CN114380660A - 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 PDF

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CN114380660A
CN114380660A CN202210112295.6A CN202210112295A CN114380660A CN 114380660 A CN114380660 A CN 114380660A CN 202210112295 A CN202210112295 A CN 202210112295A CN 114380660 A CN114380660 A CN 114380660A
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hydrogenolysis
hexanol
hydroxymethylfurfural
ring
opening
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CN114380660B (en
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刘琪英
胡晓虹
马隆龙
王海永
李志坚
王晨光
辛浩升
李松
刘思炜
张同
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Guangzhou Institute of Energy Conversion of CAS
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a method for preparing 2-hexanol by 5-hydroxymethylfurfural ring-opening hydrogenolysis, which is characterized in that 5-hydroxymethylfurfural is converted into 2-hexanol by utilizing an Au-based catalyst in one step, the efficiency is high, the energy is saved, the catalyst activity is high, the ring-opening hydrogenolysis effect is excellent, and the product selectivity is high. The Au-based catalyst has 1-7 wt% of Au load and Al as a carrier2O3、TiO2、Nb2O5Sulfated ZrO2And ZrO2Any of these five different metal oxides.

Description

Method for preparing 2-hexanol by ring-opening hydrogenolysis of 5-hydroxymethylfurfural
The technical field is as follows:
the invention relates to a method for preparing 2-hexanol by ring-opening hydrogenolysis of 5-hydroxymethylfurfural.
Background art:
lignocellulose is a sustainable resource that has received much attention as fossil fuels are consumed. Lignocellulose contains 55-65% of carbohydrates and can be converted into a series of high-value platform molecules, wherein 5-Hydroxymethylfurfural (HMF) and Furfural (FA) are produced by acid-catalyzed dehydration of glucose or xylose. These furan compounds can be further converted into other target products, such as aviation fuel, diesel, lubricants, and the like.
2-hexanol (2-HOL) is a versatile platform molecule that can be used to prepare plasticizers, lubricants, perfumes, tobacco, etc., and can also undergo carbon-carbon self-coupling and hydrodeoxygenation to C9-C24 hydrocarbons for use as aviation fuels and diesel substitutes; can also be mixed with other C2 to C11 alcohols for the production of jet fuel and other heavy fuels. The main route for the synthesis of 2-hexanol (2-HOL) involves the hydrogenolysis of 2, 5-Dimethylfuran (DMF) over various heterogeneous or homogeneous catalysts or the direct hydrogenation of 2-hexanone (2-HON). In fact, DMF is also derived from hydrodeoxygenation by HMF. There have been few attempts to convert HMF directly to the monohydric alcohol product by ring opening hydrogenolysis, although this one-step process appears to be more economically efficient. The lack of research in the one-step process from HMF to monohydric alcohols is due to the difficulty in suppressing side reactions of the pendant reactive carbonyl and hydroxymethyl groups to control the selectivity of the reaction. In addition, 1-pentanol (1-POL) and 2-pentanol (2-POL) prepared by ring-opening hydrogenolysis of furfural, which is a biomass derivative, can be widely used as organic synthesis raw materials, solvents and cosolvents, medical raw materials and the like, and can also be used as raw materials of edible spices.
The invention content is as follows:
the invention aims to provide a method for preparing 2-hexanol by 5-Hydroxymethylfurfural (HMF) ring-opening hydrogenolysis, 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 conservation, high catalyst activity, excellent ring-opening hydrogenolysis effect and high product selectivity.
The invention is realized by the following technical scheme:
a method for preparing 2-hexanol by 5-hydroxymethylfurfural ring-opening hydrogenolysis is characterized in that 5-hydroxymethylfurfural is used as a raw material, dioxane is used as a solvent, and 2-hexanol (2-HOL) is prepared by the one-step hydrogenolysis reaction under the action of an Au-based catalyst, the reaction temperature is 220-260 ℃, the preferable temperature is 240-260 ℃, the most preferable temperature is 250 ℃, the reaction time is 3-18h, the preferable time is 9-18h, the most preferable time is 12h, and the hydrogen pressure in a reaction system is 2.0-6.0MPa, the preferable pressure is 4-6MPa, and the most preferable pressure is 5 MPa; the Au-based catalyst has 1 to 7 weight percent of Au loading, preferably 3 to 7 weight percent, most preferably 5 weight percent and Al as a carrier2O3、TiO2、Nb2O5Sulfated ZrO2(ZrO2(ZS)) and ZrO2Any of these five different metal oxides, most preferably ZrO2。
The Au-based catalyst is prepared by two steps of a precipitation-deposition method, and specifically comprises the following steps: al (Al)2O3、TiO2、Nb2O5Sulfated ZrO2(ZrO2(ZS)) and ZrO2Any one of metal oxides, water and chloroauric acid (HAuCl)4·XH2O) aqueous solution is mixed and ultrasonically treated for 5-15min, stirred at 55-65 ℃, adjusted pH to 7.5-8.5 by 0.3-0.6mol/L KOH solution, refluxed for 1.5-2.5H, washed and dried, the powder obtained after grinding is heated to 290 ℃ at the heating rate of 3-5 ℃/min and is heated to 310 ℃ at 10% H2/N2Reducing for 1.5-2.5h under atmosphere to obtainTo the target catalyst.
