CN116925014A - Method for preparing 2-methyl furan from biomass raw material - Google Patents
Method for preparing 2-methyl furan from biomass raw material Download PDFInfo
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- CN116925014A CN116925014A CN202310832180.9A CN202310832180A CN116925014A CN 116925014 A CN116925014 A CN 116925014A CN 202310832180 A CN202310832180 A CN 202310832180A CN 116925014 A CN116925014 A CN 116925014A
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- xylose
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- hydrodechlorination
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- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000002994 raw material Substances 0.000 title claims abstract description 13
- 239000002028 Biomass Substances 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims abstract description 64
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims abstract description 36
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims abstract description 36
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000012267 brine Substances 0.000 claims abstract description 12
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 7
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- -1 halide salt Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 35
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 16
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000006317 isomerization reaction Methods 0.000 description 6
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- ZAQJHHRNXZUBTE-WUJLRWPWSA-N D-xylulose Chemical compound OC[C@@H](O)[C@H](O)C(=O)CO ZAQJHHRNXZUBTE-WUJLRWPWSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 3
- 239000000811 xylitol Substances 0.000 description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 3
- 229960002675 xylitol Drugs 0.000 description 3
- 235000010447 xylitol Nutrition 0.000 description 3
- WOPKYMRPOKFYNI-UHFFFAOYSA-N 2-hydroxycyclopent-2-en-1-one Chemical compound OC1=CCCC1=O WOPKYMRPOKFYNI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229920001221 xylan Polymers 0.000 description 2
- 150000004823 xylans Chemical class 0.000 description 2
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940035676 analgesics Drugs 0.000 description 1
- 239000000730 antalgic agent Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The application discloses a route for preparing 2-methyl furan by taking hemicellulose as a raw material. Xylose can be converted to 2-methylfuran in one step in a high concentration brine/organic extractant system. The highest yield can reach 82 percent. The process skillfully utilizes the hydrodechlorination reaction, and successfully regulates and controls the selectivity of the final product by regulating and controlling the concentration of brine. The whole reaction process is acid-free and alkali-free, and has no great corrosion to reaction equipment, thereby being beneficial to large-scale production. Has great significance for sustainable development of energy sources in China, environmental protection and rapid realization of carbon neutralization and carbon peak.
Description
Technical Field
The application relates to a novel method for preparing 2-methyl furan by catalytically converting biomass raw materials. In particular, hemicellulose can be converted into 2-methyl furan in one step under a high-concentration brine/organic extractant system. The yield can reach 82 percent at most
Background
2-methyl furan is an important organic synthesis intermediate and has wide application prospect. Can be used for preparing various medicines, such as antibiotics, analgesics, antitumor medicines, etc. In addition, 2-methyl furan can also be used as an additive in the fields of foods, fragrances, dyes and the like, so that the 2-methyl furan has important significance in the research of efficient, economic and green synthesis methods. In the traditional 2-methyl furan synthesis method, sulfuric acid is used as a catalyst, 2-methyl-2-butanol and formaldehyde are used as raw materials, esterification reaction is carried out under the heating condition, and then dehydration and cyclization are carried out to obtain the 2-methyl furan. However, this method has problems of complicated operation, severe reaction conditions, difficulty in purifying the product, and the like. Therefore, researchers seek to develop a simple, efficient and environment-friendly method for synthesizing 2-methylfuran to solve the problems of the existing methods.
The biomass energy is widely distributed and has low cost. The exploitation and utilization of fossil energy has in recent years increasingly highlighted environmental impact compared to biomass energy. Research on the preparation of 2-methylfuran using biomass energy has become a hotspot in research in the field of biomass energy today. So far, the preparation of 2-methylfuran is mostly prepared by selective hydrogenation of furfural. In recent years, the price of furfural is higher and higher, and the furfural is not easy to preserve and is easy to form furoic acid. Therefore, optimizing the raw materials for preparing 2-methylfuran, and researching a new production process is very necessary. Hemicellulose is one of the three major components of lignocellulose, mainly C 5 The sugar is formed by connecting glycosidic bonds. Through research in recent years, authors in scientific research have found that hemicellulose is very easy to extract from lignocellulosic species, and can be present in the extract in the form of xylose and is easy to preserve. Compared with furfural, the extraction process of xylose is more green. It is reported in the literature that xylose can be extracted from lignocellulosic species using a gamma valerolactone/water/low co-solvent system under reaction conditions of 120 ℃. Therefore, it is necessary to study a process for preparing 2-methylfuran from xylose as a raw material.
