Preparation method of 2-furfural diethyl acetal
By using ceria-supported metal catalyst to convert furfural to 2-furfural diethanol, the problems of uneconomic preparation methods and unstable products in the prior art are solved, and an efficient and economical preparation process is achieved, and it is characterized by environmental protection and sustainable development.
Patent Information
- Application Number
- CN202510117297.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-24
- Publication Date
- 2025-04-25
AI Technical Summary
The prior art is difficult to efficiently and economically prepare 2-furfural diethanol, and its application is limited by high toxicity and instability.
Using a ceria-supported metal catalyst, 2-furfural diethanol was generated by reaction between furfural and ethanol at room temperature ~100°C. The catalyst consists of metal salts, organic matter and cerium acetate, and is prepared by calcination. It has the characteristics of low cost and high efficiency.
The efficient conversion of furfural to 2-furfural diethanol is achieved, with a yield of more than 90%, which has the advantages of low cost and high efficiency. It can also use lignocellulose-derived furfural to solve the problems of resource waste and environmental pollution.
Smart Images
Figure CN119874645A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of organic compound synthesis, and in particular to a method for preparing 2-furfural diethyl acetal. Background Art
[0002] Since the 2-furfural acetal molecule contains furfural and diethanol groups, it has certain activity and can undergo condensation reactions with other compounds containing active groups. For example, in the presence of an appropriate catalyst, it can undergo condensation reactions with aldehydes, ketones, etc. to generate compounds with more complex structures, which have potential application value in the fields of spices, medicines, etc. The furfural group in 2-furfural acetal can be hydrogenated under the action of a catalyst and converted into corresponding alcohols or other saturated compounds. The hydrogenation reaction can change its chemical properties, making it less toxic and more stable, and also provides the possibility for its application in certain specific fields, such as as a fuel additive or an intermediate for the synthesis of other fine chemicals. The hydroxyl group in the molecule can undergo etherification reactions with other compounds to generate ether compounds. The etherification reaction can change its physical properties such as solubility and volatility, further expanding its application range. For example, compounds with higher boiling points and better solubility can be prepared through etherification reactions, which are used in the fields of coatings, adhesives, etc. Therefore, it is imperative to develop an environmentally friendly and economical method for preparing 2-furfural acetal. Summary of the invention
[0003] In order to solve the above technical problems, the present invention provides a method for preparing 2-furfural diethyl acetal. The cerium dioxide-supported metal catalyst is used to efficiently convert furfural into 2-furfural diethyl acetal chemicals. The method has the advantages of low cost, high efficiency, and large-scale promotion and application; the catalyst is relatively cheap, has excellent catalytic activity, and good catalytic stability.
[0004] The present invention adopts the following technical solutions:
[0005] A method for preparing 2-furfural acetal is obtained by the following steps: using furfural as a raw material and ethanol as a solvent, generating 2-furfural acetal under the action of a cerium dioxide-supported metal catalyst, the reaction temperature is room temperature to 100°C, the reaction time is 4-8 hours, and the nitrogen pressure in the reaction system is 0-4MPa; the molar ratio of the ethanol to the furfural is not less than 2:1, and the mass ratio of the raw material to the catalyst is 10:1-5:3. Room temperature means that the reaction does not require heating.
[0006] Wherein, the reaction temperature is room temperature ~ 60 ° C.
[0007] Wherein, the nitrogen pressure in the reaction system is 2~4MPa.
[0008] The metal in the cerium dioxide-loaded metal catalyst is one or two of Pt, Ce, Pd, Ni, Co, and Ru, the loading amount of the metal is no more than 2.0%, and the particle size of the metal in the cerium dioxide-loaded metal catalyst is nanometer-scale.
[0009] The method for preparing the cerium dioxide-supported metal catalyst comprises the following steps:
[0010] The metal salt, organic matter, cerium acetate and deionized water are fully mixed and uniformly mixed; after a certain reaction time, the mixture is dried; the amount of deionized water used is sufficient to dissolve various solutes;
[0011] The product obtained after drying is calcined in a N2 atmosphere for a certain period of time to obtain the cerium dioxide-supported metal catalyst.
