Method for synthesizing tetrahydrofurfuryl alcohol by hydrogenation catalysis of furfural
By using a composite catalyst composed of metal phosphate and nickel element, catalyzed hydrogenation of furfural under low pressure and mild conditions, the problems of high cost, low selectivity and harsh reaction conditions in the prior art are solved, and a low-cost and efficient furfural conversion process is achieved.
Patent Information
- Application Number
- CN202510775392.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-11
- Publication Date
- 2025-08-19
AI Technical Summary
In the prior art, the process of producing tetrahydrofurfurfurfurol of furfurfurfurol has high cost, low selectivity, harsh reaction conditions (high temperature and high pressure) and special solvent requirements, which hinder its large-scale application.
Tetrahydrofurfuryl alcohol is prepared by using a composite catalyst composed of metal phosphate and nickel element to catalyze the hydrogenation of furfural under low pressure and mild conditions, and the reaction efficiency is improved by regulating the acidity and alkalinity of the catalyst.
It realizes a low-cost, high-selectivity and high-efficiency process for converting furfural into tetrahydrofurfurfurol, which is suitable for industrial and large-scale production, with low catalyst costs and stable structure.
Smart Images
Figure CN120504647A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of biomass fine chemical industry, and more particularly relates to a method for synthesizing tetrahydrofurfuryl alcohol by hydrogenating catalytic furfural. Background Art
[0002] Today's chemical production mostly relies on fossil resources such as oil, natural gas, and coal. The depletion of these resources and the harmful effects of refining and using these resources, such as environmental pollution and the greenhouse effect, are becoming increasingly serious. Biomass materials are considered to be "zero-carbon" resources throughout their life cycle. Lignocellulosic biomass is a complex polymer network composed of three components: cellulose, hemicellulose, and lignin. These components can be chemically or catalytically converted into many useful downstream platform chemicals, which can be further used to produce valuable chemicals, fuels, and materials. Among them, the catalytic conversion of hemicellulose-derived furfural has attracted widespread attention due to its wide application in the production of solvents and pharmaceutical intermediates.
[0003] Furfural, a platform molecule, can be converted into a variety of important chemicals, including furfuryl alcohol, tetrahydrofurfuryl alcohol, and cyclopentanone. These chemicals have significant potential applications in the production of solvents, polymers, biofuels, and pharmaceutical intermediates. While numerous studies have been conducted on the hydrogenation of furfural to tetrahydrofurfuryl alcohol, several process bottlenecks have hindered the large-scale or industrial application of these reactions. These include: 1) Current research focuses on precious metal catalysts, which are expensive and hinder practical application; 2) low selectivity for single alcohols; 3) the reaction requires high temperatures and pressures, particularly hydrogenation, where hydrogen pressures typically must be maintained above 2.0 MPa, making operation difficult and posing significant safety risks; and 4) some reactions have specific solvent requirements, particularly when using water or simple alcohols, resulting in suboptimal reaction efficiency. Summary of the Invention
[0004] The present invention aims to provide a method for synthesizing tetrahydrofurfuryl alcohol from furfural by hydrogenation catalysis, so as to solve the problems existing in the above-mentioned prior art and provide a method for synthesizing tetrahydrofurfuryl alcohol from furfural by hydrogenation catalysis, which has low cost, mild reaction conditions, high selectivity and high reaction efficiency.
[0005] To achieve the above object, the present invention provides the following solutions:
[0006] One of the technical solutions of the present invention is to provide a method for preparing tetrahydrofurfuryl alcohol by catalytic hydrogenation of furfural, comprising the following steps: adding a hydrogenation catalyst to a furfural solution, and heating the solution under a hydrogen atmosphere to react to obtain tetrahydrofurfuryl alcohol.
[0007] Preferably, the concentration of the furfural solution is 0.05 to 0.6 mol / L, more preferably 0.1 mol / L.
[0008] Preferably, the usage ratio of the hydrogenation catalyst to the furfural solution is 5-15 mg:1-2 mL, more preferably 5 mg:1 mL.