Disclosure of Invention
In order to solve the problems, the application provides a new route for preparing 2-methyl furan by taking xylose as a raw material. Xylose can be converted to 2-methylfuran in one step in a high concentration brine/organic extractant system. The highest yield can reach 82 percent. The process skillfully utilizes the hydrodechlorination reaction, and the selectivity of the final product is successfully regulated and controlled by regulating and controlling the concentration of brine. The whole reaction process is acid-free and alkali-free, and has no great corrosion to reaction equipment, thereby being beneficial to large-scale production. Has great significance for sustainable development of energy sources in China, environmental protection and quick realization of carbon neutralization and carbon realization.
The application relates to a novel method for preparing 2-methyl furan by catalytically converting hemicellulose, which is realized by the following means.
Adopts a high-concentration halogenated salt water/organic solvent two-phase system and a common hydrodechlorination catalyst, and the reaction raw materials are directly converted into 2-methylfuran through one-step hydrodechlorination reaction by isomerism and dehydration under the hydrogen atmosphere and at a specific reaction temperature.
Further, in the above technical scheme, the reaction raw material is hemicellulose component of biomass species and monomer thereof, including one or more than two mixtures of xylose and arabinose species.
Further, in the above-described embodiments, the high concentration brine halide, i.e., the salt concentration required to be in excess of 50wt.% at the reaction conditions, provides sufficient halide ions to promote hydrodehalogenation at the reaction conditions.
Further, in the above-described embodiments, the halogen salt requiring a solubility of more than 50wt.% under the reaction conditions comprises a mixture of one or more of KCl, KBr and NaBr.
Furthermore, in the above technical scheme, the organic solvent in the two-phase system of halogenated brine/organic solvent is a plurality of organic solvents which have extraction function and are not mutually soluble with brine, and include toluene, methyltetrahydrofuran, tetrahydrofuran and methyl isobutyl ketone.
Further, in the above technical solution, the conventional hydrodechlorination catalyst includes: pd/C, niAu, pt/C, pdCu, ruCu.
Further, in the technical scheme, under the hydrogen atmosphere, the hydrogen pressure is 2-8 MPa, and the reaction temperature is 140-240 ℃.
Further, in the above technical scheme, the volume ratio of the halogenated brine to the organic solvent is 1:10 to 1:1.
Detailed Description
Examples 1 to 3
The Pd/C catalyst is used for the conversion experiment of xylan, xylose and arabinose. 0.3g of reaction substrate was charged into the reaction vessel, and 20mL of 70wt.% NaBr solution and 20mL of toluene were added. Hydrogen gas was introduced into the autoclave at 3MPa, and the mixture was reacted at 160℃and 500rpm for 4 hours. The reaction results are shown below.
TABLE 1 preparation of 2-methylfuran by catalytic conversion of xylose with different reaction substrates
Reaction conditions: 160 ℃ and 500rpm reaction for 4 hours
Under the reaction conditions, xylan, xylose and arabinose all produced methyl furan as described in table 1. Wherein cyclopentanone is the major byproduct. As shown in the reaction scheme 1, the method is a reaction scheme for preparing 2-methyl furan by catalytic conversion of xylose. The reaction steps are as follows: 1 xylose undergoes isomerization reaction to generate xylulose; 2, carrying out dehydration reaction on xylulose to generate furfural; furfurol is generated by furfural under the action of a hydrogenation catalyst. After the xylose produces furfuryl alcohol, the reaction route is divided into the following three steps: 1) Furfuryl alcohol is directly hydrogenated to generate tetrahydrofurfuryl alcohol; 2) Hydrodechlorination of furfuryl alcohol to 2-methylfuran (target product); 3) Furfuryl alcohol is dehydrated and hydrogenated to produce cyclopentanone.
Under the reaction system, since the hydrogenation catalyst Pd/C is poisoned by Br in a high-concentration NaBr solution, the transition hydrogenation reaction hardly occurs to produce tetrahydrofurfuryl alcohol. However, the isomerisation dehydration and the rehydrogenation of furfuryl alcohol still form a competitive relationship with the aggressive dechlorination, and cyclopentanone is a major byproduct.
