WO2016080839A1 - Production of furans - Google Patents
Production of furans Download PDFInfo
- Publication number
- WO2016080839A1 WO2016080839A1 PCT/NL2015/050816 NL2015050816W WO2016080839A1 WO 2016080839 A1 WO2016080839 A1 WO 2016080839A1 NL 2015050816 W NL2015050816 W NL 2015050816W WO 2016080839 A1 WO2016080839 A1 WO 2016080839A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tetrahydroxybutane
- furan
- previous
- catalyst
- acid
- Prior art date
Links
- 150000002240 furans Chemical class 0.000 title abstract description 6
- 238000004519 manufacturing process Methods 0.000 title description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 84
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims abstract description 49
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- PAQZWJGSJMLPMG-UHFFFAOYSA-N 2,4,6-tripropyl-1,3,5,2$l^{5},4$l^{5},6$l^{5}-trioxatriphosphinane 2,4,6-trioxide Chemical compound CCCP1(=O)OP(=O)(CCC)OP(=O)(CCC)O1 PAQZWJGSJMLPMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 229940071870 hydroiodic acid Drugs 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007848 Bronsted acid Substances 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000003586 protic polar solvent Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000002028 Biomass Substances 0.000 abstract description 12
- 229920005862 polyol Polymers 0.000 abstract description 2
- 150000003077 polyols Chemical class 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 11
- 235000019414 erythritol Nutrition 0.000 description 10
- 239000004386 Erythritol Substances 0.000 description 9
- 229940009714 erythritol Drugs 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000000346 sugar Nutrition 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 3
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UNXHWFMMPAWVPI-QWWZWVQMSA-N D-threitol Chemical compound OC[C@@H](O)[C@H](O)CO UNXHWFMMPAWVPI-QWWZWVQMSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000006324 decarbonylation Effects 0.000 description 2
- 238000006606 decarbonylation reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000003133 Elaeis guineensis Species 0.000 description 1
- 235000001950 Elaeis guineensis Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- UNXHWFMMPAWVPI-IMJSIDKUSA-N L-threitol Chemical compound OC[C@H](O)[C@@H](O)CO UNXHWFMMPAWVPI-IMJSIDKUSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- FTGDANDPNJTDHA-UHFFFAOYSA-N O1C=CC=C1.CCCC Chemical compound O1C=CC=C1.CCCC FTGDANDPNJTDHA-UHFFFAOYSA-N 0.000 description 1
- RRADGHCTSAIUBJ-QDVFRVIPSA-N OC(C(C)(O)O)(C)O.C([C@H](O)[C@@H](O)CO)O.C([C@@H](O)[C@H](O)CO)O Chemical compound OC(C(C)(O)O)(C)O.C([C@H](O)[C@@H](O)CO)O.C([C@@H](O)[C@H](O)CO)O RRADGHCTSAIUBJ-QDVFRVIPSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000005293 duran Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000105 evaporative light scattering detection Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 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
-
- 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
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no 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
- C07D307/08—Preparation of tetrahydrofuran
Definitions
- the invention relates to obtaining furans from biomass.
- the invention relates to obtaining furans from polyols, such as tetr ahy droxybutane .
- Furan is an important base chemical. It serves e.g. as a building block in the production of several specialty chemicals.
- a current process for the production of furan is a heavy metal (e.g. copper) catalyzed oxidation of 1,3-butadiene.
- 1,3-Butadiene is obtained from fossil feedstock such as natural oil and gas. Due to the depletion of the fossil feedstock, alternative sources and methods for the production of furan are desired.
- Biomass is considered to advantageously lack many of the drawbacks of fossil feedstock. It is renewable, its use does not increase the C02-levels in the atmosphere, and processing of biomass is less harmful to the environment. Biomass may be obtained as dead trees, yard clippings, wood chips, plant residues or even municipal solid waste and the like.
- biomass is actively produced as corn, sugarcane, bamboo and the like or as a variety of tree species such as oil palm (palm oil).
- a major component of biomass is polymeric sugar such as starch, cellulose and hemi-cellulose.
- sugars such as glucose and xylose, as well as sugar derivatives such as erythritol, can be obtained.