[0009] Preferably, the heating reaction is carried out at a pressure of 0.1-2 MPa, a temperature of 120-180° C., and a time of 3-6 h, more preferably at a pressure of 1 MPa, a temperature of 150° C., and a time of 4 h.
[0010] Increasing the hydrogen pressure and reaction temperature can accelerate the reaction rate, but too high a hydrogen pressure and reaction temperature will lead to an increase in by-products, thereby reducing the yield of tetrahydrofurfuryl alcohol.
[0011] Preferably, the hydrogenation catalyst is a composite of metal phosphate and nickel.
[0012] Preferably, the mass fraction of nickel in the hydrogenation catalyst is 0.5 to 20%, more preferably 10%.
[0013] Preferably, in the hydrogenation catalyst, the metal elements in the metal phosphate include two of lanthanum, cerium, praseodymium, samarium, gadolinium, dysprosium, yttrium, lithium, magnesium and aluminum.
[0014] Preferably, the preparation step of the hydrogenation catalyst comprises:
[0015] The nitrate is dissolved in water, and then an aqueous solution of diammonium hydrogen phosphate is added to separate the obtained precipitate; the precipitate and a nickel source are dispersed in water, and then an alkali solution is added, and the obtained precipitate is subjected to a reduction heat treatment under a hydrogen atmosphere to obtain the hydrogenation catalyst.
[0016] Preferably, the nickel source includes nickel nitrate; the alkali solution includes one or more of potassium hydroxide, sodium hydroxide and ammonia water; the concentration of the alkali solution is 0.5-3 mol / L; and the temperature of the reduction heat treatment is 400-600°C.
[0017] The present invention uses a composite of metal phosphate and nickel as a hydrogenation catalyst to catalyze the hydrogenation of furfural to prepare tetrahydrofurfuryl alcohol. The principle is that nickel has the function of activating the substrate furfural, but its own activity in the hydrogenation reaction is relatively low because it does not strongly activate hydrogen. At the same time, it is found that metal phosphate has a significant activation effect on hydrogen, and the mutual doping of different metal phosphates has a modulating effect on the acidity and alkalinity of the catalyst, which is also the key to achieving efficient conversion of biomass platform molecules such as furfural. Therefore, after the two components are combined, the conversion efficiency of the furfural hydrogenation conversion reaction, especially under low-pressure hydrogen, is significantly improved, and is even comparable to the performance of traditional precious metal catalysts.
[0018] The present invention discloses the following technical effects:
[0019] The present invention utilizes a composite catalyst composed of an inexpensive, stable, and non-toxic metal phosphate and nickel to catalyze the hydrogenation of aldehydes to produce tetrahydrofurfuryl alcohol. By doping different metal phosphates, the acidity and alkalinity of the hydrogenation catalyst are regulated, enabling efficient conversion of furfural under low pressure and mild reaction conditions. This also improves the yield of tetrahydrofurfuryl alcohol, thus achieving a new process for efficient furfural conversion under green, mild, and safe reaction conditions using an inexpensive, stable, and non-toxic catalyst. This process is readily industrializable and suitable for large-scale production. Compared to existing processes, the present invention features a low catalyst cost, a tightly bound metal phosphate, and uniformly distributed nickel particles on the metal phosphate, resulting in high activity and structural stability in applications. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Figure 1 1 is the XRD pattern of the hydrogenation catalysts obtained in Example 1, Example 5 and Example 6;
[0021] Figure 2 These are SEM images of the hydrogenation catalysts obtained in Example 1, Example 5, and Example 6, where a is Example 1, b is Example 5, and c is Example 6. DETAILED DESCRIPTION
[0022] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.
[0023] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. The intermediate value within any stated value or stated range, and each smaller range between any other stated value or intermediate value within the stated range, is also encompassed within the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.
[0024] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.
[0025] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be illustrative only.
[0026] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.
[0027] It should be pointed out that the matters not described in detail in the present invention are conventional operating means in this field and are not the focus of the present invention.
