3 ) 2 CO 3 、NaOH、KOH、NaHCO 3 、KHCO 3 One of ammonium bicarbonate, urea and ammonia water solution. The concentration of the alkali solution is preferably 10 to 25 wt%.
The aging temperature is preferably 40 to 80 ℃; the aging time is 4 to 10 hours.
The roasting temperature is preferably 300 to 500 ℃; the baking time is 4 to 10 hours.
Example 1 a method for preparing alkyl furoate by oxidative esterification of furfural, which is to add 30 g of 20 wt% furfural-methanol solution together with 0.3 g of supported Au-based catalyst into a 100 mL stainless steel high-pressure reaction vessel, replace nitrogen three times, pressurize oxygen to 2.0 MPa, rapidly heat to 120 ℃ and react for 10 hours. And (3) after the reaction is finished, introducing condensed water, cooling to room temperature, slowly discharging gas and reducing pressure to obtain reaction liquid, namely the furoic acid alkyl ester.
Wherein: the supported Au-based catalyst comprises 1% of active component Au and an auxiliary agent Fe in percentage by mass 2 O 3 5 percent of the content and the balance of SiO carrier 2 . The preparation process comprises the following steps:
20 g of chloroauric acid solution (Au content 0.5 wt%), 2.53 g of Fe (NO) 3 ) 3 ·9H 2 O500 mL of an aqueous solution, 9.4g of SiO 2 The carrier was dispersed in the mixed solution, and then a sodium carbonate solution (10 wt%) was added thereto under vigorous stirring until the solution pH>7, after the dropwise addition is finished, heating the mixture to 50 ℃ and aging for 10 hours to obtain a solid; filtering and washing the solid until no Cl is detected in the filtrate - Drying at 110 deg.c for 10 hr, and roasting at 400 deg.c in air atmosphere for 5 hr to obtain catalyst A.
Example 2 a process for the oxidative esterification of furfural to produce alkyl furoate is the same as in example 1.
Wherein: the supported Au-based catalyst comprises 5 mass percent of active component Au and an auxiliary agent Co 3 O 4 5 percent of the total weight, and the balance of MgO as a carrier. The preparation process comprises the following steps:
100 g of chloroauric acid solution (Au content 0.5 wt%), 1.81 g of Co (NO) 3 ) 2 ·6H 2 O was prepared into a 500 mL aqueous solution, 9.0 g of MgO carrier was dispersed in the mixed solution, and then a potassium carbonate solution (10 wt%) was added thereto under vigorous stirring until the solution pH>7, after the dropwise addition is finished, heating the mixture to 50 ℃ and aging for 10 hours to obtain a solid; filtering and washing the solid until no Cl is detected in the filtrate - Drying at 110 deg.c for 10 hr, and roasting at 400 deg.c in air atmosphere for 5 hr to obtain catalyst B.
Example 3 a process for the oxidative esterification of furfural to produce alkyl furoate is the same as in example 1.
Wherein: the supported Au-based catalyst comprises, by mass, 10% of active component Au, 50% of auxiliary agent NiO and the balance of carrier Al 2 O 3 . The preparation process comprises the following steps:
200 g of chloroauric acid solution (Au content 0.5 wt%), 19.46 g of Ni (NO) 3 ) 2 ·6H 2 O was prepared as a 500 mL aqueous solution, 4.0 g Al 2 O 3 The carrier was dispersed in the mixed solution, and then ammonium carbonate solution (10 wt%) was added thereto under vigorous stirring until the solution pH>7, after the dropwise addition is finished, heating the mixture to 50 ℃ and aging for 10 hours to obtain a solid; filtering and washing the solid until no Cl is detected in the filtrate - Drying at 110 deg.c for 10 hr, and roasting at 400 deg.c in air atmosphere for 5 hr to obtain catalyst C.
Example 4 a process for the preparation of alkyl furoates by oxidative esterification of furfural is the same as in example 1.