- Erythritol is a 1,2,3,4-tetrahydroxybutane. Apart from erythritol, there are two more isomers of 1,2,3,4-tetrahydroxybutane: D-threitol and L- threitol. In the context of the present invention these three isomers will be referred to as tetr ahy droxybutane. These compounds have structures according to the following formulae:
- a current process for the preparation of furan aiming to take advantage of the favorable properties of biomass, is the decarbonylation of furfural.
- Furfural can be obtained from e.g. xylose which is obtainable from biomass.
- a two-step process is required.
- the present invention is directed to the preparation of furan directly from a sugar derivative which is obtainable from biomass, thus no intermediate step or compound is required.
- the present invention is directed to a reaction according to the following scheme:
- Atom-efficiency expresses the efficiency with which atoms from the starting material are incorporated into the final product. The higher the atom-efficiency of a reaction, the less waste typically results from that reaction.
- xylose C5H10O5
- furan C4H4O
- CH6O4 is rejected throughout the processes as waste in the form of carbon monoxide (CO) and water (3x H2O).
- CO carbon monoxide
- 3x H2O water
- CO is emitted, as is generally the case in the process of decarbonylation of furfural.
- Required safety measures for the present invention may therefore be less strict.
- WO-A-03/042200 discloses the use of erythritol as starting material for the synthesis of tetrahydrofuran (THF) under hydrogenation conditions in the presence of a rhenium catalyst. Furan is an intermediate in this process and is accidentally obtained only as a minor side product.
- US4939277 discloses the reaction of erythritol to cis-3,4- dimethoxytetrahydrofuran under acidic conditions. No furan is obtained.
- the present invention does not require hydrogenation conditions. It neither requires presence of a rhenium catalyst or any other heavy metals. For these reasons, the present invention is environmentally more benign and operationally more simple.
- the present invention is thus directed to a method to obtain furan comprising providing the tetrahydroxybutane and converting the
- the environmental friendliness is a major advantage of the present invention, i.e. the present invention is particularly green. No heavy metals, toxic solvents or explosive gasses are required.
- the tetrahydroxybutane is dissolved in a solvent.
- the solvent is a green solvent, viz. a solvent that is known to be environmentally friendly. Green solvents are for instance water, acetone, methyl ethyl ketone, ethyl acetate, isopropyl acetate, and Ci- C 4 alcohols such as ethanol, methanol, propanols and butanols.
- Organic solvent such as diethyl ether, dichloromethane and dioxane are not considered to be green solvents and are therefore less preferred.
- polar solvents for efficient conversions of the tetrahydroxybutane to furan, polar solvents, in particular polar protic solvents, are preferred. Most preferably, water is used as the solvent. Water is additionally advantageous because many components from biomass dissolve readily in water or already contain amounts of water.
- polar solvents are dimethyl sulfoxide (DMSO), N- methylpyrrolidone (NMP) and dimethyl formaldehyde (DMF). These are also suitable for the present invention, however, these solvents are currently less preferred as they are currently not considered to be green. In a particular embodiment of the present invention, two or more solvents may be combined and used as such.
- DMSO dimethyl sulfoxide
- NMP N- methylpyrrolidone
- DMF dimethyl formaldehyde
- Preferred concentrations of the tetrahydroxybutane in the solvent are 1 to 1500 g/L, preferably, 2 to 500 g/L, more preferably 4 to 200 g/L, most preferably about 10 g/L.
- This concentration may be kept constant by constantly feeding tetrahydroxybutane to the process in the case of a continuous process.
- the concentration may be an initial concentration of the tetrahydroxybutane i.e. the concentration at the start of the conversion of the tetrahydroxybutane to fur an.
- a dehydration reaction is required for the tetrahydroxybutane to be converted to furan.
- This reaction can typically be catalyzed by an acid or a base.
- the catalyst is typically an acid or a base, preferably a Bronsted acid.
- Anhydrides may also be suitable as catalyst.
- simple mineral acids such as sulfuric acid and/or phosphoric acid, can effectively catalyze the conversion of the tetrahydroxybutane to furan.
- the catalyst is immobilized on a solid support such as silica, aluminate, zirconia, zeolite, carbon, polymer or the like.
- Preferred catalysts are selected from the group consisting of sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, acetic acid, formic acid, propylphosphonic anhydride, and combinations thereof.
- the catalyst is an acid, the acidity of the catalyst was found to be of considerable importance.