[0012] Furthermore, the calcination temperature is 500-800°C, and the calcination time is 1-5h.
[0013] Furthermore, the metal salt is a transition metal salt; and the organic matter is oxalic acid and / or ethylenediaminetetraacetic acid.
[0014] Furthermore, the mass ratio of the metal salt, the organic matter and the cerium acetate is 1-3:1-3:6-8.
[0015] Furthermore, the metal loading in the ceria-supported metal catalyst is 0.1-1.0%;
[0016] and / or, the calcination temperature of the ceria-supported metal catalyst is 600-700° C.;
[0017] And / or, the metal in the ceria-supported metal catalyst is Pt or Co.
[0018] Furthermore, the raw material is furfural derived from lignocellulose, preferably furfural derived from waste tobacco biomass. With the increasing global attention to sustainable development and resource recycling, the effective utilization of waste tobacco biomass has become a research hotspot. A large amount of tobacco waste has not only caused waste of resources but also brought environmental pollution due to the lack of proper treatment. From the perspective of composition, waste tobacco biomass contains lignocellulose, which can be converted into furfural after treatment. After furfural is extracted, due to the active chemical properties of furfural, the molecule contains aldehyde groups and furan rings, it can undergo various reactions, and a series of high value-added products can be prepared through catalytic conversion.
[0019] Compared with the prior art, the present invention has the following beneficial effects:
[0020] (1) The cerium dioxide-supported platinum metal catalyst proposed in the present invention has abundant raw materials, low price, simple and convenient preparation, excellent catalytic effect, good stability, and can efficiently catalyze the conversion of furfural into 2-furfural diethyl acetal.
[0021] (2) The use of cerium dioxide-loaded metal catalysts has enabled the efficient conversion of furfural into 2-furfural diethyl acetal chemicals with a yield of up to 90%. This method has the advantages of low cost, high efficiency, and can be widely promoted and applied.
[0022] (3) The present invention uses furfural derived from lignocellulose to replace fossil raw materials to prepare 2-furfural diethyl acetal, which not only has the advantages of a wide source of raw materials and low production costs, but also can solve the pollution problem caused by agricultural and forestry wastes and realize the concept of green development and sustainable development. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 1 is the XRD diagram of the cerium dioxide supported platinum metal catalyst obtained in Example 1 and Example 6 to Example 10.
[0024] Figure 2 It is the XPS chart of the cerium dioxide supported platinum metal catalyst obtained in Example 1 and Example 6 to Example 10.
[0025] Figure 3 This is a scanning electron microscope image of the cerium dioxide-supported metal catalyst prepared in Example 1. DETAILED DESCRIPTION
[0026] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
[0027] Unless otherwise specified, the experimental materials and reagents used in the following examples can be obtained from commercial sources. If no specific conditions are specified, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer.
[0028] Example 1
[0029] In this example, a ceria-supported metal catalyst was prepared.
[0030] The preparation method is as follows:
[0031] Add 50 ml of deionized water, 0.5 g of oxalic acid, and 0.25 g of ethylenediaminetetraacetic acid into a beaker and stir at a stirring rate of 400 rpm. Keep at 70 °C for 0.5 h until fully dissolved. Then add 1.87 g of cerium acetate and continue stirring until fully dissolved. Then add chloroplatinic acid solvent and heat to 100 °C until the sample is completely dry. Heat the obtained solid powder to 700 °C in a N2 atmosphere and keep for 3 h to obtain a cerium dioxide-supported platinum metal catalyst.
[0032] In this embodiment, the loaded metal is Pt, and the loading amount is 1.0%.
[0033] Figure 3 is a scanning electron microscope image of the cerium dioxide supported platinum metal catalyst obtained in Example 1. Figure 1 It can be seen from the figure that metal platinum is loaded on ceria.
[0034] Example 2
[0035] The preparation process of this embodiment is the same as that of embodiment 1, except that the metal salt is a Pd salt.
[0036] Example 3
[0037] The preparation process of this embodiment is the same as that of embodiment 1, except that the metal salt is Ni salt.
