CN108178725A - Process for producing levulinic acid from furfural - Google Patents
Process for producing levulinic acid from furfural Download PDFInfo
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- CN108178725A CN108178725A CN201711293617.7A CN201711293617A CN108178725A CN 108178725 A CN108178725 A CN 108178725A CN 201711293617 A CN201711293617 A CN 201711293617A CN 108178725 A CN108178725 A CN 108178725A
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- Prior art keywords
- catalyst
- range
- levulic acid
- furfural
- organic solvent
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 62
- 230000008569 process Effects 0.000 title abstract description 9
- 229940040102 levulinic acid Drugs 0.000 title abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- UNRNJMFGIMDYKL-UHFFFAOYSA-N aluminum copper oxygen(2-) Chemical compound [O-2].[Al+3].[Cu+2] UNRNJMFGIMDYKL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010457 zeolite Substances 0.000 claims abstract description 16
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052596 spinel Inorganic materials 0.000 claims description 8
- 239000011029 spinel Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910018565 CuAl Inorganic materials 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 239000000356 contaminant Substances 0.000 abstract 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 140
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- 235000000346 sugar Nutrition 0.000 description 8
- 239000007789 gas Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910018576 CuAl2O4 Inorganic materials 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 229960004063 propylene glycol Drugs 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002402 hexoses Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas 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
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- -1 hydrogen furans Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229940058352 levulinate Drugs 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- 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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention aims to develop a method for producing levulinic acid from furfural. The method has good stability to contaminants in the precursor. Therefore, it is not necessary to install a purifier. Furthermore, the process gives levulinic acid in good yield and the catalyst used in the process can be recycled. The method comprises the following steps: a) a solution of 0.5 to 3 moles of furfural in an organic solvent and 10 to 40 bar of hydrogen and a copper aluminum oxide catalyst (CuAl) at a temperature in the range of 120 to 200 DEG C2O4) Contacting for 1 to 4 hours; and b) contacting the product from step a) with a catalyst selected from MFI zeolite catalysts in a solvent selected from an organic solvent, water or a mixture of said solvents for 1 to 4 hours at a temperature in the range of 100 ℃ to 150 ℃.
Description
Technical field
The chemical process of the application is related to the method from furfural production levulic acid.
Background technology
At present, release of the greenhouse gases into air can be reduced, therefore to being given birth to from plant with raw material due to the use of in carbon
Substance produces bio-fuel and basic chemical is increasing sharply as the interest of Petroleum Production substitute.
Efficient production process in biorefinery is that the chemical composition from biomass is included fuel, chemicals, material
The process that the product of material and the energy etc. is integrated with the byproduct in nearly nil waste technique improves raw material with maximal efficiency and is worth.
This is all compelling mode in technology and economic aspect.
All base plants biomass are made of three key components, they are 1) celluloses, 2) hemicellulose and 3) wooden
Quality.When the separation and chemistry that these compositions carried out with lignin or biodialysis, the key component obtained includes penta
Sugar and hexose, wherein each described sugar can be converted to multifunctional chemical structural unit (chemical building block)
(such as levulic acid), can generate it is many industry in many value added chemicals (such as diphenoliac acid, methyltetrahydrofuran and
Valerolactone or for further producing polymer or plastics).
Levulic acid can be prepared by hexose or from as the C6 sugar derivatives of edible carbohydrates.Therefore, using C6 sugar
The price of table sugar may be influenced as precursor, and the C5 sugar from biomass is also used as the precursor of production levulic acid.
Therefore, the interest studied using C5 sugar as the precursor of industrial production levulic acid is increasing sharply.It can be taken off by acid catalysis
C5 sugar is converted into furfural by water reaction, and the metal catalytic for then carrying out furfural into furfuryl alcohol restores, and is then hydrolyzed and is obtained by the reaction
Levulic acid, so as to produce levulic acid by C5 sugar.
" chemical engineering periodical " (2014), volume 258, the 341-347 pages (Chemical Engineering
Journal (2014), vol.258, page 341-347) zeolite catalyst that alkali process is used under hot pressurized water is disclosed, lead to
Crystal structure, the variation of sour position and the porous size of increase and volume are crossed, so as to which single step of the xylose for levulic acid be turned
Change process.The method obtains the levulic acid of yield about 30%.