- the catalyst preferably has a pKa of less than 4, more preferably less than 2, for instance from 0.5 to 1.5.
- the catalyst is preferably present in an amount of 1 - 25 wt%, preferably 3 - 20 wt%, most preferably about 15 wt%.
- the amount of catalyst is expressed in wt% of reaction mixture at the start of the process.
- the reaction mixture consists essentially of the starting materials, the catalyst and the optional solvent.
- the tetrahydroxybutane is preferably heated in the presence of the catalyst to a temperature of at least 150 °C, preferably between 150 and 300 °C, even more preferably between 150 and 250 °C, even more preferably between 175 and 225 °C, most preferably to about 220 °C.
- Heating can be realized by external stimulation with a variety of heat sources. It was found that heating by microwave irradiation was particularly advantageous.
- the heating of tetrahydroxybutane is typically maintained for a specific time period.
- the tetrahydroxybutane is heated in the presence of the catalyst for a period that depends on the type of heating.
- heating is typically performed for a period of 1 to 60 minutes, preferably 5 to 30 minutes, more preferably between 10 and 20 minutes, most preferably about 16 minutes.
- the time period may be different, in particular longer time periods may be required compared to when heating by microwave irradiation.
- pressure By heating the tetrahydroxybutane in a closed system to certain temperatures, pressure may increase. This may in particular occur when a solvent is present.
- the pressure may be controlled by a variety of methods. For instance, the size of the closed system may be varied or a valve may be present to regulate the escaping of gas. Alternatively, a gas may be introduced to increase the pressure. It was found that the conversion is preferably performed at a pressure, typically at 0 to 200 bar. Preferably the pressure is 5 to 50 bar, more preferably 10 to 30 bar, most preferably about 20 bar.
- the furan is selectively evaporated.
- Furan has a relatively low boiling point of about 31 °C, while for instance erythritol has a boiling point of about 330 °C.
- Reaction intermediates will most likely have boiling points in between those of furan and the
- the conversion of the tetrahydroxybutane to furan may also be facilitated by the selective evaporation of the furan. This may result in a more efficient conversion.
- reaction equilibrium may be pulled to the side of the furan. For instance through a continuous process in which the furan is selectively removed once it is formed, e.g. through pervaporation or distillation procedures. Moreover, the residence time of the furan in the reaction, i.e. the time that the furan is in contact with the catalyst under reaction conditions, such as high temperatures, may be reduced. This may prevent decomposition and, as such, increase conversion efficiency.
- a high conversion is advantageous for the ease of isolation of the furan.
- the conversion is relatively low, e.g. 1-2 mol%, isolation is more cumbersome than when the conversion is relatively high. Therefore, the tetrahydroxybutane is preferably converted to furan in a conversion of at least 5 mol%, preferably at least 15 mol%, more preferably at least 30 mol%.
- Isolation of the furan may be effected by distillation. Distillation may be performed during the reaction process or it may be performed at the end of the reaction process.
- a high concentration of the furan in the solvent is advantageous for an efficient isolation of the furan. This is
- concentration of the furan is at least 100 ⁇ g/L, preferably at least 500 ⁇ g/L, more preferably at least 900 ⁇ g/L.
- mol% means molecular percentage. As such, conversion is expressed as the percentage starting materials molecules that are converted to product molecules.
- Reaction mixtures were prepared according to the following procedure.
- 500 mL duran bottles were charged with either 5, 50 or 725 gram of erythritol and a 1 wt.%, 3 wt.% or 15wt.% H2SO4 solution such that a total volume of 500 mL was obtained.
- the bottle was placed in an ultrasonic bath, connected to a vacuum pump and evacuated during 15 min while the ultrasonic batch was turned on. Next, the headspace of the bottle was flushed with nitrogen and the cap of the bottle was replaced by a septum.
- a reaction vessel was charged with 10 mL of the prepared reaction mixture and sealed with a septum.
- the reaction vessel was loaded in a microwave (Monowave 300 from Anton Paar GmbH, Austria).
- the desired temperature and reaction time were programmed in the microwave according to Table 1 and the reaction was started.
- reaction vessel was removed from the microwave, cooled and the gas in the headspace of the reaction vessel was transferred to a headspace vial for analysis.