[0028] Unless otherwise specified, the raw materials used in the following examples and comparative examples of the present invention are all commercially available products, and the sources of the commercially available products do not affect the technical effects of the present invention.
[0029] Example 1
[0030] Preparation of a hydrogenation catalyst: Aluminum nitrate and samarium nitrate are co-dissolved in water at a molar ratio of 1:0.5 to obtain a mixed solution with a concentration of 0.2 mol / L. A 0.2 mol / L aqueous solution of diammonium hydrogen phosphate is added to the mixed solution (the volume ratio of the mixed solution to the aqueous solution of diammonium hydrogen phosphate is 1:1). The resulting precipitate is separated and dried. The precipitate and nickel nitrate are then dispersed in water to obtain a mixed solution, which is mixed with a 1 mol / L sodium hydroxide solution to obtain a precipitate (the volume ratio of the mixed solution to the sodium hydroxide solution is 1:0.05). The precipitate is reduced at 400°C for 240 minutes to obtain a hydrogenation catalyst (wherein the mass fraction of nickel is 10%).
[0031] Preparation of tetrahydrofurfuryl alcohol: 20 mL of a 0.1 mol / L furfural isopropanol solution was added to a 100 mL pressure reactor, followed by the addition of 100 mg of the prepared hydrogenation catalyst. After the pressure reactor was sealed, the air inside the reactor was replaced with nitrogen, and then with hydrogen five times. The internal hydrogen pressure was maintained at 1 MPa, the reaction temperature was set at 130°C, the rotation speed was 350 r / min, and the reaction time was 4 h. After 4 h, the reaction liquid was subjected to gas chromatography quantitative detection.
[0032] Example 2
[0033] Preparation of a hydrogenation catalyst: Aluminum nitrate and samarium nitrate are co-dissolved in water at a molar ratio of 1:0.5 to obtain a mixed solution with a concentration of 0.2 mol / L. A 0.2 mol / L aqueous solution of diammonium hydrogen phosphate is added to the mixed solution (the volume ratio of the mixed solution to the aqueous solution of diammonium hydrogen phosphate is 1:1). The resulting precipitate is separated and dried. The precipitate and nickel nitrate are then dispersed in water to obtain a mixed solution, which is mixed with a 1 mol / L sodium hydroxide solution to obtain a precipitate (the volume ratio of the mixed solution to the sodium hydroxide solution is 1:0.05). The precipitate is reduced at 400°C for 240 minutes to obtain a hydrogenation catalyst (wherein the mass fraction of nickel is 10%).
[0034] Preparation of tetrahydrofurfuryl alcohol: 20 mL of a 0.1 mol / L furfural isopropanol solution was added to a 100 mL pressure reactor, followed by the addition of 100 mg of the prepared hydrogenation catalyst. After the pressure reactor was sealed, the air inside the reactor was replaced with nitrogen, and then with hydrogen five times. The internal hydrogen pressure was maintained at 1 MPa, the reaction temperature was set at 150°C, the rotation speed was 350 r / min, and the reaction time was 4 h. After 4 h, the reaction liquid was subjected to gas chromatography quantitative detection.
[0035] Example 3
[0036] Preparation of a hydrogenation catalyst: Aluminum nitrate and samarium nitrate are co-dissolved in water at a molar ratio of 1:1 to obtain a mixed solution with a concentration of 0.2 mol / L. A 0.2 mol / L aqueous diammonium hydrogen phosphate solution is added to the mixed solution (the volume ratio of the mixed solution to the diammonium hydrogen phosphate solution is 1:1). The resulting precipitate is separated and dried. The precipitate and nickel nitrate are then dispersed in water to obtain a mixed solution, which is mixed with a 1 mol / L sodium hydroxide solution to obtain a precipitate (the volume ratio of the mixed solution to the sodium hydroxide solution is 1:0.05). The precipitate is reduced at 400°C for 240 minutes to obtain a hydrogenation catalyst (wherein the mass fraction of nickel is 10%).