Reaction route 1. Reaction route for preparing dimethylfuran by catalytic conversion of xylose
Examples 4 to 9
The xylose conversion experiments were performed with Pd/C catalyst. 0.3g of the reaction substrate was charged into the reaction vessel, and 20mL of NaBr solution and 20mL of toluene were added. Hydrogen gas was introduced into the autoclave at 3MPa, and the mixture was reacted at 160℃and 500rpm for 4 hours. The reaction results are shown below.
TABLE 2 preparation of 2-methylfuran by catalytic conversion of xylose at different NaBr concentrations [a]
Reaction conditions: 160 ℃ and 500rpm reaction for 4 hours
As shown in Table 2, when the brine concentration was 20wt.%, the product selectivity was poor, and the main products were 2-methyltetrahydrofuran, 2-methylfuran, cyclopentanone, cyclopentanol, tetrahydrofurfuryl alcohol, and xylitol.
In this reaction, the Br in the high concentration NaBr solution acts mainly at the following two points: 1) Facilitating isomerisation of the compound, e.g. isomerisation of xylose to xylulose and isomerisation of furfuryl alcohol to hydroxycyclopentenone; 2) And (3) properly poisoning the catalyst and preventing the transition hydrogenation to products such as 2-methyltetrahydrofuran, xylitol, tetrahydrofurfuryl alcohol and the like. As shown in scheme 1, pd/C will over-hydrogenate the substrate to xylitol, tetrahydrofurfuryl alcohol and cyclopentanol when the concentration of NaBr is too low. Meanwhile, part of furfuryl alcohol which is not subjected to transitional hydrogenation is used as an intermediate and is converted into cyclopentanone and 2-methyl furan. In the reaction system, the isomerization and dehydration, the hydrogenation and the hydrodechlorination of furfuryl alcohol form a competitive relationship. When the halogen ion content was low, the results were shown in example 5 and example 6. Furfuryl alcohol isomerically dehydrates and then hydrogenates to form cyclopentanone. As the concentration of NaBr increases gradually, hydrodechlorination becomes the dominant reaction. This is also why the preparation of 2-methylfuran requires high concentrations of brine in this patent.
Examples 10 to 12
The solubility of NaBr, KCl and KBr in water at 20℃was 90.5g/100mL, 31.5g/100mL and 75.0g/100mL, respectively. The solubility of KCl in water at 100℃can reach 56.7g/100mL. Examples according to the above properties are as follows. The xylose conversion experiments were performed with Pd/C catalyst. 0.3g of the reaction substrate was charged into the reaction vessel, 20mL of distilled water and appropriate amounts of NaBr, KCl and KBr were added, a brine concentration of 50wt.% was required, and then 20mL of toluene was added. Hydrogen gas was introduced into the autoclave at 3MPa, and the mixture was reacted at 160℃and 500rpm for 4 hours. The reaction results are shown below.
TABLE 3 preparation of 2-methylfuran by catalytic conversion of xylose with different salts
Reaction conditions: the reaction was carried out at 160℃and 500rpm for 4 hours.
As shown in table 3, naBr, KCl, KBr all produced 2-methylfuran by catalytic conversion of xylose. The species of the halogen ion are not significantly different in the reaction system. Halogen ions of sufficiently high concentration appear to be an important indicator to facilitate hydrodechlorination reactions. While inhibiting the conversion of xylose to cyclopentanone.
Examples 13 to 16
The xylose conversion experiments were performed with Pd/C catalyst. 0.3g of the reaction substrate was charged into the reaction vessel, and 20mL of 70wt.% NaBr solution and 20mL of an organic solvent were added. Hydrogen gas was introduced into the autoclave at 3MPa, and the mixture was reacted at 160℃and 500rpm for 4 hours. The reaction results are shown below.
TABLE 4 preparation of 2-methylfuran by catalytic conversion of xylose with different reaction substrates
Reaction conditions: 160 ℃ and 500rpm reaction for 4 hours
As shown in the table above, different solvents have little effect on the preparation of 2-methylfuran by catalytic conversion of xylose, and under the four solvent conditions, the xylose can be prepared into 2-methylfuran by catalytic conversion. The highest yield was 82% in toluene solvent.