- the furan concentration in both the liquid and the gas resulting from the reaction was determined by a gas chromatography/mass
- GC-MS spectroscopy apparatus
- Mass spectroscopy was performed on a Agilent 5973N MSD, with an EI ionization modus and mass detection range of 25-550 m/z.
- the liquid resulting from the reaction was prepared for GS-MS analysis by extracting 1 mL reaction mixture with 1 mL dichlorom ethane or ethyl acetate and injecting the organic layer in the GS-MS.
- Example 1 was repeated using different acids than H2SO4.
- the use of hydroiodic acid (HI), phosphoric acid (H3PO4) and hydrochloric acid produced similar results as in Example 1.
- furan may be obtained using different concentrations of erythritol, different acids and acid concentrations at various temperatures for various reaction times.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to obtaining furans from biomass. In particular, the invention relates to obtaining furans from polyols, such as tetrahydroxybutane. In accordance with the invention tetrahydroxybutane is converted to furan in the presence of a catalyst. The tetrahydroxybutane may be dissolved in a solvent such as water.
Description
Title: Production of furans
The invention relates to obtaining furans from biomass. In particular, the invention relates to obtaining furans from polyols, such as tetr ahy droxybutane .
Furan is an important base chemical. It serves e.g. as a building block in the production of several specialty chemicals. A current process for the production of furan is a heavy metal (e.g. copper) catalyzed oxidation of 1,3-butadiene. 1,3-Butadiene is obtained from fossil feedstock such as natural oil and gas. Due to the depletion of the fossil feedstock, alternative sources and methods for the production of furan are desired.
Biomass is considered to advantageously lack many of the drawbacks of fossil feedstock. It is renewable, its use does not increase the C02-levels in the atmosphere, and processing of biomass is less harmful to the environment. Biomass may be obtained as dead trees, yard clippings, wood chips, plant residues or even municipal solid waste and the like.
Alternatively, biomass is actively produced as corn, sugarcane, bamboo and the like or as a variety of tree species such as oil palm (palm oil).
A major component of biomass is polymeric sugar such as starch, cellulose and hemi-cellulose. By processing biomass, sugars such as glucose and xylose, as well as sugar derivatives such as erythritol, can be obtained.
Erythritol is a 1,2,3,4-tetrahydroxybutane. Apart from erythritol, there are two more isomers of 1,2,3,4-tetrahydroxybutane: D-threitol and L- threitol. In the context of the present invention these three isomers will be referred to as tetr ahy droxybutane. These compounds have structures according to the following formulae:
erythritol D-threitol L-threitol tetrahydroxybutane
A current process for the preparation of furan, aiming to take advantage of the favorable properties of biomass, is the decarbonylation of furfural. Furfural can be obtained from e.g. xylose which is obtainable from biomass. Hence, a two-step process is required. The present invention is directed to the preparation of furan directly from a sugar derivative which is obtainable from biomass, thus no intermediate step or compound is required. Hence, the present invention is directed to a reaction according to the following scheme:
tetrahydrox butane furan
Such a process is highly advantageous since it allows for less process steps and a higher atom-efficiency. Atom-efficiency expresses the efficiency with which atoms from the starting material are incorporated into the final product. The higher the atom-efficiency of a reaction, the less waste typically results from that reaction. In a process wherein xylose (C5H10O5) is the starting material for furan (C4H4O), CH6O4 is rejected throughout the processes as waste in the form of carbon monoxide (CO) and water (3x H2O). However, in a process wherein the tetrahydroxybutane (C4H10O4) is the starting material for furan, only three water molecules (3x H2O) are rejected as waste. When dealing with small molecular weights, as is the case for the present invention, this results in a significant improvement in atom- efficiency, which may be more than 34% in accordance with the present invention.
An additional advantage of the present invention is that no toxic
CO is emitted, as is generally the case in the process of decarbonylation of
furfural. Required safety measures for the present invention may therefore be less strict.
WO-A-03/042200 discloses the use of erythritol as starting material for the synthesis of tetrahydrofuran (THF) under hydrogenation conditions in the presence of a rhenium catalyst. Furan is an intermediate in this process and is accidentally obtained only as a minor side product.
US4939277 discloses the reaction of erythritol to cis-3,4- dimethoxytetrahydrofuran under acidic conditions. No furan is obtained.