Green Chemistry (2015), volume 17, the 4618-4627 pages (Green Chemistry (2015), vol.17, page
It 4618-4627) discloses using Water-soluble catalyst as catalyst together with formic acid, from the side of furfural production levulic acid
Method, this method operate at a temperature of about 80-100 DEG C.The method obtains the levulic acid of yield about 62%.
Nevertheless, the method for above-mentioned step production levulic acid causes levulic acid yield relatively low, and generate many pairs
Product.Accordingly, it is difficult to levulic acid is produced on an industrial scale.In order to overcome the above problem, the continuous production of levulic acid is one
A compelling selection.Line focus and the two step continuity methods for developing production levulic acid, furfuryl alcohol is converted into from furfural
Start, then following step is to purify the crude furfuryl alcohol that furfural is converted to obtained in the step of converting of furfuryl alcohol, passes through water
Solution preocess generates levulic acid.
In general, furfural can utilize appropriate catalyst, furfuryl alcohol is converted by hydrogenation reaction.However, it is obtained by biomass
The furfural precursor obtained has high water content, is difficult in addition, detaching water from furfural.Therefore, the catalyst needs
It is stable in water contained by precursor.
Catalyst communicates (2012), volume 24, the 90-95 pages (Catalyst Communications (2012),
Vol.24, page 90-95) disclose the copper aluminum oxide spinel oxide for being prepared by sol-gel method and there is nanocrystal
Catalyst (CuAl2O4Spinelle) for the hydrogenolysis process of glycerine.The catalyst include 100 weight % surface area be
42m2The copper of/g-alumina spinel structure.Porous a diameter of 27nm.The catalyst makes glycerine be converted into 1,2-PD,
And the high selectivity of 1,2- propylene glycol is in 90%.
US4386219 discloses the hydrogenation of aldehyde, is used to that the copper aluminum oxide spinelle prepared by co-precipitation to be used to urge
Agent prepares propylene glycol.The surface area of the catalyst is 50-150m2, porous a diameter of 4,000 to 16,000nm.It is described
Catalyst is converted to the conversion ratio of propylene glycol in continuous system experiment with 98% aldehyde.
In order to which furfuryl alcohol is converted into levulic acid, US7265239 discloses furfuryl alcohol and is converted into levulic acid or levulic acid
The method for transformation of Arrcostab, this method include making furfuryl alcohol porous with being made of peracidity ion exchange resin with water or alkylol
The step of homogeneous catalyst contacts.The yield of document report ethyl levulinate is about 80-90%.But the document
The % yields of levulic acid are not reported.
Chemical ＆ sustainable development sources ＆ materials, ChemSusChem (2009), volume 2, the 437-441 pages
(Chemistry&Sustainability Energy&Materials,ChemSusChem(2009),vol.2,page 437–
441) it discloses and is reacted in acidic catalyst (sulfuric acid, ion exchange resin or zeolite) by furfuryl alcohol and ethyl alcohol, so as to by chaff
Alcohol prepares levulinate, and ethyl levulinate is obtained with about 80% yield.But the document does not report the % of levulic acid
Yield.
Catalytic action (2015), volume 5, the 3354-3359 pages (Catalysis (2015), vol.5, page 3354-
3359) it discloses using H-ZSM-5 zeolite catalysts, is in the ratio of silica and aluminium oxide (aluminum dioxide)
In the case of 23, by the method for furfuryl alcohol production levulic acid in tetrahydrofuran and aqueous solvent.Using H-ZSM-5 zeolites
Catalyst, and in the case that the ratio of silica and aluminium oxide is about 23, the yield of the levulic acid of the method is more than
70%.
In addition, RSC Advance (2014), volume 4, the 14985-14992 pages (RSC Advance (2014), vol.4,
Page 14985-14992) and WO2012162001A1 disclose and levulic acid, the diphasic system prepared by diphasic system
Start from forming furfuryl alcohol by furfurol reaction in gas phase, then by the hydrolysis of furfuryl alcohol and acid, furfuryl alcohol be converted, to be made
Levulic acid for product.
However, the above method need high-purity furfural or furfuryl alcohol as reacting precursor.Therefore, it is necessary to purification process to obtain
Obtain pure precursor.This brings difficulty to the method for production levulic acid.In addition, above-mentioned document is without studying the impurity from furfuryl alcohol
The influence reduced to levulic acid yield.
