CN114380660B - Method for preparing 2-hexanol by ring-opening hydrogenolysis of 5-hydroxymethylfurfural - Google Patents
Method for preparing 2-hexanol by ring-opening hydrogenolysis of 5-hydroxymethylfurfural Download PDFInfo
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- CN114380660B CN114380660B CN202210112295.6A CN202210112295A CN114380660B CN 114380660 B CN114380660 B CN 114380660B CN 202210112295 A CN202210112295 A CN 202210112295A CN 114380660 B CN114380660 B CN 114380660B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses a method for preparing 2-hexanol by ring-opening hydrogenolysis of 5-hydroxymethylfurfural, which utilizes an Au-based catalyst to convert the 5-hydroxymethylfurfural into 2-hexanol in one step, and has the advantages of high efficiency, energy saving, high catalyst activity, excellent ring-opening hydrogenolysis effect and high product selectivity. The Au-based catalyst has Au loading of 1-7wt% and Al as a carrier 2 O 3 、TiO 2 、Nb 2 O 5 Sulfated ZrO 2 ZrO (ZrO) 2 Any of these five different metal oxides.
Description
Technical field:
the invention relates to a method for preparing 2-hexanol by ring-opening hydrogenolysis of 5-hydroxymethylfurfural.
The background technology is as follows:
lignocellulose is a sustainable resource that has received widespread attention as fossil fuels are consumed. The carbohydrate content in lignocellulose accounts for 55-65%, and can be converted into a series of high-value platform molecules, wherein 5-Hydroxymethylfurfural (HMF) and Furfural (FA) are produced by acid catalytic dehydration of glucose or xylose. These furan compounds can be further converted into other target products such as aviation fuel, diesel fuel, lubricants, and the like.
2-hexanol (2-HOL) is a versatile platform molecule useful for the preparation of plasticizers, lubricants, perfumes, tobacco, and the like, as well as carbon-carbon self-coupling and hydrodeoxygenation to C9-C24 hydrocarbons for aviation fuels and diesel substitutes; can also be mixed with other C2 to C11 alcohols for producing jet fuel and other heavy fuels. The main routes for 2-hexanol (2-HOL) synthesis include hydrogenolysis of 2, 5-Dimethylfuran (DMF) over various heterogeneous or homogeneous catalysts or direct hydrogenation of 2-hexanone (2-HON). In fact, DMF is also a hydrodeoxygenation derived from HMF. There have been few attempts to directly convert HMF to a monohydric alcohol product by ring-opening hydrogenolysis, although this one-step process appears to be more economical. The reason why the one-step method from HMF to monohydric alcohol is lack of study is that it is very difficult to suppress side reactions of side chain reactive carbonyl groups and hydroxymethyl groups to control the selectivity of the reaction. In addition, the 1-amyl alcohol (1-POL) and 2-amyl alcohol (2-POL) prepared by taking biomass derivative-furfural as raw material through ring-opening hydrogenolysis can be widely used as organic synthesis raw materials, solvents, cosolvents, medical raw materials and the like, and can also be used as raw materials of edible flavors.
The invention comprises the following steps:
the invention aims to provide a method for preparing 2-hexanol by ring-opening hydrogenolysis of 5-hydroxymethylfurfural, which utilizes an Au-based catalyst to convert 5-Hydroxymethylfurfural (HMF) into 2-hexanol (2-HOL) in one step, and has the advantages of high efficiency, energy saving, high catalyst activity, excellent ring-opening hydrogenolysis effect and high product selectivity.
