CN117820262A - Thermal catalytic coupling method of 5-methylfurfural - Google Patents
Thermal catalytic coupling method of 5-methylfurfural Download PDFInfo
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- 238000010168 coupling process Methods 0.000 title claims abstract description 49
- OUDFNZMQXZILJD-UHFFFAOYSA-N 5-methyl-2-furaldehyde Chemical compound CC1=CC=C(C=O)O1 OUDFNZMQXZILJD-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 230000003197 catalytic effect Effects 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
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- 239000002184 metal Substances 0.000 claims description 10
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- 238000010438 heat treatment Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910021642 ultra pure water Inorganic materials 0.000 description 8
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- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- -1 furan aldehyde Chemical class 0.000 description 5
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- 238000005406 washing Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
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- MWEXRLZUDANQDZ-RPENNLSWSA-N (2s)-3-hydroxy-n-[11-[4-[4-[4-[11-[[2-[4-[(2r)-2-hydroxypropyl]triazol-1-yl]acetyl]amino]undecanoyl]piperazin-1-yl]-6-[2-[2-(2-prop-2-ynoxyethoxy)ethoxy]ethylamino]-1,3,5-triazin-2-yl]piperazin-1-yl]-11-oxoundecyl]-2-[4-(3-methylsulfanylpropyl)triazol-1-y Chemical compound N1=NC(CCCSC)=CN1[C@@H](CO)C(=O)NCCCCCCCCCCC(=O)N1CCN(C=2N=C(N=C(NCCOCCOCCOCC#C)N=2)N2CCN(CC2)C(=O)CCCCCCCCCCNC(=O)CN2N=NC(C[C@@H](C)O)=C2)CC1 MWEXRLZUDANQDZ-RPENNLSWSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- ZRKKCRMLSFIPBE-UHFFFAOYSA-N 2,5-dimethoxy-3-methylfuran Chemical compound COC1=CC(C)=C(OC)O1 ZRKKCRMLSFIPBE-UHFFFAOYSA-N 0.000 description 1
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 description 1
- SSXJHQZOHUYEGD-UHFFFAOYSA-N 3,3',4',5,6,7,8-Heptamethoxyflavone Natural products C1=C(OC)C(OC)=CC=C1C1=C(OC)C(=O)C2=C(OC)C(OC)=C(OC)C(OC)=C2O1 SSXJHQZOHUYEGD-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
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- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
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- 229940094933 n-dodecane Drugs 0.000 description 1
- DLVYTANECMRFGX-UHFFFAOYSA-N norfuraneol Natural products CC1=C(O)C(=O)CO1 DLVYTANECMRFGX-UHFFFAOYSA-N 0.000 description 1
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- 238000001107 thermogravimetry coupled to mass spectrometry Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention provides a thermocatalytic coupling method of 5-methylfurfural, and relates to the technical field of carbon chain extension. The method comprises the following steps: in the atmosphere of solvent and hydrogen, under the condition of thermal catalyst, controlling reaction temperature to 80-160 deg.C, and making 5-methyl furfural produce reaction to obtain the coupling product. The method provided by the invention can carry out coupling catalysis on the 5-methylfurfural under mild conditions, so that a long-carbon chain compound is generated, an acid-base environment is not required to be used in the reaction process, the reaction rate is high, the selectivity is high, and the obtained coupling product can be used as a fuel precursor to be applied to further synthesis of fuel.
Description
Technical Field
The invention relates to the technical field of carbon chain extension, in particular to a thermocatalytic coupling method of 5-methylfurfural.
Background
With the continuous acceleration of global industrialization, the consumption of fossil energy is also increasing, and with the exhaustion of fossil energy, the development of renewable fuels is becoming increasingly important, from cellulose and hemicellulose and derivatives thereofA large number of furan aldehyde derivatives, such as 5-carboxymethyl furfural, 5-methyl furfural, furfural and the like, are obtained, and the compounds are C 5-6 The oxygen-containing unit structure of (2) can obtain C through carbon chain extension 9-20 The long straight-chain alkane and branched alkane can be obtained through ring opening and hydrodeoxygenation reaction, and can be used as biodiesel or aerospace fuel.