In conclusion the side of levulic acid is prepared by furfural by producing furfuryl alcohol the purpose of the present invention is exploitation is a kind of
Method, wherein the method are stable for the impurity in precursor.This can provide good acetyl to avoid purification process
Propionic acid yield, and the catalyst used in this approach can also recycle.
Invention content
It is an object of the invention to develop a kind of method by furfural production levulic acid.The method is in precursor
Pollutant is with good stability.Therefore, there is no need to that purifier is installed.In addition, this method provides the good production of levulic acid
Catalyst used in rate and this method can recycle.It the described method comprises the following steps：
A) within the temperature range of 120 DEG C to 200 DEG C, make 0.5 mole to 3 moles of furfuryl aldehyde solution in organic solvent and
10 bars to 40 bars hydrogen and copper aluminum oxide catalyst (CuAl2O4) contact 1 to 4 hour；With
B) within the temperature range of 100 DEG C to 150 DEG C so that from the product of step a) selected from organic solvent, water or institute
It states in the solvent of the mixture of solvent and is contacted 1 to 4 hour with the catalyst selected from MFI zeolite catalysts.
Specific embodiment
The invention discloses a kind of methods that levulic acid is prepared by furfural, and wherein the method is for the impurity in precursor
It is stable.Installation purification unit is not needed to when this method starts.The method includes by make furfuryl aldehyde solution with it is organic molten
Agent and hydrogen and copper aluminum oxide catalyst (CuAl2O4) contacted under the conditions of one, so as to which furfural is converted into turning for furfuryl alcohol
Change step.Then, by the furfuryl alcohol product obtained from the first step the mixture selected from organic solvent, water or the solvent solvent
In contacted under the conditions of one with MFI zeolite catalysts.The purpose for the arrangement is that good levulic acid yield % is provided, and
Catalyst used in the method can be recycled.
Unless otherwise stated, any aspect shown by the present invention refers to include to apply it to other of the present invention
Aspect.
Unless otherwise stated, technical term used herein or scientific terminology have those of ordinary skill in the art
The definition understood.
Any tool, equipment, method or chemical substance mentioned by this paper refer to those skilled in the art usually operation or
Tool, equipment, method or the chemical substance used, unless it is only specific tool, equipment, method in the present invention to illustrate them
Or chemical substance.
Refer to "one" using the combination of singular noun or singular pronoun and "comprising" in claims or specification,
Also refer to " one or more ", " at least one " and " one or more than one ".
All compositions and/or method disclosed and claimed in this application are intended to covering and include any effect, work(
The embodiment that can, change or adjust, and without carrying out with of the invention with dramatically different trial, and although do not weighing
It is illustrated in profit requirement, but those skilled in the art can obtain the function and effect identical with embodiment of the present invention.
Therefore, to those skilled in the art the alternative or similar purpose of clearly visible embodiment of the present invention (including appointing
What small modification or adjustment), it should all be interpreted the spirit without departing from the present invention shown in appended claims, model
It encloses and concept.
In entire application, term " about " refers to any number for occurring herein or showing, thus it is possible to vary or described in deviateing
Any deviation of device and method described in equipment or method or personal use, including as caused by change in physical variation or
Deviation.
Hereafter, it shows embodiment of the present invention, is not intended to be limited to any range of the present invention.
The present invention relates to the methods from furfural production levulic acid.The method is stable for the impurity in precursor.
Installation purification unit is not needed to when this method starts.It the described method comprises the following steps：
A) within the temperature range of 120 DEG C to 200 DEG C, make a concentration of 0.5 mole in organic solvent in 3 molar ranges
Furfuryl aldehyde solution and 10 bars to 40 bars of hydrogen and copper aluminum oxide catalyst (CuAl2O4) contact 1 to 4 hour；With
B) within the temperature range of 100 DEG C to 150 DEG C so that from the product of step a) selected from organic solvent, water or institute
It states in the solvent of the mixture of solvent and is contacted 1 to 4 hour with the catalyst selected from MFI zeolite catalysts.
In one embodiment, the copper aluminum oxide catalyst in step a) is included in 85 weight % to 100 weight %
In the range of copper-alumina spinel structure, copper-alumina spinel structure of preferably 95 weight % to 100 weight %.Surface
Product is in 0.5m2/ g to 5m2/ g, preferably in 1m2/ g to 3m2In the range of/g.Porous diameter is excellent in the range of 10nm to 20nm
It is selected in the range of 10nm to 15nm, porous volume is in 0.01cm3/ g to 0.1cm3In the range of/g.