The invention is realized by the following technical scheme:
preparation of 2-hexanol by ring-opening hydrogenolysis of 5-hydroxymethylfurfuralThe method comprises the steps of preparing 2-hexanol (2-HOL) by taking 5-hydroxymethylfurfural as a raw material and dioxane as a solvent through one-step hydrogenolysis under the action of an Au-based catalyst, wherein the reaction temperature is 220-260 ℃, preferably 240-260 ℃, most preferably 250 ℃, the reaction time is 3-18h, preferably 9-18h, most preferably 12h, and the hydrogen pressure in a reaction system is 2.0-6.0MPa, preferably 4-6MPa, most preferably 5MPa; the Au-based catalyst has Au loading of 1-7wt%, preferably 3-7wt%, most preferably 5wt% and the carrier is Al 2 O 3 、TiO 2 、Nb 2 O 5 Sulfated ZrO 2 (ZrO 2 (ZS)) and ZrO 2 Any of these five different metal oxides, most preferably ZrO 2 。
The Au-based catalyst is prepared by a precipitation-deposition method in two steps, and is specifically prepared as follows: al (Al) 2 O 3 、TiO 2 、Nb 2 O 5 Sulfated ZrO 2 (ZrO 2 (ZS)) and ZrO 2 Any one of metal oxides, water, chloroauric acid (HAuCl) 4 ·XH 2 Mixing O) water solution with ultrasound for 5-15min, stirring at 55-65deg.C, regulating pH to 7.5-8.5 with 0.3-0.6mol/L KOH solution, refluxing for 1.5-2.5 hr, washing, drying, grinding to obtain powder, heating to 290-310 deg.C at 3-5deg.C/min, and adding 10% H 2 /N 2 Reducing for 1.5-2.5h under atmosphere to obtain the target catalyst.
In addition, the ring-opening hydrogenolysis can be realized by expanding the raw material 5-hydroxymethylfurfural into furfural, wherein the main ring-opening products are 1-amyl alcohol (1-POL) and 2-amyl alcohol (2-POL), the reaction temperature is 220-260 ℃, preferably 240-260 ℃, most preferably 260 ℃, the reaction time is 3-18h, preferably 9-18h, most preferably 18h, and the hydrogen pressure in the reaction system is 2.0-6.0MPa, preferably 4-6MPa, most preferably 5MPa.
The beneficial effects of the invention are as follows:
1) The one-step method for converting the 5-hydroxymethylfurfural into the 2-hexanol has the advantages of high efficiency, energy saving, high catalyst activity, excellent ring-opening hydrogenolysis effect, high product selectivity, good cycle stability and certain industrial application prospect.
2) The expansion of the reaction substrate into furfural still has excellent selectivity of ring-opening hydrogenolysis products (1-pentanol (1-POL) and 2-pentanol (2-POL)).
Description of the drawings:
FIG. 1 is an XRD pattern for Au-based catalysts of different metal oxide supports in example 1, wherein 5% Au/Al 2 O 3 The carrier of the catalyst is Al 2 O 3 ，5％Au/TiO 2 The carrier is TiO 2 ，5％Au/Nb 2 O 5 The carrier is Nb 2 O 5 ，5％Au/ZrO 2 The (ZS) carrier is sulfated ZrO 2 ，5％Au/ZrO 2 The carrier is ZrO 2 It can be seen that in addition to 5% Au/Al 2 O 3 And 5% Au/TiO 2 The other three Au-based catalysts have no diffraction peak of Au, which indicates that the particle size of Au particles is small and the dispersion degree is high.
FIG. 2 shows 5% Au/ZrO 2 TEM image of catalyst, wherein a and b are respectively TEM images of whole and partial distribution, image c is TEM image with high resolution, image d is dark field TEM image, images e-h are EDS energy spectrum, whole and partial layout, and the catalyst is spherical aggregate, and only carrier ZrO appears in high resolution TEM 2 The lattice fringes of (2) indicate that the Au particle size is small. EDS spectra illustrate the high dispersion of Au particles.
FIG. 3 is 5% Au/ZrO 2 The average particle diameter of the Au particles was found to be 1.4nm from the normal distribution of the particle diameter of the catalyst.
FIG. 4 is a graph showing XPS peak-fitting of Au 4f (panel a) and O1s (panel b) of Au-based catalysts of different metal oxide supports, illustrating 5% Au/ZrO 2 And 5% Au/ZrO 2 Au of the (ZS) catalyst has electronegative properties and has more defective oxygen (O 2 )。
FIG. 5 is a distribution diagram of the product after 5 times recycling of 5% Au/ZrO2 catalyst, illustrating 5% Au/ZrO 2 Has excellent cycle stability and still maintains higher 2-HOL yield after 5 times of use.
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention.