Wherein: the supported Au-based catalyst comprises, by mass, 1% of Au as an active component, 10% of CuO as an auxiliary agent, and the balance of TiO as a carrier 2 . The preparation process comprises the following steps:
20 g of chloroauric acid solution (Au content 0.5 wt.%.)）、3.04 g Cu(NO 3 ) 2 ·3H 2 O was prepared as a 500 mL aqueous solution, 8.9 g TiO 2 The carrier was dispersed in the mixed solution, and then a sodium hydroxide solution (20 wt%) was added thereto under vigorous stirring until the solution pH>7, after the dropwise addition is finished, heating the mixture to 30 ℃ and aging for 20 hours to obtain a solid; filtering and washing the solid until no Cl is detected in the filtrate - Drying at 110 deg.c for 10 hr, and roasting at 600 deg.c in air atmosphere for 1 hr to obtain catalyst D.
Example 5 a process for the oxidative esterification of furfural to produce alkyl furoate is the same as in example 1.
Wherein: the supported Au-based catalyst comprises 1% of active component Au and La as an auxiliary agent in percentage by mass 2 O 3 The content is 5 percent, and the balance is carrier ZrO 2 . The preparation process comprises the following steps:
20 g chloroauric acid solution (Au content 0.5 wt%), 1.33 g La (NO) 3 ) 3 ·6H 2 O500 mL of an aqueous solution, 9.4g of ZrO 2 The carrier was dispersed in the mixed solution, and then a potassium hydroxide solution (50 wt%) was added thereto under vigorous stirring until the solution pH>7, after the dropwise addition is finished, heating the mixture to 80 ℃ and aging for 5 hours to obtain a solid; filtering and washing the solid until no Cl is detected in the filtrate - Drying at 110 deg.c for 10 hr, and roasting at 200 deg.c in air atmosphere for 20 hr to obtain catalyst E.
Example 6 a process for the oxidative esterification of furfural to produce alkyl furoate is the same as in example 1.
Wherein: the supported Au-based catalyst comprises 1% of active component Au and auxiliary agent CeO in percentage by mass 2 5 percent of the content and the balance of carrier ZnO. The preparation process comprises the following steps:
20 g of chloroauric acid solution (Au content 0.5 wt%), 1.26 g of Ce (NO) 3 ) 3 ·6H 2 O was prepared into 500 mL of an aqueous solution, 9.4g of ZnO carrier was dispersed in the mixed solution, and then aqueous ammonia (5 wt%) was added thereto under vigorous stirring until the pH of the solution was reached>7, after the dropwise addition is finished, heating the mixture to 100 ℃ and aging for 1 h to obtain a solid; filtering the solidAnd washing until no Cl is detected in the filtrate - Drying at 110 deg.c for 10 hr, and roasting at 400 deg.c in air atmosphere for 10 hr to obtain catalyst F.
Example 7 a process for the oxidative esterification of furfural to produce alkyl furoates is the same as in example 1.
Wherein: the supported Au-based catalyst comprises 1% of active component Au and an auxiliary agent MoO in percentage by mass x 5% of the balance being MnO as a carrier 2 . The preparation method comprises the following specific steps:
preparing 500 mL of aqueous solution from 20 g of chloroauric acid solution (Au content of 0.5 wt%) and 0.61 g of ammonium molybdate tetrahydrate, and preparing 9.4g of MnO 2 The carrier was dispersed in the mixed solution, and then sodium bicarbonate (10 wt%) was added thereto under vigorous stirring until the solution pH>7, after the dropwise addition is finished, heating the mixture to 50 ℃ and aging for 10 hours to obtain a solid; filtering and washing the solid until no Cl is detected in the filtrate - Drying at 110 deg.c for 10 hr, and roasting at 400 deg.c in air atmosphere for 5 hr to obtain catalyst G.
Example 8 a process for the preparation of alkyl furoates by oxidative esterification of furfural is the same as in example 1.
Wherein: the supported Au-based catalyst comprises 1% of active component Au and Co as an auxiliary agent in percentage by mass 3 O 4 5 percent of the total weight of the alloy, and the balance of Mg as a carrier 3 AlO x . The preparation process comprises the following steps:
20 g of chloroauric acid solution (Au content 0.5 wt%), 1.81 g of Co (NO) 3 ) 2 ·6H 2 O was made into 500 mL aqueous solution, 9.4g Mg 3 AlO x The carrier was dispersed in the mixed solution, and then potassium hydrogencarbonate (10 wt%) was added thereto under vigorous stirring until the pH of the solution was reached>7, after the dropwise addition is finished, heating the mixture to 50 ℃ and aging for 10 hours to obtain a solid; filtering and washing the solid until no Cl is detected in the filtrate - Drying at 110 deg.c for 10 hr, and roasting at 400 deg.c in air atmosphere for 5 hr to obtain catalyst H.