[0037] Preparation of tetrahydrofurfuryl alcohol: 20 mL of a 0.1 mol / L furfural isopropanol solution was added to a 100 mL pressure reactor, followed by the addition of 100 mg of the prepared hydrogenation catalyst. After the pressure reactor was sealed, the air inside the reactor was replaced with nitrogen, and then with hydrogen five times. The internal hydrogen pressure was maintained at 1 MPa, the reaction temperature was set at 130°C, the rotation speed was 350 r / min, and the reaction time was 4 h. After 4 h, the reaction liquid was subjected to gas chromatography quantitative detection.
[0038] Example 4
[0039] Preparation of a hydrogenation catalyst: Aluminum nitrate and samarium nitrate are co-dissolved in water at a molar ratio of 1:1 to obtain a mixed solution with a concentration of 0.2 mol / L. A 0.2 mol / L aqueous diammonium hydrogen phosphate solution is added to the mixed solution (the volume ratio of the mixed solution to the diammonium hydrogen phosphate solution is 1:1). The resulting precipitate is separated and dried. The precipitate and nickel nitrate are then dispersed in water to obtain a mixed solution, which is mixed with a 1 mol / L sodium hydroxide solution to obtain a precipitate (the volume ratio of the mixed solution to the sodium hydroxide solution is 1:0.05). The precipitate is reduced at 400°C for 240 minutes to obtain a hydrogenation catalyst (wherein the mass fraction of nickel is 10%).
[0040] Preparation of tetrahydrofurfuryl alcohol: 20 mL of a 0.1 mol / L furfural isopropanol solution was added to a 100 mL pressure reactor, followed by the addition of 100 mg of the prepared hydrogenation catalyst. After the pressure reactor was sealed, the air inside the reactor was replaced with nitrogen, and then with hydrogen five times. The internal hydrogen pressure was maintained at 1 MPa, the reaction temperature was set at 150°C, the rotation speed was 350 r / min, and the reaction time was 4 h. After 4 h, the reaction liquid was subjected to gas chromatography quantitative detection.
[0041] Example 5
[0042] Preparation of a hydrogenation catalyst: Samarium nitrate is dissolved in water to obtain a mixed solution with a concentration of 0.2 mol / L, a 0.2 mol / L aqueous diammonium hydrogen phosphate solution is added to the mixed solution (the volume ratio of the mixed solution to the diammonium hydrogen phosphate solution is 1:1), and the resulting precipitate is separated and dried; the precipitate and nickel nitrate are then dispersed in water to obtain a mixed solution, which is mixed with a 1 mol / L sodium hydroxide solution to obtain a precipitate (the volume ratio of the mixed solution to the sodium hydroxide solution is 1:0.05), and the precipitate is reduced at 400°C for 240 minutes to obtain a hydrogenation catalyst (wherein the mass fraction of nickel is 10%).
[0043] Preparation of tetrahydrofurfuryl alcohol: 20 mL of a 0.1 mol / L furfural isopropanol solution was added to a 100 mL pressure reactor, followed by the addition of 100 mg of the prepared hydrogenation catalyst. After the pressure reactor was sealed, the air inside the reactor was replaced with nitrogen, and then with hydrogen five times. The internal hydrogen pressure was maintained at 1 MPa, the reaction temperature was set at 150°C, the rotation speed was 350 r / min, and the reaction time was 4 h. After 4 h, the reaction liquid was subjected to gas chromatography quantitative detection.
[0044] Example 6
[0045] Preparation of a hydrogenation catalyst: Aluminum nitrate is dissolved in water to obtain a mixed solution with a concentration of 0.2 mol / L, a diammonium hydrogen phosphate aqueous solution with a concentration of 0.2 mol / L is added to the mixed solution (the volume ratio of the mixed solution to the diammonium hydrogen phosphate aqueous solution is 1:1), and the obtained precipitate is separated and dried; then the precipitate and nickel nitrate are dispersed in water to obtain a mixed solution, which is mixed with a 1 mol / L sodium hydroxide solution to obtain a precipitate (the volume ratio of the mixed solution to the sodium hydroxide solution is 1:0.05), and the precipitate is reduced at 400°C for 240 minutes to obtain a hydrogenation catalyst (wherein the mass fraction of nickel is 10%).