The present invention does not require hydrogenation conditions. It neither requires presence of a rhenium catalyst or any other heavy metals. For these reasons, the present invention is environmentally more benign and operationally more simple.
The present invention is thus directed to a method to obtain furan comprising providing the tetrahydroxybutane and converting the
tetrahydroxybutane to furan in the presence of a catalyst, wherein the tetrahydroxybutane is heated in the presence of the catalyst to a
temperature of at least 130 °C. Preferably this conversion is carried out in a single step.
The environmental friendliness is a major advantage of the present invention, i.e. the present invention is particularly green. No heavy metals, toxic solvents or explosive gasses are required. In a preferred embodiment of the present invention, the tetrahydroxybutane is dissolved in a solvent. Preferably the solvent is a green solvent, viz. a solvent that is known to be environmentally friendly. Green solvents are for instance water, acetone, methyl ethyl ketone, ethyl acetate, isopropyl acetate, and Ci- C4 alcohols such as ethanol, methanol, propanols and butanols. Organic solvent such as diethyl ether, dichloromethane and dioxane are not considered to be green solvents and are therefore less preferred.
For efficient conversions of the tetrahydroxybutane to furan, polar solvents, in particular polar protic solvents, are preferred. Most preferably,
water is used as the solvent. Water is additionally advantageous because many components from biomass dissolve readily in water or already contain amounts of water.
Examples of polar solvents are dimethyl sulfoxide (DMSO), N- methylpyrrolidone (NMP) and dimethyl formaldehyde (DMF). These are also suitable for the present invention, however, these solvents are currently less preferred as they are currently not considered to be green. In a particular embodiment of the present invention, two or more solvents may be combined and used as such.
Preferred concentrations of the tetrahydroxybutane in the solvent are 1 to 1500 g/L, preferably, 2 to 500 g/L, more preferably 4 to 200 g/L, most preferably about 10 g/L. This concentration may be kept constant by constantly feeding tetrahydroxybutane to the process in the case of a continuous process. Alternatively, in the case of e.g. a batch process, the concentration may be an initial concentration of the tetrahydroxybutane i.e. the concentration at the start of the conversion of the tetrahydroxybutane to fur an.
For the tetrahydroxybutane to be converted to furan, a dehydration reaction is required. This reaction can typically be catalyzed by an acid or a base. Hence, for the present invention the catalyst is typically an acid or a base, preferably a Bronsted acid. Anhydrides may also be suitable as catalyst. The inventors found that simple mineral acids, such as sulfuric acid and/or phosphoric acid, can effectively catalyze the conversion of the tetrahydroxybutane to furan. Optionally, the catalyst is immobilized on a solid support such as silica, aluminate, zirconia, zeolite, carbon, polymer or the like.
Preferred catalysts are selected from the group consisting of sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, acetic acid, formic acid, propylphosphonic anhydride, and combinations thereof.
In case the catalyst is an acid, the acidity of the catalyst was found to be of considerable importance. The catalyst preferably has a pKa of less than 4, more preferably less than 2, for instance from 0.5 to 1.5.
The catalyst is preferably present in an amount of 1 - 25 wt%, preferably 3 - 20 wt%, most preferably about 15 wt%. The amount of catalyst is expressed in wt% of reaction mixture at the start of the process. The reaction mixture consists essentially of the starting materials, the catalyst and the optional solvent.
Without heating the tetrahydroxybutane the conversion to furan is relatively slow. Therefore, in accordance with the present invention the tetrahydroxybutane is preferably heated in the presence of the catalyst to a temperature of at least 150 °C, preferably between 150 and 300 °C, even more preferably between 150 and 250 °C, even more preferably between 175 and 225 °C, most preferably to about 220 °C.
Heating can be realized by external stimulation with a variety of heat sources. It was found that heating by microwave irradiation was particularly advantageous.
The heating of tetrahydroxybutane is typically maintained for a specific time period. Typically, the tetrahydroxybutane is heated in the presence of the catalyst for a period that depends on the type of heating. When microwave irradiation is used, heating is typically performed for a period of 1 to 60 minutes, preferably 5 to 30 minutes, more preferably between 10 and 20 minutes, most preferably about 16 minutes.
When heating by thermal heating (viz. electric heating, heating by gas flame, and the like), the time period may be different, in particular longer time periods may be required compared to when heating by microwave irradiation.