Example 9 a process for the oxidative esterification of furfural to produce alkyl furoates is the same as in example 1.
Wherein: the supported Au-based catalyst comprises 1% of active component Au and an auxiliary agent Co in percentage by mass 3 O 4 5 percent of the carrier Zn 3 AlO x . The preparation process comprises the following steps:
20 g of chloroauric acid solution (Au content 0.5 wt%), 1.81 g of Co (NO) 3 ) 2 ·6H 2 O was prepared as a 500 mL aqueous solution, 9.4g Zn 3 AlO x The carrier was dispersed in the mixed solution, and then ammonium hydrogencarbonate (10 wt%) was added thereto under vigorous stirring until the pH of the solution was reached>7, after the dropwise addition is finished, heating the mixture to 50 ℃ and aging for 10 hours to obtain a solid; filtering and washing the solid until no Cl is detected in the filtrate - Drying at 110 deg.c for 10 hr, and roasting at 400 deg.c in air atmosphere for 5 hr to obtain catalyst I.
Example 10 a process for the oxidative esterification of furfural to produce alkyl furoates is the same as in example 1.
Wherein: the supported Au-based catalyst comprises 1% of active component Au and Co as an auxiliary agent in percentage by mass 3 O 4 5 percent of the active carbon, and the balance of the active carbon. The preparation process comprises the following steps:
20 g of chloroauric acid solution (Au content 0.5 wt%), 1.81 g of Co (NO) 3 ) 2 ·6H 2 O was prepared into a 500 mL aqueous solution, 9.4g of an activated carbon carrier was dispersed in the mixed solution, and then a urea solution (10 wt%) was added thereto under vigorous stirring until the solution pH>7, after the dropwise addition is finished, heating the mixture to 80 ℃ and aging for 10 hours to obtain a solid; filtering and washing the solid until no Cl is detected in the filtrate - Drying at 110 deg.c for 10 hr, and roasting at 400 deg.c in air atmosphere for 5 hr to obtain catalyst J.
The results of analyzing the reaction solutions obtained in examples 1 to 10 by GC are shown in Table 1. As can be seen from Table 1, under the action of the catalysts obtained in examples 1 to 10, furfural can be very efficiently oxidized and esterified to prepare alkyl furoate, and the conversion rate and the selectivity of the alkyl furoate are both more than 95%.
TABLE 1 test results of furfural oxidative esterification to prepare methyl furoate by different catalysts
Figure DEST_PATH_IMAGE001
Example 11 a method for preparing alkyl furoate by oxidative esterification of furfural, which comprises adding 30 g of 50 wt% furfural-methanol solution together with 0.15 g of supported Au catalyst B into a 100 mL stainless steel autoclave, displacing nitrogen three times, pressurizing oxygen to 2.0 MPa, rapidly heating to 150 ℃ and reacting for 2 hours. And after the reaction is finished, introducing condensed water, cooling to room temperature, slowly discharging gas and reducing pressure to obtain reaction liquid, namely the alkyl furoate.
Example 12 a method for preparing alkyl furoate by oxidative esterification of furfural, which comprises adding 30 g of 5 wt% furfural-methanol solution together with 0.3 g of supported Au catalyst B into a 100 mL stainless steel autoclave, displacing with nitrogen three times, pressurizing with oxygen to 2.0 MPa, rapidly heating to 50 ℃ and reacting for 20 hours. And (3) after the reaction is finished, introducing condensed water, cooling to room temperature, slowly discharging gas and reducing pressure to obtain reaction liquid, namely the furoic acid alkyl ester.