[0046] Preparation of tetrahydrofurfuryl alcohol: 20 mL of a 0.1 mol / L furfural isopropanol solution was added to a 100 mL pressure reactor, followed by the addition of 100 mg of the prepared hydrogenation catalyst. After the pressure reactor was sealed, the air inside the reactor was replaced with nitrogen, and then with hydrogen five times. The internal hydrogen pressure was maintained at 1 MPa, the reaction temperature was set at 150°C, the rotation speed was 350 r / min, and the reaction time was 4 h. After 4 h, the reaction liquid was subjected to gas chromatography quantitative detection.
[0047] Figure 1 1 is the XRD pattern of the hydrogenation catalysts obtained in Example 1, Example 5 and Example 6; Figure 2 These are SEM images of the hydrogenation catalysts obtained in Example 1, Example 5, and Example 6, where a is Example 1, b is Example 5, and c is Example 6.
[0048] Depend on Figure 1 and Figure 2 It can be seen that the Ni / (Al-Sm 0.5 )PO4, Ni / SmPO4 obtained in Example 5, and Ni / AlPO4 obtained in Example 6 all correspond to their respective PDF cards. The XRD patterns of the composite material described in Example 1 all exhibit characteristic peaks of aluminum phosphate and samarium phosphate. The XRD pattern of the composite material described in Example 5 exhibits a characteristic peak of samarium phosphate, and the XRD pattern of the composite material described in Example 6 exhibits a characteristic peak of aluminum phosphate, indicating the successful synthesis of the aforementioned composite materials. However, no characteristic peak of nickel was observed in the XRD pattern of the composite material described in Example 1, indicating that nickel is uniformly distributed throughout the composite metal phosphate.
[0049] Example 7
[0050] Preparation of a hydrogenation catalyst: Lanthanum nitrate is dissolved in water to obtain a mixed solution with a concentration of 0.2 mol / L, a 0.2 mol / L diammonium hydrogen phosphate aqueous solution is added to the mixed solution (the volume ratio of the mixed solution to the diammonium hydrogen phosphate aqueous solution is 1:1), and the obtained precipitate is separated and dried; then the precipitate and nickel nitrate are dispersed in water to obtain a mixed solution, which is mixed with a 1 mol / L sodium hydroxide solution to obtain a precipitate (the volume ratio of the mixed solution to the sodium hydroxide solution is 1:0.05), and the precipitate is reduced at 400°C for 240 minutes to obtain a hydrogenation catalyst (wherein the mass fraction of nickel is 10%).
[0051] Preparation of tetrahydrofurfuryl alcohol: 20 mL of a 0.1 mol / L furfural isopropanol solution was added to a 100 mL pressure reactor, followed by the addition of 100 mg of the prepared hydrogenation catalyst. After the pressure reactor was sealed, the air inside the reactor was replaced with nitrogen, and then with hydrogen five times. The internal hydrogen pressure was maintained at 1 MPa, the reaction temperature was set at 150°C, the rotation speed was 350 r / min, and the reaction time was 4 h. After 4 h, the reaction liquid was subjected to gas chromatography quantitative detection.
[0052] Example 8
[0053] Preparation of a hydrogenation catalyst: Cerium nitrate is dissolved in water to obtain a mixed solution with a concentration of 0.2 mol / L, a 0.2 mol / L diammonium hydrogen phosphate aqueous solution is added to the mixed solution (the volume ratio of the mixed solution to the diammonium hydrogen phosphate aqueous solution is 1:1), and the obtained precipitate is separated and dried; the precipitate and nickel nitrate are then dispersed in water to obtain a mixed solution, which is mixed with a 1 mol / L sodium hydroxide solution to obtain a precipitate (the volume ratio of the mixed solution to the sodium hydroxide solution is 1:0.05), and the precipitate is reduced at 400°C for 240 minutes to obtain a hydrogenation catalyst (wherein the mass fraction of nickel is 10%).