By heating the tetrahydroxybutane in a closed system to certain temperatures, pressure may increase. This may in particular occur when a solvent is present. The pressure may be controlled by a variety of methods.
For instance, the size of the closed system may be varied or a valve may be present to regulate the escaping of gas. Alternatively, a gas may be introduced to increase the pressure. It was found that the conversion is preferably performed at a pressure, typically at 0 to 200 bar. Preferably the pressure is 5 to 50 bar, more preferably 10 to 30 bar, most preferably about 20 bar.
In particular embodiments, the furan is selectively evaporated. Furan has a relatively low boiling point of about 31 °C, while for instance erythritol has a boiling point of about 330 °C. Reaction intermediates will most likely have boiling points in between those of furan and the
tetrahydroxybutane. These differences in boiling point allow for a selective evaporation, i.e. distillation of the furan during the conversion of the tetrahydroxybutane to furan. Advantageously, because of this selective evaporation, furan may be directly obtained as a major component.
Furthermore, the conversion of the tetrahydroxybutane to furan may also be facilitated by the selective evaporation of the furan. This may result in a more efficient conversion.
Without wishing to be bound by theory, the inventors believe that the reaction equilibrium may be pulled to the side of the furan. For instance through a continuous process in which the furan is selectively removed once it is formed, e.g. through pervaporation or distillation procedures. Moreover, the residence time of the furan in the reaction, i.e. the time that the furan is in contact with the catalyst under reaction conditions, such as high temperatures, may be reduced. This may prevent decomposition and, as such, increase conversion efficiency.
A high conversion is advantageous for the ease of isolation of the furan. When the conversion is relatively low, e.g. 1-2 mol%, isolation is more cumbersome than when the conversion is relatively high. Therefore, the tetrahydroxybutane is preferably converted to furan in a conversion of at least 5 mol%, preferably at least 15 mol%, more preferably at least 30 mol%.
Isolation of the furan may be effected by distillation. Distillation may be performed during the reaction process or it may be performed at the end of the reaction process. For an efficient isolation of the furan, a high concentration of the furan in the solvent is advantageous. This is
particularly the case if the distillation is performed at the end of the reaction process. Therefore, in a preferred embodiment, the final
concentration of the furan is at least 100 μg/L, preferably at least 500 μg/L, more preferably at least 900 μg/L.
In the context of this invention, mol% means molecular percentage. As such, conversion is expressed as the percentage starting materials molecules that are converted to product molecules.
For the purpose of clarity and a concise description, features are described herein as part of the same or separate embodiments. However, it will be appreciated that the scope of the invention may include
embodiments having combinations of all or some of the features described.
The invention is further illustrated by the following experimental examples. Example 1
Preparation
Reaction mixtures were prepared according to the following procedure.
Solutions of sulfuric acid (H2SO4) in water were prepared to obtain 1 wt.%, 3 wt.% and 15 wt.% aqueous H2SO4 solutions.
500 mL duran bottles were charged with either 5, 50 or 725 gram of erythritol and a 1 wt.%, 3 wt.% or 15wt.% H2SO4 solution such that a total volume of 500 mL was obtained. The bottle was placed in an ultrasonic bath, connected to a vacuum pump and evacuated during 15 min while the
ultrasonic batch was turned on. Next, the headspace of the bottle was flushed with nitrogen and the cap of the bottle was replaced by a septum.
Reaction
In an anaerobic glovebox, a reaction vessel was charged with 10 mL of the prepared reaction mixture and sealed with a septum. The reaction vessel was loaded in a microwave (Monowave 300 from Anton Paar GmbH, Austria). The desired temperature and reaction time were programmed in the microwave according to Table 1 and the reaction was started.
Sample preparation and analysis
After completion of the programmed reaction time, the reaction vessel was removed from the microwave, cooled and the gas in the headspace of the reaction vessel was transferred to a headspace vial for analysis. The furan concentration in both the liquid and the gas resulting from the reaction was determined by a gas chromatography/mass
spectroscopy apparatus (GC-MS) using standard techniques.
Gas chromatography was performed on a HP6890 with a Factorfour VF-1301 column of 30 m * 0.25 mm, df. 1 μιη, with helium as the carrier gas using an optimized temperature program.