[0038] Example 4
[0039] The preparation process of this embodiment is the same as that of embodiment 1, except that the metal salt is a Co salt.
[0040] Example 5
[0041] The preparation process of this embodiment is the same as that of embodiment 1, except that the metal salt is Ru salt.
[0042] Comparative Example 6
[0043] The preparation process of this embodiment is the same as that of embodiment 1, except that no metal salt is added.
[0044] Example 7
[0045] The preparation process of this embodiment is the same as that of embodiment 1, except that the loading amount of Pt is 0.1%.
[0046] Example 8
[0047] The preparation process of this embodiment is the same as that of embodiment 1, except that the loading amount of Pt is 0.5%.
[0048] Example 9
[0049] The preparation process of this embodiment is the same as that of embodiment 1, except that the loading amount of Pt is 1.5%.
[0050] Example 10
[0051] The preparation process of this embodiment is the same as that of embodiment 1, except that the loading amount of Pt is 2.0%.
[0052] The XRD patterns of the catalysts obtained in Example 1 and Example 6 to Example 10 are as follows: Figure 1 As shown, from Figure 1 It can be seen that the (111), (200), (220), (311), (222), (400), (331) and (420) faces of CeO2 indicate the presence of cubic fluorite oxide CeO2. The characteristic peak of Pt (39.8° shoulder peak) is difficult to observe in all catalysts, which is mainly due to the low content, small particle size and high dispersion of Pt, forming small nano-sized particles.
[0053] Figure 2 is the XPS graph of the catalyst obtained in Example 1 and Example 6 to Example 10. Table 0 is based on Figure 2 Calculated element contents.
[0054] Table 0
[0055] Embodiment 11
[0056] The preparation process of this embodiment is the same as that of embodiment 1, except that the calcination temperature is 500°C.
[0057] Example 12
[0058] The preparation process of this embodiment is the same as that of embodiment 1, except that the calcination temperature is 600°C.
[0059] Example 13
[0060] The preparation process of this embodiment is the same as that of embodiment 1, except that the calcination temperature is 800°C.
[0061] Embodiment 14
[0062] The preparation process of this embodiment is the same as that of Embodiment 1, except that the mass ratio of platinum salt: organic matter: cerium acetate is 1:1:7.
[0063] Embodiment 15
[0064] The preparation process of this embodiment is the same as that of embodiment 1, except that the mass ratio of platinum salt: organic matter: cerium acetate is 1:3:7.
[0065] Example 16
[0066] The preparation process of this embodiment is the same as that of embodiment 1, except that the mass ratio of platinum salt: organic matter: cerium acetate is 1:2:6.
[0067] Embodiment 17
[0068] The preparation process of this embodiment is the same as that of embodiment 1, except that the mass ratio of platinum salt: organic matter: cerium acetate is 1:2:8.
[0069] Embodiment 18
[0070] The preparation process of this embodiment is the same as that of embodiment 1, except that the mass ratio of platinum salt: organic matter: cerium acetate is 2:2:7.
[0071] Embodiment 19
[0072] The preparation process of this embodiment is the same as that of embodiment 1, except that the mass ratio of platinum salt: organic matter: cerium acetate is 3:2:7.
[0073] Embodiment 20
[0074] In this example, cerium dioxide-supported metal catalyst was used to prepare 2-furfural diethyl acetal.
[0075] The specific preparation process is as follows:
[0076] 0.005 g of the cerium dioxide-supported metal catalyst prepared above, 0.05 g of furfural extracted from waste tobacco, and 5.0 ml of ethanol were placed in a 20 ml high-pressure reactor, the reactor was sealed, the gas in the reactor was replaced with N2 three times, the pressure was increased to 4 MPa with N2, the stirring paddle was turned on (800 rpm), the reaction was carried out at room temperature, and the timing reaction was started. The reaction time was 6 h, and 2-furfural diethyl acetal was prepared.
[0077] The reaction equation is:
[0078] .