[0054] Preparation of tetrahydrofurfuryl alcohol: 20 mL of a 0.1 mol / L furfural isopropanol solution was added to a 100 mL pressure reactor, followed by the addition of 100 mg of the prepared hydrogenation catalyst. After the pressure reactor was sealed, the air inside the reactor was replaced with nitrogen, and then with hydrogen five times. The internal hydrogen pressure was maintained at 2 MPa, the reaction temperature was set at 150°C, the rotation speed was 350 r / min, and the reaction time was 4 h. After 4 h, the reaction liquid was subjected to gas chromatography quantitative detection.
[0055] Example 9
[0056] Preparation of a hydrogenation catalyst: Nickel nitrate and silicon dioxide were dispersed in water, mixed with a 1 mol / L sodium hydroxide solution to obtain a precipitate (the volume ratio of the mixed solution to the sodium hydroxide solution was 1:0.05), and the precipitate was reduced at 400°C for 240 min to obtain a hydrogenation catalyst (wherein the mass fraction of nickel was 10%).
[0057] Preparation of tetrahydrofurfuryl alcohol: 20 mL of a 0.1 mol / L furfural isopropanol solution was added to a 100 mL pressure reactor, followed by the addition of 100 mg of the prepared hydrogenation catalyst. After the pressure reactor was sealed, the air inside the reactor was replaced with nitrogen, and then with hydrogen five times. The internal hydrogen pressure was maintained at 1 MPa, the reaction temperature was set at 150°C, the rotation speed was 350 r / min, and the reaction time was 4 h. After 4 h, the reaction liquid was subjected to gas chromatography quantitative detection.
[0058] Example 10
[0059] Preparation of hydrogenation catalyst: Chloropaldic acid and silica were dispersed in water, ultrasonically vibrated for 15 minutes, immersed in the sample for 24 hours, dried at 100°C for 12 hours, and the precipitate was reduced with hydrogen at 400°C for 240 minutes to obtain a hydrogenation catalyst (wherein the mass fraction of palladium was 0.5%).
[0060] Preparation of tetrahydrofurfuryl alcohol: 20 mL of a 0.1 mol / L furfural isopropanol solution was added to a 100 mL pressure reactor, followed by the addition of 100 mg of the prepared hydrogenation catalyst. After the pressure reactor was sealed, the air inside the reactor was replaced with nitrogen, and then with hydrogen five times. The internal hydrogen pressure was maintained at 3 MPa, the reaction temperature was set at 130°C, the rotation speed was 350 r / min, and the reaction time was 5 h. After 5 h, the reaction liquid was subjected to gas chromatography quantitative detection.
[0061] Example 11
[0062] Preparation of a hydrogenation catalyst: Aluminum nitrate and samarium nitrate are co-dissolved in water at a molar ratio of 1:0.5 to obtain a mixed solution with a concentration of 0.2 mol / L. A 0.2 mol / L aqueous solution of diammonium hydrogen phosphate is added to the mixed solution (the volume ratio of the mixed solution to the aqueous solution of diammonium hydrogen phosphate is 1:1). The resulting precipitate is separated and dried. The precipitate and nickel nitrate are then dispersed in water to obtain a mixed solution, which is mixed with a 1 mol / L sodium hydroxide solution to obtain a precipitate (the volume ratio of the mixed solution to the sodium hydroxide solution is 1:0.05). The precipitate is reduced at 400°C for 240 minutes to obtain a hydrogenation catalyst (wherein the mass fraction of nickel is 10%).
[0063] Preparation of tetrahydrofurfuryl alcohol: 20 mL of a 0.1 mol / L furfural isopropanol solution was added to a 100 mL pressure reactor, followed by the addition of 100 mg of the prepared hydrogenation catalyst. After the pressure reactor was sealed, the air inside the reactor was replaced with nitrogen, and then with hydrogen five times. The internal hydrogen pressure was maintained at 2 MPa, the reaction temperature was set at 150°C, the rotation speed was 350 r / min, and the reaction time was 4 h. After 4 h, the reaction liquid was subjected to gas chromatography quantitative detection.