Mass spectroscopy was performed on a Agilent 5973N MSD, with an EI ionization modus and mass detection range of 25-550 m/z.
The liquid resulting from the reaction was prepared for GS-MS analysis by extracting 1 mL reaction mixture with 1 mL dichlorom ethane or ethyl acetate and injecting the organic layer in the GS-MS.
Results
Results of the experiments are shown in Table 1.
Table 1
Example 2
Example 1 was repeated using different acids than H2SO4. The use of hydroiodic acid (HI), phosphoric acid (H3PO4) and hydrochloric acid produced similar results as in Example 1.
From the results of Examples 1 and 2 it may be derived that furan may be obtained using different concentrations of erythritol, different acids and acid concentrations at various temperatures for various reaction times.
Claims
1. Method to obtain furan comprising providing tetrahydroxybutane and converting said tetrahydroxybutane to furan in the presence of a catalyst, wherein the tetrahydroxybutane is heated in the presence of the catalyst to a temperature of at least 130 °C.
2. Method according to the previous claim, wherein the
tetrahydroxybutane is dissolved in a solvent, preferably a polar solvent, more preferably a polar protic solvent, most preferably water.
3. Method according to any of the previous claims, wherein the tetrahydroxybutane is heated in the presence of the catalyst to a
temperature of at least 150 °C, preferably between 150 and 300 °C, more preferably between 150 and 250 °C, even more preferably between 175 and 225 °C, most preferably about 220 °C.
4. Method according to any of the previous claims, wherein the tetrahydroxybutane is heated in the presence of the catalyst for a period of 1 to 60 minutes, preferably 5 to 30 minutes, more preferably between 10 and 20 minutes, most preferably about 16 minutes.
5. Method according to any of the previous claims, wherein the catalyst is an acid, base or an anhydride, preferably a Bronsted acid having a pKa of less than 4, preferably less than 2, and is optionally immobilized on a solid support.
6. Method according to any of the previous claims, wherein the catalyst is preferably selected from the group consisting of sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, acetic acid, formic acid, propylphosphonic anhydride and combinations thereof.
7. Method according to any of the previous claims, wherein the tetrahydroxybutane is dissolved in the solvent in an concentration of 1 to 1450 g/L, preferably, 2 to 500 g/L, more preferably 4 to 200 g/L, most preferably about 10 g/L.
8. Method according to any of the previous claims, wherein the tetrahydroxybutane is heated by microwave irradiation.
9. Method according to any of the previous claims, wherein the tetrahydroxybutane is converted to furan at a pressure of 0 to 200 bar, preferably 5 to 50 bar, more preferably 10 to 30 bar, most preferably about 20 bar.
10. Method according to any of the previous claims, wherein furan is selectively evaporated from the reaction mixture.
11. Method according to any of the previous claims, wherein the tetrahydroxybutane is converted to furan in a conversion of at least 5 mol%, preferably at least 15 mol%, more preferably at least 30%.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/526,022 US10100025B2 (en) | 2014-11-20 | 2015-11-20 | Production of furans |
EP15828687.2A EP3230269A1 (en) | 2014-11-20 | 2015-11-20 | Production of furans |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14194062 | 2014-11-20 | ||
EP14194062.7 | 2014-11-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016080839A1 true WO2016080839A1 (en) | 2016-05-26 |
Family
ID=51951673
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL2015/050816 WO2016080839A1 (en) | 2014-11-20 | 2015-11-20 | Production of furans |
Country Status (3)
Country | Link |
---|---|
US (1) | US10100025B2 (en) |
EP (1) | EP3230269A1 (en) |
WO (1) | WO2016080839A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11261198B2 (en) | 2016-06-20 | 2022-03-01 | Shionogi & Co., Ltd. | Process for preparing substituted polycyclic pyridone derivative and crystal thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114705769B (en) * | 2022-03-04 | 2022-10-28 | 石家庄四药有限公司 | Method for detecting related substances in isopropyl tropine |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4939277A (en) | 1987-08-11 | 1990-07-03 | Mitsubishi Kasei Corporation | Tetrahydrofuran derivatives and process for their production |