At present, a number of methods for extending the carbon chain of furans have been developed, such as Hydroxyalkylation (HAA) reactions, typically by condensing molecules with aldehyde or carbonyl groups with 2-methylfuran, for example using furfural, HMF, acetone, butyraldehyde, valeraldehyde and acetylacetonate with 2-methylfuran.
Thus, the prior art provides a method for producing HAA products with 75% yield using 2-methylfuran and furfural as substrates, catalyzed by perfluorosulfonic acid resin-212. In addition, homogeneous acid catalysts can be used, and various heterogeneous acid catalysts (or solid acid catalysts such as heteropolyacid, zeolite, mesoporous solid acid and the like) can be used for extending carbon chains through aldol condensation, etherification and other reactions, and the reaction of 2, 5-dimethylol furan and methanol can be carried out by the mukul et al in the presence of an acidic ZSM-5 molecular sieve (HZSM-5) to obtain 70 percent of corresponding 2, 5-dimethoxy methyl furan (BMMF), and the target product BMMF is an excellent cetane improver of diesel oil (Applied Catalysis A: general 481 (2014) 49-53). It has also been reported that coupling furfural by NHC organic catalyst gives a coupled product, uses a renewable solvent and allows direct utilization of furan aldehydes synthesized from biomass, yields of 5,5 '-dimethylfurin from furfural as substrate approaching 90%, and they further succeeded in converting the coupled product 5,5' -dimethylfurin to dodecane using zeolite supported Pd catalyst with a high yield (70%) and a selectivity to n-dodecane of 94% (ChemSusChem 2014,7, 2742-2747).
However, the reaction conditions of the methods provided in the prior art are severe, and thus it is necessary to provide a solution capable of elongating the carbon chain under mild conditions.
Disclosure of Invention
The invention aims to provide a thermocatalytic coupling method of 5-methylfurfural, which can carry out coupling catalysis on 5-methylfurfural under mild conditions so as to generate long-carbon chain compounds, the reaction process does not need to use an acid-base environment, the reaction rate is high, the selectivity is high, and the obtained coupling product can be used as a fuel precursor to be applied to further synthesis of fuel.
The invention provides a thermocatalytic coupling method of 5-methylfurfural, which comprises the following steps: in the atmosphere of solvent and hydrogen, controlling the reaction temperature to be 80-160 ℃ in the presence of a thermal catalyst, and reacting furan aldehyde compound I to generate a compound shown in a formula II;
alternatively, the thermal catalyst comprises a support and a metal catalyst supported on the support, and the metal catalyst comprises Ru.
Optionally, the metal catalyst further comprises Cu.
Optionally, the mass ratio of Ru to Cu in the supported metal catalyst is 2: (5-15).
Alternatively, the supported metal catalyst is supported in an amount of 2 to 17wt%.
Optionally, the carrier comprises at least one of ceria and hydroxyapatite.
Optionally, when the 5-methylfurfural I reacts, the reaction time of the reaction system is controlled to be 1-4h.
Optionally, when the 5-methylfurfural I reacts in the solvent and hydrogen atmosphere, the hydrogen pressure in the reaction system is controlled to be 1-5Mpa.
Optionally, the solvent includes at least one of water, cyclohexane, ethyl acetate, dichloromethane, and toluene.
Drawings
FIG. 1 is a mass spectrum of the product prepared in example 1 of the present invention;
FIG. 2 is a hydrogen spectrum of the product prepared in example 1 of the present invention;
FIG. 3 is a carbon spectrum of the product prepared in example 1 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Unless otherwise defined, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. As used herein, the word "comprising" and the like means that elements or items preceding the word are included in the element or item listed after the word and equivalents thereof without precluding other elements or items.