In addition, the ring-opening hydrogenolysis of the 5-hydroxymethylfurfural can also be realized for the expansion of the raw material into furfural, when the main ring-opening products are 1-pentanol (1-POL) and 2-pentanol (2-POL), the reaction temperature is 220-260 ℃, the preferred temperature is 240-260 ℃, the most preferred temperature is 260 ℃, the reaction time is 3-18h, the preferred time is 9-18h, the most preferred time is 18h, and the hydrogen pressure in the reaction system is 2.0-6.0MPa, the preferred time is 4-6MPa, and the most preferred time is 5 MPa.
The invention has the following beneficial effects:
1) the one-step method for converting 5-hydroxymethylfurfural into 2-hexanol has the advantages of high efficiency, energy conservation, high catalyst activity, excellent ring-opening hydrogenolysis effect, high product selectivity, good cycle stability and certain industrial application prospect.
2) The reaction substrate is developed into furfural, and the ring-opening hydrogenolysis product (1-pentanol (1-POL) and 2-pentanol (2-POL)) selectivity is excellent.
Description of the drawings:
FIG. 1 is an XRD pattern of Au-based catalysts of different metal oxide supports in example 1, with 5% Au/Al2O3The carrier of the catalyst is Al2O3，5％Au/TiO2The carrier being TiO2，5％Au/Nb2O5The carrier is Nb2O5，5％Au/ZrO2(ZS) the support being a sulfated ZrO2，5％Au/ZrO2The support being ZrO2It can be seen that except for 5% Au/Al2O3And 5% Au/TiO2And the other three Au-based catalysts have no Au diffraction peak, which shows that the Au particles have small particle size and high dispersion degree.
FIG. 2 is 5% Au/ZrO2TEM image of catalyst, wherein a and b are TEM image of whole and local distribution, respectively, fig. c is TEM image with high resolution, fig. d is dark field TEM image, fig. e-h are EDS energy spectrum, whole and local distribution, visible catalyst is spherical aggregate, only ZrO appears in high resolution TEM2The lattice fringes of (a) indicate that the particle size of Au is small. The EDS spectrum indicates a high dispersion of Au particles.
FIG. 3 is 5% Au/ZrO2The normal distribution of the catalyst particle size indicates that the average particle size of the Au particles is 1.4 nm.
FIG. 4 is an XPS peak fit of Au 4f (FIG. a) and O1s (FIG. b) for Au-based catalysts of different metal oxide supports, illustrating 5% Au/ZrO2And 5% Au/ZrO2Au of the (ZS) catalyst has electronegative characteristics and is relatively deficient in oxygen (O)2)。
FIG. 5 is a graph of the product distribution after 5 cycles of 5% Au/ZrO2 catalyst, illustrating 5% Au/ZrO2Has excellent cycle stability, and can keep higher 2-HOL yield after being used for 5 times.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1: preparation of the catalyst
Weighing 2.5g of metal oxide carrier, wherein the metal oxide is Al2O3、TiO2、Nb2O5Sulfated ZrO2(ZrO2(ZS)) and ZrO2Any of the above was transferred to a 500ml round bottom flask and 200ml deionized water was added. Adding chloroauric acid solution according to the 5% Au loading amount, carrying out ultrasonic treatment on the mixed solution for 10min, then placing the mixed solution into a 60 ℃ oil bath kettle for stirring, dropwise adding strong alkaline solution KOH (0.5mol/L) into the mixed solution to adjust the pH value to 8, and keeping the state and refluxing for 2 h. And centrifuging and washing the obtained mixed solution to be neutral, and drying in a drying oven at 60 ℃ overnight to obtain the Au-based catalyst precursor. Before use, the temperature is raised to 300 ℃ at the heating rate of 5 ℃/min, and the precursor is heated to 10% H2/N2The reduction was carried out under an atmosphere for 2 h. XRD patterns of Au-based catalysts of different metal oxide supports are shown in FIG. 1, wherein 5% Au/Al2O3The carrier of the catalyst is Al2O3，5％Au/TiO2The carrier being TiO2，5％Au/Nb2O5The carrier is Nb2O5，5％Au/ZrO2(ZS) the support being a sulfated ZrO2，5％Au/ZrO2The support being ZrO2It can be seen that except for 5% Au/Al2O3And 5% Au/TiO2And the other three Au-based catalysts have no Au diffraction peak, which shows that the Au particles have small particle size and high dispersion degree.
Example 2:
0.07g of 5% Au/ZrO prepared in example 12Catalyst, 0.126g HMF and 20ml dioxane solution were added to a 50ml autoclave which was sealed and then charged with H2Replacing gas in the kettle for 6 times, and charging H2Pressurizing to 5 MPa. The stirring paddle (600rpm) is started, the reaction kettle is heated to 250 ℃ at the heating rate of 5 ℃/min, and the reaction time is 12 h. The yield of 2-hexanol product was 65.8%.
Examples 3 to 7:
example 3 reference was made to example 2 with the exception that the reaction temperature was 230 ℃.
Examples 4-7, reference example 2, except that the reaction temperature was 230 ℃, and the catalyst was different in metal oxide support, see table 1 for details.
TABLE 1
Figure BDA0003495158460000051
Examples 8 to 23:
reference example 2 at 5% Au/ZrO2The catalysts were varied in reaction temperature, pressure, time and metal loading, see in particular table 2.
TABLE 2
Figure BDA0003495158460000052
Figure BDA0003495158460000061
Examples 24 to 33:
reference example 2 at 5% Au/ZrO2The catalyst is different in that the reaction substrate is furfural, and the reaction temperature, pressure and time are different, see table 3 specifically.
TABLE 3
Figure BDA0003495158460000062