Example 1: preparation of the catalyst
Weighing 2.5g of metal oxide carrier and goldThe metal oxide is Al 2 O 3 、TiO 2 、Nb 2 O 5 Sulfated ZrO 2 (ZrO 2 (ZS)) and ZrO 2 Any of which was transferred to a 500ml round bottom flask and 200ml deionized water was added. Chloroauric acid solution was added according to 5% au loading, after the mixed solution was sonicated for 10min, put into an oil bath at 60 ℃ and stirred, the mixed solution was added dropwise with strong alkaline solution KOH (0.5 mol/L) to adjust pH to 8, and this state was maintained at reflux for 2h. And centrifugally washing the obtained mixed solution to be neutral, and drying the mixed solution in a drying oven at 60 ℃ overnight to obtain the Au-based catalyst precursor. Before use, the temperature is raised to 300 ℃ at a heating rate of 5 ℃/min, and the precursor is heated to 10% H 2 /N 2 The reduction was carried out in an atmosphere for 2 hours. XRD patterns of Au-based catalysts of different metal oxide supports are shown in FIG. 1, in which 5% Au/Al 2 O 3 The carrier of the catalyst is Al 2 O 3 ，5％Au/TiO 2 The carrier is TiO 2 ，5％Au/Nb 2 O 5 The carrier is Nb 2 O 5 ，5％Au/ZrO 2 The (ZS) carrier is sulfated ZrO 2 ，5％Au/ZrO 2 The carrier is ZrO 2 It can be seen that in addition to 5% Au/Al 2 O 3 And 5% Au/TiO 2 The other three Au-based catalysts have no diffraction peak of Au, which indicates that the particle size of Au particles is small and the dispersion degree is high.
Example 2:
0.07g of 5% Au/ZrO as prepared in example 1 2 Catalyst, 0.126g HMF and 20ml dioxane solution were added to a 50ml autoclave, which was sealed and then treated with H 2 Replacing the gas in the kettle for 6 times and filling H 2 Pressurizing to 5MPa. The stirring paddle (600 rpm) was turned on, and the reaction vessel was warmed to 250℃at a heating rate of 5℃per minute for a reaction time of 12 hours. The yield of 2-hexanol product was 65.8%.
Examples 3 to 7:
example 3 with reference to example 2, the difference is that the reaction temperature is 230 ℃.
Examples 4-7, see example 2, except that the reaction temperature was 230 ℃ and the metal oxide support of the catalyst was different, see in particular table 1.
TABLE 1
Examples 8 to 23:
reference example 2, 5% Au/ZrO 2 As catalysts, the difference was in reaction temperature, pressure, time and metal loading, see in particular table 2.
TABLE 2
Examples 24 to 33:
reference example 2, 5% Au/ZrO 2 Is a catalyst, except that the reaction substrate is furfural, and the reaction temperature, pressure and time are different, see in particular table 3.
TABLE 3 Table 3
Claims (10)
1. A method for preparing 2-hexanol by ring-opening hydrogenolysis of 5-hydroxymethylfurfural is characterized in that 5-hydroxymethylfurfural is used as a raw material, dioxane is used as a solvent, 2-hexanol is prepared by one-step hydrogenolysis reaction under the action of an Au-based catalyst, the reaction temperature is 220-260 ℃, the reaction time is 3-18h, and the hydrogen pressure in a reaction system is 2.0-6.0 MPa; the Au-based catalyst has Au loading of 1-7wt% and TiO as a carrier 2 、Nb 2 O 5 Sulfated ZrO 2 ZrO (ZrO) 2 Any one of them.
2. The 5-hydroxymethylbran according to claim 1The method for preparing 2-hexanol by aldehyde ring-opening hydrogenolysis is characterized in that the Au-based catalyst is prepared by a precipitation-deposition method in two steps, and specifically comprises the following steps: tiO (titanium dioxide) 2 、Nb 2 O 5 Sulfated ZrO 2 ZrO (ZrO) 2 Mixing any one of water, chloroauric acid water solution, ultrasonic treatment for 5-15min, stirring at 55-65deg.C, regulating pH to 7.5-8.5 with 0.3-0.6mol/L KOH solution, refluxing 1.5-2.5H, washing, drying, grinding to obtain powder, heating to 290-310 deg.C at 3-5deg.C/min, and treating with 10% H 2 /N 2 Reducing 1.5-2.5h under atmosphere to obtain the target catalyst.