The experimental methods in the examples below are conventional methods, and the reagents and instruments according to the present invention are commercially available without identifying the manufacturer, unless otherwise indicated.
In the following examples of the present invention, a RuCu/HAP catalyst was prepared by impregnation calcination, 500mg of HAP powder and 20.5mg of RuCl were first prepared 3 And 189mgCu (NO) 3 ) 2 ·3H 2 The dispersion of O was stirred in 15mL of ultrapure water for 24 hours. And then washed three times by centrifugation. Finally, the flow rate is 100 mL.min through a tube furnace -1 At 10 ℃ for min in the hydrogen flow -1 Is calcined and reduced for 4 hours at 400 ℃.
In the invention, a gas chromatograph (Agilent 7890B) is adopted for quantitatively analyzing the yield, and a chromatographic column is an Agilent HP-5 capillary column (30 m is 32 μm is 0.25 μm). The qualitative analysis used a gas mass spectrometer Thermo scientificTRACE1310 and a nuclear magnetic resonance spectrometer AVANCE III HD MHZ column of Thermoscientific TG-MS capillary column (30 m x 32 μm x 0.25 μm).
Preparation example 1
The preparation example 1 of the invention provides a preparation method of a RuCu/HAP catalyst, which comprises the following steps:
d1, 500mg of HAP powder, 20.5mg of RuCl 3 189mg of Cu (NO) 3 ) 2 ·3H 2 Dispersing O into 15mL of ultrapure water, and stirring for 24 hours to prepare a load suspension;
d2, after carrying out centrifugal washing on the load suspension for three times, filtering out solids, placing the solids in a tube furnace, heating up the solids at a heating rate of 10 ℃/min in an environment with a hydrogen flow of 100mL/min, and calcining and reducing the solids at 400 ℃ for 4 hours to obtain a RuCu/HAP catalyst; the Ru loading in the rucu\hap catalyst was calculated to be 2.0wt.%, and the Cu loading was calculated to be 10wt.%.
Preparation example 2
Preparation example 2 of the present invention provides a method for preparing RuCu/HAP catalyst, which is different from preparation example 1 in that 500mg of HAP powder and 20.5mg of RuCl are added in step D1 3 And 94.5mg of Cu (NO) 3 ) 2 ·3H 2 O was dispersed into 15mL of ultrapure water; in step D2, the loading of Ru in the rucu\hap catalyst was calculated to be 2.0wt.%, and the loading of Cu was calculated to be 5wt.%.
Preparation example 3
Preparation example 3 of the present invention provides a method for preparing RuCu/HAP catalyst, which is different from preparation example 1 in that 500mg of HAP powder and 20.5mg of RuCl are added in step D1 3 283.5mg of Cu (NO) 3 ) 2 ·3H 2 O was dispersed into 15mL of ultrapure water; in step D2, the loading of Ru in the rucu\hap catalyst was calculated to be 2.0wt.%, and the loading of Cu was calculated to be 15wt.%.
Example 1
The embodiment 1 of the invention provides a thermocatalytic coupling method of 5-methylfurfural, which comprises the following steps:
s1, putting 110mg of 5-methylfurfural, 50mg of RuCu/HAP catalyst prepared in preparation example 1, 5.0mL of cyclohexane and 5.0mL of deionized water into a reaction kettle for uniform dispersion, and after replacing air in the reaction kettle for five times by using hydrogen, introducing hydrogen into the reaction kettle until the pressure in the reaction kettle reaches 4Mpa;
s2, heating the reaction kettle to 80 ℃ and preserving heat for reaction for 4 hours, separating an organic phase and a water phase, repeatedly extracting the water phase for three times by using ethyl acetate, and calculating the molar yield to be 4.6% by using GC analysis after volume fixing.