Example 13 a method for preparing alkyl furoate by oxidative esterification of furfural, which comprises adding 30 g of 1 wt% furfural-methanol solution together with 0.015 g of supported Au catalyst B into a 100 mL stainless steel high-pressure reaction vessel, displacing with nitrogen three times, pressurizing with oxygen to 5.0 MPa, rapidly heating to 100 ℃, and reacting for 10 hours. And (3) after the reaction is finished, introducing condensed water, cooling to room temperature, slowly discharging gas and reducing pressure to obtain reaction liquid, namely the furoic acid alkyl ester.
Example 14 a method for the oxidative esterification of furfural to alkyl furoate, which is to add 30 g of 20 wt% furfural-n-butanol solution together with 0.3 g of supported Au catalyst B into a 100 mL stainless steel autoclave, replace nitrogen three times, pressurize oxygen to 2.0 MPa, rapidly heat to 120 ℃ and react for 10 h. And (3) after the reaction is finished, introducing condensed water, cooling to room temperature, slowly discharging gas and reducing pressure to obtain reaction liquid, namely the furoic acid alkyl ester.
The results of analyzing the reaction solutions obtained in examples 11 to 14 by GC and GC are shown in Table 2. As can be seen from Table 2, different reaction conditions have a significant effect on the catalytic performance, and catalyst B shows excellent catalytic performance.
TABLE 2 influence of reaction conditions on Furfural oxidative esterification reaction Performance for preparation of alkyl Furfurates
Figure 708981DEST_PATH_IMAGE002

Claims (3)

1. A method for preparing alkyl furoate by oxidizing and esterifying furfural is characterized by comprising the following steps: adding a furfural-alkyl alcohol solution and a supported Au-based catalyst into a high-pressure reaction kettle, and reacting for 2 to 20 hours under the conditions that the reaction temperature is 50 to 150 ℃ and the initial pressure is 0.1 to 5 MPa in an oxygen or air atmosphere to obtain alkyl furoate; wherein: the mass part of the furfural in the furfural-alkyl alcohol solution is 1 to 50 wt%; the mass ratio of the supported Au-based catalyst to the furfural is 0.05-2; the content of metal Au in the supported Au-based catalyst is 1 to 10 wt%; the content of the metal oxide in the supported Au-based catalyst is 1 to 50 wt%; the supported Au-based catalyst is prepared by the following method: mixing the mixed solution of chloroauric acid and non-noble metal salt with carrier powder according to a ratio of 500 mL: uniformly mixing 4.0 to 9.4g, and dropwise adding an alkali solution with the concentration of 5 to 50 wt% to the pH value of the solution under vigorous stirring>7, aging at 30-100 ℃ for 1-20 h to obtain a solid; filtering and washing the solid, drying the solid for 10 hours at 110 ℃, and roasting the solid for 1 to 20 hours at 200 to 600 ℃ in an air atmosphere to obtain the solid; the carrier is MgO or SiO 2 、Al 2 O 3 、TiO 2 、ZrO 2 、ZnO、MnO 2 And activated carbon; the mixed solution of the chloroauric acid and the non-noble metal salt is prepared by mixing the chloroauric acid with 0.5 wt% of Au and the non-noble metal salt according to the weight ratio of 5-100: 1, and dissolving the mixture in water to prepare 500 mL of aqueous solution; the metal oxide in the supported Au-based catalyst is Fe 2 O 3 、Co 3 O 4 、NiO、CuO、La 2 O 3 、CeO 2 One of (1); the non-noble metal salt is Fe (NO) 3 ) 3 ·9H 2 O、Co(NO 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O、La(NO 3 ) 3 ·6H 2 O、Ce(NO 3 ) 3 ·6H 2 O and ammonium molybdate tetrahydrate.
2. The method for preparing alkyl furoate through oxidative esterification of furfural according to claim 1, wherein: the alkyl alcohol in the furfural-alkyl alcohol solution is at least one of methanol, ethanol, propanol, isopropanol and n-butanol.
3. The method for preparing alkyl furoate through oxidative esterification of furfural according to claim 1, wherein: the alkaline solution is Na 2 CO 3 、K 2 CO 3 、(NH 4 ) 2 CO 3 、NaOH、KOH、NaHCO 3 、KHCO 3 One of ammonium bicarbonate, urea and ammonia water solution.
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