Examples 17 to 19
Taking Al 2 O 3 1g was added to a beaker; then 0.017g of AuCl was added to another beaker 3 0.493g Ni (NO) 3 ) 26 H 2 O. Adding a certain amount of water to mix the two salts into a uniform solution, and then pouring the solution into a container filled with Al 2 O 3 Is impregnated in equal amounts in the beaker. And placing the sample in a cool and windless place for standing for 24 hours, and then placing the sample in an oven for drying. After the sample is dried, roasting the sample for 4 hours at 400 ℃ in an air atmosphere, and then placing the sample into a tube furnace for reduction for 4 hours at 500 ℃ in a mixed gas of hydrogen and nitrogen. After the reduction is completed and the tube furnace is cooled to room temperature, the sample is passivated for 24 hours under the mixed gas of nitrogen and air. The sample is named NiAu/Al 2 O 3 . And PtCu/Al was prepared in the same manner 2 O 3 RuCu/Al 2 O 3 Catalysts, i.e. using Al 2 O 3 As a carrier, the co-impregnated hair was used.
With Pd/C, niAu/Al 2 O 3 The Pt/C catalyst is used for xylose conversion experiments. 0.3g of reaction substrate was charged into the reaction vessel, and 20mL of 70wt.% NaBr solution and 20mL of toluene were added. Hydrogen gas was introduced into the autoclave at 3MPa, and the mixture was reacted at 160℃and 500rpm for 4 hours. The reaction results are shown below.
TABLE 5 preparation of 2-methylfuran by catalytic conversion of xylose with different reaction substrates
Reaction conditions: 160 ℃ and 500rpm reaction for 4 hours
As shown in the table, all three catalysts in examples 17-19 are metal catalysts with better hydrodechlorination effect, wherein the hydrodechlorination activity of Pd/C is obviously better than that of the other two catalysts.
Examples 22 to 28
The xylose conversion experiments were performed with Pd/C catalyst. 0.3g of reaction substrate was charged into the reaction vessel, and 20mL of 70wt.% NaBr solution and 20mL of toluene were added. Hydrogen was introduced into the reaction vessel, and the mixture was reacted at 160℃and 500rpm for 4 hours. The reaction results are shown below.
TABLE 6 preparation of 2-methylfuran by the catalytic conversion of xylose under different hydrogen pressures
Reaction conditions: 160 ℃ and 500rpm reaction for 4 hours
From the above table, it can be seen that xylose is converted to furfural when the hydrogen pressure is small. As shown in scheme 1, this scheme requires furfuryl alcohol as an intermediate, and therefore requires sufficient hydrogen pressure to promote selective hydrogenation of furfural to furfuryl alcohol. Furfuryl alcohol is subjected to hydrodechlorination to prepare 2-methylfuran. As is clear from the results of the above table, the optimum pressure was 3MPa.
Claims (6)
1. A method for preparing 2-methyl furan from biomass raw materials, which is characterized by comprising the following steps:
the method comprises the steps of (1) adopting a high-concentration halogenated salt water/organic solvent two-phase system and a common hydrodechlorination catalyst, and directly converting reaction raw materials into 2-methylfuran through one-step hydrodechlorination reaction by isomerism and dehydration under a hydrogen atmosphere and at a specific reaction temperature;
the reaction raw material is hemicellulose component of biomass species and monomer thereof, and comprises one or more than two mixtures of xylose and arabinose species;
the high concentration brine is a brine salt concentration of at least 50wt.%.
2. The method according to claim 1, wherein:
the halide salt comprises one or more of KCl, KBr and NaBr.
3. The method according to claim 1, wherein:
the organic solvent in the two-phase system of halogenated brine/organic solvent is various organic solvents which have extraction function and are not mutually soluble with brine, and the solvents comprise toluene, methyltetrahydrofuran, tetrahydrofuran and methyl isobutyl ketone.
4. The method as claimed in claim 1, wherein:
the common hydrodechlorination catalysts include: pd/C, niAu catalyst, pt/C, pdCu catalyst and RuCu catalyst.
5. The method according to claim 1, wherein:
under the hydrogen atmosphere, the hydrogen pressure is 2-8 MPa, and the reaction temperature is 140-240 ℃.
6. The method according to claim 1, wherein:
the volume ratio of the halogenated brine to the organic solvent is 1:10 to 1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310832180.9A CN116925014A (en) | 2023-07-07 | 2023-07-07 | Method for preparing 2-methyl furan from biomass raw material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310832180.9A CN116925014A (en) | 2023-07-07 | 2023-07-07 | Method for preparing 2-methyl furan from biomass raw material |
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| CN116925014A true CN116925014A (en) | 2023-10-24 |
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| CN202310832180.9A Pending CN116925014A (en) | 2023-07-07 | 2023-07-07 | Method for preparing 2-methyl furan from biomass raw material |
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