[0064] Example 12
[0065] Preparation of a hydrogenation catalyst: Aluminum nitrate and samarium nitrate are co-dissolved in water at a molar ratio of 1:0.5 to obtain a mixed solution with a concentration of 0.2 mol / L. A 0.2 mol / L aqueous solution of diammonium hydrogen phosphate is added to the mixed solution (the volume ratio of the mixed solution to the aqueous solution of diammonium hydrogen phosphate is 1:1). The resulting precipitate is separated and dried. The precipitate and nickel nitrate are then dispersed in water to obtain a mixed solution, which is mixed with a 1 mol / L sodium hydroxide solution to obtain a precipitate (the volume ratio of the mixed solution to the sodium hydroxide solution is 1:0.05). The precipitate is reduced at 400°C for 240 minutes to obtain a hydrogenation catalyst (wherein the mass fraction of nickel is 10%).
[0066] Preparation of tetrahydrofurfuryl alcohol: 20 mL of a 0.1 mol / L furfural isopropanol solution was added to a 100 mL pressure reactor, followed by the addition of 100 mg of the prepared hydrogenation catalyst. After the pressure reactor was sealed, the air inside the reactor was replaced with nitrogen, and then with hydrogen five times. The internal hydrogen pressure was maintained at 2 MPa, the reaction temperature was set at 150°C, the rotation speed was 350 r / min, the reaction time was 2 h, and after 4 h, the reaction liquid was subjected to gas chromatography quantitative detection.
[0067] The gas chromatography quantitative detection results of the above embodiments and comparative examples are shown in Table 1.
[0068] Table 1 Gas chromatography quantitative detection results of each embodiment and comparative example
[0069]
[0070]
[0071] As shown in Table 1, the two-metal composite hydrogenation catalyst exhibits superior catalytic performance compared to single-metal doped hydrogenation catalysts. It can also achieve higher tetrahydrofurfuryl alcohol yields at lower hydrogen pressures compared to conventional hydrogenation catalysts.
[0072] The various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referenced to each other.
[0073] The above description of the disclosed embodiments is intended to enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is intended to conform to the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A method for preparing tetrahydrofurfuryl alcohol by catalytic hydrogenation of furfural, characterized in that: The following steps are involved: A hydrogenation catalyst is added to the furfural solution, and the solution is heated to react in a hydrogen atmosphere to obtain tetrahydrofurfuryl alcohol.
2. The method according to claim 1, characterized in that The concentration of the furfural solution is 0.05-0.6 mol / L.
3. The method according to claim 1, characterized in that The usage ratio of the hydrogenation catalyst and the furfural solution is 5-15 mg:1-2 mL.
4. The method according to claim 1, wherein The heating reaction is carried out at a pressure of 0.1 to 2 MPa, a temperature of 120 to 180° C., and a time of 3 to 6 hours.
5. The method according to claim 1, wherein The hydrogenation catalyst is a composite composed of metal phosphate and nickel.
6. The method according to claim 5, characterized in that In the hydrogenation catalyst, the mass fraction of nickel is 0.5-20%.
7. The method according to claim 5, characterized in that In the hydrogenation catalyst, the metal elements in the metal phosphate include two of lanthanum, cerium, praseodymium, samarium, gadolinium, dysprosium, yttrium, lithium, magnesium and aluminum.
8. The method according to claim 5, characterized in that The preparation steps of the hydrogenation catalyst include: The nitrate is dissolved in water, and then an aqueous solution of diammonium hydrogen phosphate is added to separate the obtained precipitate; the precipitate and a nickel source are dispersed in water, and then an alkali solution is added to perform a reduction heat treatment on the obtained precipitate under a hydrogen atmosphere to obtain the hydrogenation catalyst.
9. The method according to claim 8, characterized in that The nickel source includes nickel nitrate; the alkali solution includes one or more of potassium hydroxide, sodium hydroxide and ammonia water; the concentration of the alkali solution is 0.5-3 mol / L; and the temperature of the reduction heat treatment is 400-600°C.