In one embodiment, the copper aluminum oxide catalyst in step a) can be prepared by following methods：
(i) by mantoquita and the dissolving of the mixture of aluminium salt in a solvent；
(ii) organic acid is added in the mixture of step (i) acquisition；
(iii) it is heated at a temperature of higher than 150 DEG C from the mixture that step (ii) obtains until the mixture burns
Into solid；With
(iv) solid obtained from step (iii) is made to be calcined at a temperature in the range of 700 DEG C to 1,000 DEG C.
In one embodiment, in step a) water content of furfural precursor in the range of 0 to 30 volume %.
In one embodiment, the concentration for the furfural precursor in the organic solvent of step a) is rubbed at 0.5 mole to 3
In the range of you.Preferably, for the concentration of the furfural precursor in the organic solvent of step a) at 0.75 mole to 1.5 moles
In the range of.
In one embodiment, in step a) suitable ratio of furfural precursor and catalyst in 2.50-17.50g furfurals
Precursor:In the range of 1.00g catalyst, preferably in 4.00-9.00g furfural precursors:1.00g in the range of catalyst.
In one embodiment, the organic solvent for furfural precursor in step a) can be selected from, but not limited to, isopropyl
Alcohol, methanol, propyl alcohol and tetrahydrofuran organic solvent.Preferably, the organic solvent of furfural precursor is tetrahydrofuran.
In one embodiment, in step a) with the pressure of the hydrogen of furfurol reaction in the range of 10 bars to 40 bars.
Preferably, the pressure of hydrogen is in the range of 30 bars to 40 bars.
In one embodiment, in step a), at 120 DEG C to 200 DEG C, preferably in 150 DEG C to 190 DEG C of temperature model
Enclose it is interior carry out reaction 1 to 4 hour, preferably 2 to 3 hours.
In one embodiment, the MFI zeolite catalysts in step b) can be selected from, but not limited to, MCM-22, MCM-
36th, TNU-9, ZSM-5, ZSM-12, ITQ-39, Y- zeolite and beta-zeolite catalyst.Most preferred zeolite catalyst is that ZSM5 is urged
Agent.
In one embodiment, the ratio of silica and aluminium oxide is 20 in the ZSM5 catalyst used in step b)
To in the range of 50.It is preferred that the ratio of silica and aluminium oxide is in the range of 30 to 40.
In one embodiment, the product for being used to be converted to levulic acid obtained by step a) in step b) is dense
Spend is 0.1 mole to 0.5 mole.Preferably, concentration is in the range of 0.1 mole to 0.3 mole.
In one embodiment, in step b), by a) product of acquisition and the ratio of ZSM5 catalyst in 0.25-
1.50g by a) obtain product:In the range of 1g catalyst, preferably in 0.25-1.00g by the product that a) obtains:1g catalyst
In the range of.
In one embodiment, for the organic solvent of step b) can be selected from, but not limited to, methyl ethyl ketone, acetone,
Tetrahydrofuran, ethyl acetate, water or these solvents mixture.
Preferably, it is 4 that can be selected from the ratio of tetrahydrofuran and water for the organic solvent of step b):1、3:2 or 2:3
The ratio of mixed solvent, more preferable tetrahydrofuran and water is 4:1 mixed solvent.
In another embodiment, in step b), at 100 DEG C to 500 DEG C, preferably 110 DEG C to 130 DEG C of temperature model
Enclose it is interior carry out reaction 1 to 4 hour, preferably 1 to 2 hour.
In another embodiment, the process in step b) may further include with being selected from, but not limited to, nitrogen, helium
The inert gas of gas or argon gas pressurizes, and wherein pressure is in the range of 15 bars to 40 bars.
In an aspect, it can be operated in the reactor by the method for furfural production levulic acid, reactor is not limited to
Fixed bed reactors.It can be conducted batch-wise or be carried out continuously.
Following embodiment is used to illustrate one aspect of the present invention, the range of but do not limit the invention in any way.
Step 1：Furfuryl alcohol is prepared by furfural
The copper aluminum oxide catalyst comprising copper-alumina spinel structure can be used to complete to prepare furfuryl alcohol by furfural
Process.