Claims (10)

1. A method for preparing 2-hexanol by 5-hydroxymethylfurfural ring-opening hydrogenolysis is characterized in that 5-hydroxymethylfurfural is used as a raw material, dioxane is used as a solvent, and 2-hexanol is prepared by one-step hydrogenolysis reaction under the action of an Au-based catalyst, wherein the reaction temperature is 220 ℃ and 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 1-7 wt% of Au load and Al as a carrier2O3、TiO2、Nb2O5Sulfated ZrO2And ZrO2Any of these five different metal oxides.
2. The method for preparing 2-hexanol by 5-hydroxymethylfurfural ring-opening hydrogenolysis according to claim 1, characterized in that the Au-based catalyst is prepared by a precipitation-deposition method in two steps, and specifically comprises the following steps: al (Al)2O3、TiO2、Nb2O5Sulfated ZrO2And ZrO2Mixing any one of the five different metal oxides, water and chloroauric acid aqueous solution, performing ultrasonic treatment for 5-15min, stirring at 55-65 ℃, adjusting pH to 7.5-8.5 by using 0.3-0.6mol/L KOH solution, refluxing for 1.5-2.5H, washing, drying, grinding to obtain powder, heating to 310 ℃ at a heating rate of 3-5 ℃/min, and performing ultrasonic treatment at 10% H2/N2Reducing for 1.5-2.5h under the atmosphere to obtain the target catalyst.
3. The method for preparing 2-hexanol by 5-hydroxymethylfurfural ring-opening hydrogenolysis according to claim 1, wherein the reaction temperature is 240 ℃ and 260 ℃, the reaction time is 9-18h, and the hydrogen pressure in the reaction system is 4-6 MPa.
4. The method for preparing 2-hexanol by 5-hydroxymethylfurfural ring-opening hydrogenolysis 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 5 MPa.
5. The process for the preparation of 2-hexanol by ring-opening hydrogenolysis of 5-hydroxymethylfurfural according to claim 1 wherein the Au-based catalyst has a Au loading of 3-7 wt%.
6. The process for the preparation of 2-hexanol by ring-opening hydrogenolysis of 5-hydroxymethylfurfural according to claim 1 wherein the Au-based catalyst has a Au loading of 5 wt%.
7. A method for preparing 1-pentanol and 2-pentanol by furfural ring-opening hydrogenolysis is characterized in that dioxane is used as a solvent, and 1-pentanol and 2-pentanol are prepared by one-step hydrogenolysis reaction under the action of an Au-based catalyst, wherein 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 1-7 wt% of Au load and Al as a carrier2O3、TiO2、Nb2O5Sulfated ZrO2And ZrO2Any of these five different metal oxides.
8. The method as claimed in claim 7, wherein the reaction temperature is 240 ℃ and 260 ℃, the reaction time is 9-18h, and the hydrogen pressure in the reaction system is 4-6 MPa.
9. The method according to claim 7, wherein the reaction temperature is 260 ℃ and the hydrogen pressure in the reaction system is 5 MPa.
10. The method of claim 7, wherein the Au-based catalyst has an Au loading of 5 wt%.
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Citations (5)

* Cited by examiner, † Cited by third party
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Title
HU, XIAOHONG等: "Selective Hydrogenolysis of 5-Hydroxymethylfurfural to 2-Hexanol over Au/ZrO2 Catalysts", 《CHEMSUSCHEM》, vol. 15, no. 13, pages 1 - 12 *

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