3. The method for preparing 2-hexanol by ring-opening hydrogenolysis of 5-hydroxymethylfurfural according to claim 1, wherein the reaction temperature is 240-260 ℃, the reaction time is 9-18h, and the hydrogen pressure in the reaction system is 4-6MPa.
4. The method for preparing 2-hexanol by ring-opening hydrogenolysis of 5-hydroxymethylfurfural according to claim 1, wherein the reaction temperature is 250 ℃, the reaction time is 12 hours, and the hydrogen pressure in the reaction system is 5MPa.
5. The method for preparing 2-hexanol by ring-opening hydrogenolysis of 5-hydroxymethylfurfural according to claim 1, wherein the Au-based catalyst has Au loading of 3-7wt%.
6. The method for preparing 2-hexanol by ring-opening hydrogenolysis of 5-hydroxymethylfurfural according to claim 1, wherein the Au-based catalyst has Au loading of 5wt%.
7. A method for preparing 1-pentanol and 2-pentanol by ring-opening hydrogenolysis of furfural is characterized in that dioxane is used as a solvent to prepare 1-pentanol and 2-pentanol through one-step hydrogenolysis reaction under the action of an Au-based catalyst, the reaction temperature is 220-260 ℃, the reaction time is 3-18h, and the hydrogen pressure in a reaction system is 2.0-6.0 MPa; the Au-based catalyst has Au loading of 1-7wt% and ZrO carrier 2 。
8. The method according to claim 7, wherein the reaction temperature is 240-260 ℃, the reaction time is 9-18h, and the hydrogen pressure in the reaction system is 4-6MPa.
9. The method according to claim 7, wherein the reaction temperature is 260℃and the hydrogen pressure in the reaction system is 5MPa.
10. The method of claim 7, wherein the Au-based catalyst has an Au loading of 5wt%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013163540A1 (en) * | 2012-04-27 | 2013-10-31 | E. I. Du Pont De Nemours And Company | Production of alpha, omega-diols |
| CN110799504A (en) * | 2017-06-30 | 2020-02-14 | 韩国生产技术研究院 | Method for preparing dimethyl 2, 5-furandicarboxylate from hydroxymethylfurfural |
| WO2020161750A1 (en) * | 2019-02-08 | 2020-08-13 | Ganapati Dadasaheb Yadav | Process of preparation of 1,2-pentanediol from furfural |
| CN113318735A (en) * | 2020-02-28 | 2021-08-31 | 中国科学院大连化学物理研究所 | Application of composite oxide supported Pt catalyst in preparation of pentanediol from furfural |
| CN113908841A (en) * | 2021-10-11 | 2022-01-11 | 华东师范大学 | Application of Cu-based catalyst in preparation of pentanediol through furfuryl alcohol hydrogenolysis |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013163540A1 (en) * | 2012-04-27 | 2013-10-31 | E. I. Du Pont De Nemours And Company | Production of alpha, omega-diols |
| CN110799504A (en) * | 2017-06-30 | 2020-02-14 | 韩国生产技术研究院 | Method for preparing dimethyl 2, 5-furandicarboxylate from hydroxymethylfurfural |
| WO2020161750A1 (en) * | 2019-02-08 | 2020-08-13 | Ganapati Dadasaheb Yadav | Process of preparation of 1,2-pentanediol from furfural |
| CN113318735A (en) * | 2020-02-28 | 2021-08-31 | 中国科学院大连化学物理研究所 | Application of composite oxide supported Pt catalyst in preparation of pentanediol from furfural |
| CN113908841A (en) * | 2021-10-11 | 2022-01-11 | 华东师范大学 | Application of Cu-based catalyst in preparation of pentanediol through furfuryl alcohol hydrogenolysis |
Non-Patent Citations (1)
| Title |
|---|
| Selective Hydrogenolysis of 5-Hydroxymethylfurfural to 2-Hexanol over Au/ZrO2 Catalysts;Hu, Xiaohong等;《ChemSusChem》;第15卷(第13期);第1-12页 * |
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