The reaction formula of the thermocatalytic coupling method of 5-methylfurfural provided in the embodiment 1 of the invention is as follows:
example 2
The embodiment 2 of the invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from the embodiment 1 in that in the step S2, a reaction kettle is heated to 100 ℃ and is subjected to thermal insulation reaction for 4 hours; the molar yield was calculated to be 74.3%.
Example 3
The embodiment 3 of the invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from the embodiment 1 in that in the step S2, a reaction kettle is heated to 120 ℃ and is subjected to thermal insulation reaction for 4 hours; the molar yield was calculated to be 72.2%.
Example 4
The embodiment 4 of the invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from the embodiment 1 in that in the step S2, a reaction kettle is heated to 140 ℃ and is subjected to thermal insulation reaction for 4 hours; the molar yield was calculated to be 36.0%.
Example 5
The embodiment 5 of the invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from the embodiment 1 in that in the step S2, a reaction kettle is heated to 160 ℃ and is subjected to thermal insulation reaction for 4 hours; the molar yield was calculated to be 27.7%.
Example 6
The embodiment 6 of the invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from the embodiment 2 in that in the step S2, a reaction kettle is heated to 100 ℃ and is subjected to heat preservation reaction for 1h; the molar yield was calculated to be 38.1%.
Example 7
The embodiment 7 of the invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from the embodiment 2 in that in the step S2, a reaction kettle is heated to 100 ℃ and is subjected to heat preservation reaction for 2 hours; the molar yield was calculated to be 53.9%.
Example 8
The embodiment 8 of the invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from the embodiment 2 in that in the step S2, a reaction kettle is heated to 100 ℃ and is subjected to heat preservation reaction for 3 hours; the molar yield was calculated to be 55.2%.
Example 9
The embodiment 9 of the invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from the embodiment 2 in that in the step S1, hydrogen is introduced into a reaction kettle until the pressure in the reaction kettle reaches 1Mpa; in step S2, the molar yield was calculated to be 44.6%.
Example 10
The embodiment 10 of the invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from the embodiment 2 in that in the step S1, hydrogen is introduced into a reaction kettle until the pressure in the reaction kettle reaches 2Mpa; in step S2, the molar yield was calculated to be 61.5%.
Example 11
The embodiment 11 of the invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from the embodiment 2 in that in the step S1, hydrogen is introduced into a reaction kettle until the pressure in the reaction kettle reaches 3Mpa; in step S2, the molar yield was calculated to be 68.4%.
Example 12
The embodiment 12 of the invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from the embodiment 2 in that in the step S1, hydrogen is introduced into a reaction kettle until the pressure in the reaction kettle reaches 5Mpa; in step S2, the molar yield was calculated to be 54.3%.
Example 13
Embodiment 13 of the present invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from embodiment 2 in that in step S1, 5.0mL of toluene is used instead of 5.0mL of cyclohexane; in step S2, the molar yield was calculated to be 36.6%.
Example 14
Embodiment 14 of the present invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from embodiment 2 in that 5.0mL of ethyl acetate is used to replace 5.0mL of cyclohexane in step S1; in step S2, the molar yield was calculated to be 12.0%.
Example 15
Embodiment 15 of the present invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from embodiment 2 in that in step S1, 5.0mL of dichloromethane is used to replace 5.0mL of cyclohexane; in step S2, the molar yield was calculated to be 5.3%.
Example 16
The embodiment 16 of the present invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from the embodiment 2 in that in the step S1, 50mg of RuCu/HAP catalyst is replaced by 50mg of Ru/HAP catalyst; in step S2, the molar yield was calculated to be 46.5%.
Specifically, the preparation method of the Ru/HAP catalyst in the embodiment 16 includes the following steps:
d1, 500mg of HAP powder and 20.5mg of RuCl 3 Dispersing into 15mL of ultrapure water, stirring for 24 hours, and preparing a load suspension;
d2, after carrying out centrifugal washing on the load suspension for three times, filtering out solids, placing the solids in a tube furnace, heating up the load suspension at a heating rate of 10 ℃/min in an environment with a hydrogen flow of 100mL/min, and calcining and reducing the load suspension at 400 ℃ for 4 hours to prepare the Ru/HAP catalyst; the calculated Ru loading in the ru\hap catalyst was 2.0wt.%.