Copper aluminum oxide catalyst comprising copper-alumina spinel structure can be by a temperature of about 60 DEG C, inciting somebody to action
About 23.73g cupric nitrate trihydrates mix to prepare in water with about 76.56g aluminum nitrates.Then about 88.70g citric acids are added
Enter into the mixture.Mixture is stirred and heated, and held at a temperature of 300 DEG C or so at a temperature of about 100 DEG C
Continuous heating is until obtaining solid matter.Obtained solid is calcined at a temperature of about 700 DEG C to 1000 DEG C, heating rate is about
200 DEG C/h.The obtained surface area of copper aluminum oxide catalyst is 0.5m2/ g to 5m2/ g, and it is containing having more than 85 weights
Measure copper-alumina spinel structure of %.
Then, before the reaction, in 150mL high-pressure reactors, opened within about 4 hours from copper aluminum oxide catalyst contact hydrogen
Begin, carry out conversion reaction of the furfural to furfuryl alcohol.Then, the copper aluminum oxide catalyst prepared by about 0.5g and 25mL are dissolved in
1.5 moles of furfurals in tetrahydrofuran solvent are added in the reactor.Hydrogen is fitted into reactor, makes initial pressure about
It it is 40 bars, stirring while heats, until temperature reaches about 170 DEG C.Before stopping reacting, reaction is made to carry out about 1 hour to 3
Hour.Then, with the amount of gas chromatographic analysis furfural and furfuryl alcohol.The conversion ratio % and chaff of furfuryl alcohol are converted to by following formula calculating furfural
The yield % of alcohol.The yield % of furfuryl alcohol is as shown in table 1.
Table 1：Processing time is converted to furfural the influence of the conversion ratio % and furfuryl alcohol yield % of furfuryl alcohol
Step 2：Levulic acid is prepared by furfuryl alcohol
ZSM-5 zeolite catalyst can be used, levulic acid is prepared by furfuryl alcohol.In ZSM-5 catalyst for the present invention, two
The ratio of silica and aluminium oxide is about 30.
Conversion reaction of the furfuryl alcohol to levulic acid originates in into the high pressure batch reactor of about 150mL, adds 30mL
Be dissolved in solvent 0.2 mole of furfuryl alcohol and the ZSM-5 zeolite catalyst of about 0.5g to 2g.Then, nitrogen is added to
In reactor.Initial pressure is about 15 bars.Then, it is heated while stirring, until reaching about 120 DEG C of temperature.
Before stopping reaction, reaction is made to carry out about 1 to 3 hour.Then, the amount of furfuryl alcohol and levulic acid is analyzed with gas chromatographic technique.
Furfuryl alcohol is calculated by following formula and is converted to the conversion ratio % of levulic acid and the yield % of levulic acid：
Solvent is converted to furfuryl alcohol the influence research of the conversion ratio % of levulic acid
The influence of the conversion ratio % of levulic acid is converted into study solvent to furfuryl alcohol, by tetrahydrofuran and water and four
The ratio of hydrogen furans is 1:4 mixture is used as preparing the solvent in levulic acid by furfuryl alcohol as described above.As a result such as 2 institute of table
Show.
As shown in Table 2 as a result, it has been found that, the use of water and tetrahydrofuran ratio is in the reaction 1:4 mixture ratio is used only
Tetrahydrofuran obtains higher levulic acid yield % as solvent.
Table 2：Influence of the solvent to levulic acid yield % after solvent changes
Influence of the temperature to levulic acid yield %
The research of the influence of the conversion reaction of levulic acid is converted into furfuryl alcohol about temperature, can be existed according to the method described above
It is tested to complete at 80 DEG C, 120 DEG C and 150 DEG C different of reaction temperatures.
It is found from table 3, under 120 DEG C for the treatment of temperatures and the processing time of 2 hours, the yield % of levulic acid is most
Height, about 86.2%.
Table 3：Influence of the temperature to levulic acid yield %
Influence of the amount of catalyst to levulic acid yield %
The research of the influence of the conversion reaction of levulic acid is converted into furfuryl alcohol about catalyst amount, it can be according to above-mentioned
Method is simultaneously carried out by changing catalyst amount for 0.5g, 1.0g and 2.0g.
From table 4, it can be seen that catalyst amount is higher, the yield % of levulic acid is higher.