[0079] Examples 21 to 25 respectively use the catalysts prepared in Examples 2 to 6, and other parameters are the same as in Example 20. The yield of the obtained product 2-furfural diethyl acetal is shown in Table 1:
[0080] Table 1
[0081] As can be seen from Table 1, when the metal in the ceria-supported metal catalyst is Pt, Co, Pd, Ru, or Ni, the product yield can be improved relative to the catalyst without metal loading. However, the preferred metals are Pt and Co, because the catalyst loaded with Pt or Co has good electron transfer ability and appropriate catalytic ability, and thus exhibits the best performance in catalyzing the selective conversion of furfural into 2-furfural diethyl acetal.
[0082] Examples 26 to 29 respectively use the catalysts prepared in Examples 7 to 10, and other parameters are the same as in Example 20. The yield of the obtained product 2-furfural diethyl acetal is shown in Table 2:
[0083] Table 2
[0084] It can be seen from Table 2 that the loading amount of the ceria-supported metal catalyst in the present invention has a relatively small effect on the catalytic performance of the catalyst, and a catalyst with a loading amount of 0.1-1.0% is preferred.
[0085] The XPS patterns of the catalysts obtained with different Pt loadings of 0.1%, 0.5%, 1.0%, 1.5% and 2.0% are shown in Figure 2. Figure 2 The calculation results are shown in Table 0. Figure 2 From Table 0, the inventors believe that when the content of oxygen vacancies is greater than 30% (preferably 37.1% to 47.3%), the catalytic effect on furfural is best.
[0086] Examples 30 to 32 respectively use the catalysts prepared in Examples 11 to 13, and other parameters are the same as in Example 20. The yield of the obtained product 2-furfural diethyl acetal is shown in Table 3:
[0087] Table 3
[0088] As can be seen from Table 3, the calcination temperature in the preparation process of the ceria-supported metal catalyst of the present invention has a great influence on the catalytic performance of the catalyst, and should not be too high or too low. At 700°C, platinum atoms can better embed into the lattice defects or surface active sites of ceria to form stable and efficient active centers. It also helps the platinum particles to be evenly dispersed on the surface of the ceria carrier to form platinum nanoparticles of moderate size and uniform distribution. In this way, platinum can fully expose its active sites, fully contact with the reactants, and improve the catalytic efficiency. The preferred calcination temperature is 600-700°C.
[0089] Examples 33 to 36 all use the catalyst prepared in Example 1, except that the nitrogen pressure in the preparation process in Example 20 is adjusted, and other parameters are the same as in Example 20. The obtained product yields are shown in Table 4:
[0090] Table 4
[0091] As can be seen from Table 4, during the preparation of 2-furfural diethyl acetal, the influence of nitrogen pressure is small. The preferred nitrogen pressure is 4 MPa.
[0092] Examples 37 to 40 all use the catalyst prepared in Example 1, except that the temperature in the preparation process in Example 20 is adjusted, and other parameters are the same as in Example 20. The obtained product yields are shown in Table 5:
[0093] Table 5
[0094] As can be seen from Table 5, the reaction temperature has a great influence on the preparation process of 2-furfural diethyl acetal, and the reaction temperature should not be too high. When the temperature is low, the active sites of the Pt / CeO2 catalyst are in a relatively stable and efficient state, which can adsorb and activate furfural and ethanol molecules well and promote the reaction. However, as the temperature rises, the active sites of the catalyst may change. For example, high temperature causes the metal atoms on the active sites to aggregate and the structure of the catalyst carrier to change, thereby reducing the activity of the catalyst. Preferably, the reaction temperature does not exceed 60°C, and more preferably the reaction temperature is room temperature to 40°C.
[0095] Examples 41 to 46 all use the catalyst prepared in Example 1, except that the amount of the catalyst in Example 20 is adjusted. Other parameters are the same as in Example 20. The obtained product yields are shown in Table 6:
[0096] Table 6
[0097] As can be seen from Table 6, the amount of catalyst used in the preparation process of 2-furfural acetal has a greater impact on it. The reaction is a reversible reaction. When the ratio of furfural to catalyst is 10:1, under certain reaction conditions, the forward reaction rate and the reverse reaction rate can reach a relatively suitable equilibrium state, which is conducive to the reaction in the direction of generating 2-furfural acetal and improving the yield of the product. If the amount of catalyst deviates from this ratio, this balance may be broken, so that the reaction reaches equilibrium too early but the product yield is not ideal, or the reaction rate is too fast but the equilibrium conversion rate is not high. The preferred raw material furfural and catalyst usage ratio is 10:1.