Example 17
Embodiment 17 of the present invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from embodiment 2 in that in step S1, 50mg of the rucu\hap catalyst prepared in preparation example 2 is used instead of 50mg of the rucu\hap catalyst prepared in preparation example 1; in step S2, the molar yield was calculated to be 49.7%.
Example 18
Embodiment 18 of the present invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from embodiment 2 in that in step S1, 50mg of the rucu\hap catalyst prepared in preparation example 3 is used instead of 50mg of the rucu\hap catalyst prepared in preparation example 1; in step S2, the molar yield was calculated to be 49.6%.
Example 19
The embodiment 19 of the invention provides a thermocatalytic coupling method of furan aldehydes, which is different from the embodiment 2 in that in the step S1, 110mg of 5-methylfurfural, 25mg of RuCu/HAP catalyst prepared in the preparation example 1, 5.0mL of cyclohexane and 5.0mL of deionized water are put into a reaction kettle; in step S2, the molar yield was calculated to be 21.3%.
Example 20
The embodiment 20 of the invention provides a thermocatalytic coupling method of furan aldehydes, which is different from the embodiment 2 in that in the step S1, 110mg of 5-methylfurfural, 75mg of RuCu/HAP catalyst prepared in the preparation example 1, 5.0mL of cyclohexane and 5.0mL of deionized water are put into a reaction kettle; in step S2, the molar yield was calculated to be 62.9%.
Example 21
Embodiment 21 of the present invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from embodiment 2 in that in step S1, 50mg of RuCu\CeO is used 2 Catalyst replacement 50mg of RuCu\HAP catalyst prepared in preparation example 1; in step S2, the molar yield was calculated to be 30%.
Specifically, ruCu\CeO in example 21 2 The preparation method of the catalyst comprises the following steps:
d1 to 500mg CeO 2 Powder, 20.5mg RuCl 3 189mg of Cu (NO) 3 ) 2 ·3H 2 Dispersing O into 15mL of ultrapure water, and stirring for 24 hours to prepare a load suspension;
d2, after carrying out centrifugal washing on the load suspension for three times, filtering out solids, placing the solids in a tube furnace, heating up at a heating rate of 10 ℃/min in an environment with hydrogen flow of 100mL/min, and calcining and reducing for 4 hours at 400 ℃ to obtain RuCu\CeO 2 A catalyst; calculated RuCu\CeO 2 The loading of Ru in the catalyst was 2.0wt.%, and the loading of Cu was 10wt.%.
Comparative example 1
Comparative example 1 of the present invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from example 2 in that 50mg of Cu/HAP catalyst is used instead of 50mg of RuCu/HAP catalyst prepared in preparation example 1 in step S1; in step S2, the molar yield was calculated to be 0%.
Specifically, the preparation method of the Cu/HAP catalyst in comparative example 1 comprises the following steps:
d1, 500mg of HAP powder and 37.8mg of Cu (NO) 3 ) 2 ·3H 2 Dispersing O into 15mL of ultrapure water, and stirring for 24 hours to prepare a load suspension;
d2, after carrying out centrifugal washing on the load suspension for three times, filtering out solids, placing the solids in a tube furnace, heating up the solids at a heating rate of 10 ℃/min in an environment with a hydrogen flow of 100mL/min, and calcining and reducing the solids at 400 ℃ for 4 hours to obtain a Cu/HAP catalyst; the calculated Cu loading in the cu\hap catalyst was 2.0wt.%.
Comparative example 2
Comparative example 2 of the present invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from example 2 in that 50mg of HAP catalyst is used instead of 50mg of RuCu\HAP catalyst prepared in preparation example 1 in step S1; in step S2, the molar yield was calculated to be 0%.