WO2003042200A1 (en) | 2001-11-13 | 2003-05-22 | E.I. Du Pont De Nemours And Company | Conversion of tetrahydroxybutane to tetrahydrofuran |
-
2015
- 2015-11-20 WO PCT/NL2015/050816 patent/WO2016080839A1/en active Application Filing
- 2015-11-20 EP EP15828687.2A patent/EP3230269A1/en not_active Withdrawn
- 2015-11-20 US US15/526,022 patent/US10100025B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4939277A (en) | 1987-08-11 | 1990-07-03 | Mitsubishi Kasei Corporation | Tetrahydrofuran derivatives and process for their production |
WO2003042200A1 (en) | 2001-11-13 | 2003-05-22 | E.I. Du Pont De Nemours And Company | Conversion of tetrahydroxybutane to tetrahydrofuran |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11261198B2 (en) | 2016-06-20 | 2022-03-01 | Shionogi & Co., Ltd. | Process for preparing substituted polycyclic pyridone derivative and crystal thereof |
US11807648B2 (en) | 2016-06-20 | 2023-11-07 | Shionogi & Co., Ltd. | Process for preparing substituted polycyclic pyridone derivative and crystal thereof |
Also Published As
Publication number | Publication date |
---|---|
US20170320843A1 (en) | 2017-11-09 |
US10100025B2 (en) | 2018-10-16 |
EP3230269A1 (en) | 2017-10-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Brand et al. | Liquefaction of major lignocellulosic biomass constituents in supercritical ethanol | |
Galletti et al. | A sustainable process for the production of γ-valerolactone by hydrogenation of biomass-derived levulinic acid | |
Verma et al. | Sustainable pathway to furanics from biomass via heterogeneous organo-catalysis | |
Xiujuan et al. | Properties of bio-oil from fast pyrolysis of rice husk | |
Wang et al. | Graphene oxide catalyzed dehydration of fructose into 5‐hydroxymethylfurfural with isopropanol as cosolvent | |
Wang et al. | Conversion of carbohydrates into 5-hydroxymethylfurfural in an advanced single-phase reaction system consisting of water and 1, 2-dimethoxyethane | |
Abou-Yousef et al. | Rapid conversion of cellulose to 5-hydroxymethylfurfural using single and combined metal chloride catalysts in ionic liquid | |
WO2010033512A1 (en) | Improved process for preparing bio-oils from biomass | |
EP3587431B1 (en) | Method for preparing levoglucosenone by catalytic pyrolysis of biomass | |
Peng et al. | Facile and efficient conversion of furfuryl alcohol into n-butyl levulinate catalyzed by extremely low acid concentration | |
Remón et al. | Simultaneous production of lignin and polysaccharide rich aqueous solutions by microwave-assisted hydrothermal treatment of rapeseed meal | |
Fu et al. | Enhancing and upgrading bio-oil during catalytic pyrolysis of cellulose: the synergistic effect of potassium cation and different anions impregnation | |
Abou-Yousef | Efficient utilization of aqueous phase bio-oil to furan derivatives through extraction and sugars conversion in acid-catalyzed biphasic system | |
Ma et al. | Directional liquefaction of lignocellulosic biomass for value added monosaccharides and aromatic compounds | |
Shi et al. | Direct degradation of cellulose to 5-hydroxymethylfurfural in hot compressed steam with inorganic acidic salts | |
Cai et al. | Conversion of cellulose to 5-hydroxymethylfurfural using inorganic acidic catalysts in the presence of pressurized water steam | |
US10100025B2 (en) | Production of furans | |
Zhou et al. | Catalytic fast pyrolysis of herbal medicine wastes over zeolite catalyst for aromatic hydrocarbons production | |
CN101628902B (en) | Glucose is the method for preparing 5-hydroxymethylfurfural as raw material | |
Feng et al. | One-step method to produce methyl-D-glucoside from lignocellulosic biomass | |
CN103626808B (en) | A kind of green method preparing the levoglucosenone of high added value | |
Mohamad et al. | Furfural production under subcritical alcohol conditions: effect of reaction temperature, time, and types of alcohol | |
Amarasekara et al. | γ-Valerolactone from pyrolysis of calcium salts of levulinic-formic acid mixtures derived from cellulose | |
CN107083254B (en) | A method of utilizing gamma-valerolactone liquid fuel was prepared | |
Garrido et al. | Influences of zinc chloride on fast pyrolysis of pinewood |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15828687 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15526022 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2015828687 Country of ref document: EP |