[0098] Examples 47 to 52 respectively use the catalysts prepared in Examples 1 and Examples 6 to 10, and at the same time adjust the nitrogen pressure in Example 20 to 0. The other parameters are the same as in Example 20. The obtained product yields are shown in Table 7:
[0099] Table 7
[0100] It can be seen from Table 7 that even without nitrogen, the cerium dioxide supported platinum metal catalyst can still achieve catalysis due to its good electron transfer ability and appropriate catalytic ability. Combined with Table 4, the inventors believe that increasing the reaction pressure can improve the catalytic ability of the catalyst.
[0101] Examples 53 to 56 all use the catalyst prepared in Example 6, and the nitrogen pressure in Example 20 is adjusted. Other parameters are the same as in Example 20. The obtained product yields are shown in Table 8:
[0102] Table 8
[0103] It can be seen from Table 8 that if the catalyst is not loaded with metal, the yield is still very low even if 4 MPa is charged during the preparation process.
[0104] Examples 57 to 56 all use the catalysts prepared in Examples 14 to 19, and the reaction time is adjusted to 8 hours; other parameters are the same as in Example 20, and the obtained product yields are shown in Table 9:
[0105] Table 9
[0106] It will be easily understood by those skilled in the art that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.
[0107] The parts not described in detail in the present description belong to the known technology in the art. The above embodiments are provided only for the purpose of describing the present invention, but not to limit the scope of the present invention. The scope of the present invention is defined by the appended claims. Various equivalent substitutions and modifications made without departing from the spirit and principle of the present invention should be included in the scope of the present invention.
Claims
1. A method for preparing 2-furfural diethyl acetal, characterized in that: The method is obtained by the following steps: using furfural as a raw material and ethanol as a solvent, generating 2-furfural acetal under the action of a cerium dioxide-supported metal catalyst, the reaction temperature is room temperature to 100°C, the reaction time is 4 to 8 hours, and the nitrogen pressure in the reaction system is 0 to 4MPa; the molar ratio of the ethanol to the furfural is not less than 2:1, and the mass ratio of the raw material to the catalyst is 10:1 to 5:
3.
2. The preparation method according to claim 1, characterized in that: The reaction temperature is room temperature to 60°C.
3. The preparation method according to claim 1, characterized in that: The nitrogen pressure in the reaction system is 2-4 MPa.
4. The preparation method according to claim 1, characterized in that: The metal in the ceria-loaded metal catalyst is one or two of Pt, Ce, Pd, Ni, Co, and Ru, the loading amount of the metal is not more than 2.0%, and the particle size of the metal in the ceria-loaded metal catalyst is nanometer-scale.
5. The preparation method according to claim 4, characterized in that: The preparation method of the ceria-supported metal catalyst comprises the following steps: The metal salt, organic matter, cerium acetate and deionized water are fully mixed and dried after reacting for a certain period of time; The product obtained after drying is calcined in a N2 atmosphere for a certain period of time to obtain the cerium dioxide-supported metal catalyst.
6. The preparation method according to claim 5, characterized in that: The calcination temperature is 500~800 ℃ and the calcination time is 1-5h.
7. The preparation method according to claim 5, characterized in that: The metal salt is a transition metal salt; the organic matter is oxalic acid and / or ethylenediaminetetraacetic acid.
8. The preparation method according to claim 5, characterized in that: The mass ratio of the metal salt, the organic matter and the cerium acetate is 1-3:1-3:6-8.
9. The preparation method according to claim 4, characterized in that: The metal loading amount in the ceria-supported metal catalyst is 0.1-1.0%; and / or, the calcination temperature of the ceria-supported metal catalyst is 600-700° C.; And / or, the metal in the ceria-supported metal catalyst is Pt or Co.
10. The preparation method according to claim 1, characterized in that: The raw material is furfural derived from lignocellulose.