Comparative example 3
Comparative example 3 of the present invention provides a thermocatalytic coupling method of 5-methylfurfural, which is different from example 2 in that 50mg of RuCu\H-ZSM-5 catalyst is used in step S1 to replace 50mg of RuCu\HAP catalyst prepared in preparation example 1; in step S2, the molar yield was calculated to be 0%.
Specifically, the preparation method of the RuCu/H-ZSM-5 catalyst in comparative example 3 comprises the following steps:
d1, 500mg of H-ZSM-5 powder, 20.5mg of RuCl 3 189mg of Cu (NO) 3 ) 2 ·3H 2 Dispersing O into 15mL of ultrapure water, and stirring for 24 hours to prepare a load suspension;
d2, after carrying out centrifugal washing on the load suspension for three times, filtering out solids, placing the solids in a tube furnace, heating up the solids at a heating rate of 10 ℃/min in an environment with a hydrogen flow of 100mL/min, and calcining and reducing the solids at 400 ℃ for 4 hours to prepare the RuCu/H-ZSM-5 catalyst; the Ru loading in the RuCu\H-ZSM-5 catalyst was calculated to be 2.0wt.%, and the Cu loading was calculated to be 10wt.%.
From examples 1-21, it can be seen that the present invention provides a process that enables thermocatalytic coupling of 5-methylfurfural, and from examples 1-5, the present invention provides a thermocatalytic coupling process with a yield that is temperature dependent, e.g., the reaction is controlled to be less than 4.6% when conducted at 80 ℃ as in example 1, and to be reduced to 27.7% when conducted at 160 ℃ as in example 5, and therefore it can be seen that the thermocatalytic coupling process provided by the present invention provides a better yield between 100-120 ℃ but still has a lower reaction temperature than other processes of the prior art.
As can be seen from examples 2 and 9-12, the better yield can be achieved by maintaining the hydrogen pressure at about 4MPa during the reaction; as can be seen from examples 2 and examples 13-15, better yields can be achieved using cyclohexane as the solvent material.
While embodiments of the present invention have been described in detail hereinabove, it will be apparent to those skilled in the art that various modifications and variations can be made to these embodiments. It is to be understood that such modifications and variations are within the scope and spirit of the present invention as set forth in the following claims. Moreover, the invention described herein is capable of other embodiments and of being practiced or of being carried out in various ways.
Claims (9)
1. A thermocatalytic coupling method of 5-methylfurfural, comprising the steps of: in the atmosphere of solvent and hydrogen, controlling the reaction temperature to be 80-160 ℃ under the condition of a thermal catalyst, and reacting 5-methylfurfural I to generate a compound shown in a formula II;
2. the thermocatalytic coupling process of claim 1, wherein the thermocatalyst comprises a support and a metal catalyst supported on the support and the metal catalyst comprises Ru.
3. The thermocatalytic coupling process of claim 2, wherein said metal catalyst further comprises Cu.
4. The thermocatalytic coupling process according to claim 3, wherein the mass ratio of Ru to Cu in the supported metal catalyst is 2: (5-15).
5. The thermocatalytic coupling process of any of claims 1 to 4, wherein the supported metal catalyst is present in an amount of 2-17wt%.
6. The thermocatalytic coupling process of claim 2, wherein the support comprises at least one of ceria and hydroxyapatite.
7. The thermocatalytic coupling process according to claim 1, wherein the reaction time of the reaction system is controlled to be 1-4h when the reaction of 5-methylfurfural I occurs.
8. The thermocatalytic coupling method according to claim 1, wherein when the reaction of 5-methylfurfural I occurs in a solvent and hydrogen atmosphere, the hydrogen pressure in the reaction system is controlled to be 1-5Mpa.
9. The thermocatalytic coupling process of claim 1, wherein the solvent comprises at least one of water, cyclohexane, ethyl acetate, methylene chloride and toluene.
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