Table 4：Influence of the amount of catalyst to levulic acid yield %
Using during levulic acid is converted into, by the not purified mistake obtained in the step of converting of furfural to furfuryl alcohol
The crude furfuryl alcohol of journey
The not purified crude furfuryl alcohol filtering obtained in the step of converting of furfuryl alcohol will be converted to from furfural as described above, from
And the catalyst in separating step 1.Then, water is added, the ratio of water and tetrahydrofuran is adjusted to 1:4.By the dense of furfuryl alcohol
Degree is adjusted to about 0.2 mole.The unpurified crude furfuryl alcohols of 30mL are converted by levulic acid by furfuryl alcohol according to the above method.
As can be found from Table 5, the unpurified furfuryl alcohol for preparing furfuryl alcohol acquisition by furfural as described above can be in conversion reaction
Before without further purification process and be converted into levulic acid.It has been found that the yield % of levulic acid is about 75% to 80%.
Table 5：The mixture that step 1 obtains is converted into furfuryl alcohol the influence of levulic acid
Claims (9)
- A kind of 1. method by furfural production levulic acid, which is characterized in that the described method comprises the following steps：A) within the temperature range of 120 DEG C to 200 DEG C, make chaff of the concentration in 0.5 mole to 3 molar ranges in organic solvent Aldehyde solution and hydrogen and copper aluminum oxide catalyst (CuAl of the pressure in the range of 10 bars to 40 bars2O4) contact 1 to 4 hour； WithB) within the temperature range of 100 DEG C to 150 DEG C so that from the product of step a) selected from organic solvent, water or described molten It is contacted 1 to 4 hour with the catalyst selected from MFI zeolite catalysts in the solvent of the mixture of agent.
- 2. the method according to claim 1 by furfural production levulic acid, wherein in step a), at 150 DEG C to 190 Within the temperature range of DEG C, furfuryl aldehyde solution of the concentration in 0.75 mole to 1.5 molar ranges in organic solvent is made to exist with pressure Hydrogen and copper aluminum oxide catalyst (CuAl in the range of 30 bars to 40 bars2O4) contact 2 to 3 hours.
- 3. the copper alumina in the method according to claim 1 or 2 by furfural production levulic acid, wherein step a) Compound catalyst is included in copper-alumina spinel structure in the range of 85 weight % to 100 weight %, the copper aluminum oxide The surface area of catalyst is in 1m2/ g to 3m2In the range of/g, in the range of 10nm to 20nm, porous volume exists porous diameter 0.01cm3/ g to 0.1cm3In the range of/g.
- 4. furfural in the method according to any one of claim 1 to 3 by furfural production levulic acid, wherein step a) Ratio with the copper aluminum oxide catalyst is in 4.00-9.00g furfural precursors:In the range of catalyst described in 1g.
- 5. the institute in the method according to any one of claim 1 to 4 by furfural production levulic acid, wherein step a) Organic solvent is stated as tetrahydrofuran.
- 6. the method according to claim 1 that levulic acid is prepared by furfural, wherein in step b), at 110 DEG C to 130 Within the temperature range of DEG C so that from the product of step a) with the concentration in 0.1 mole to 0.3 molar range in tetrahydrofuran and water In the mixed solvent contacted 1 to 2 hour with zeolite ZSM-5 catalyst.
- 7. the method according to claim 6 by furfural production levulic acid, wherein in the mixed solvent tetrahydrofuran and water Ratio be 1:4.
- 8. in the method according to claim 6 by furfural production levulic acid, wherein ZSM-5 catalyst silica with The ratio of aluminium oxide is in the range of 30 to 40.
- 9. according to the method by furfural production levulic acid described in claim 1,6,7 or 8, wherein in step b), from step The ratio of rapid product a) obtained and the ZSM-5 catalyst is in 0.25-1.00g by the product that a) obtains:Catalyst described in 1g In the range of.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548330A (en) * | 2020-04-29 | 2020-08-18 | 南京工业大学 | Method for preparing 2, 5-furan dicarbaldehyde by selective oxidation of 5-hydroxymethylfurfural on manganese-based spinel catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997034694A1 (en) * | 1996-03-21 | 1997-09-25 | Engelhard Corporation | PREPARATION AND USE OF NON-CHROME CATALYSTS FOR Cu/Cr CATALYST APPLICATIONS |
-
2017
- 2017-12-08 CN CN201711293617.7A patent/CN108178725A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997034694A1 (en) * | 1996-03-21 | 1997-09-25 | Engelhard Corporation | PREPARATION AND USE OF NON-CHROME CATALYSTS FOR Cu/Cr CATALYST APPLICATIONS |
Non-Patent Citations (2)
| Title |
|---|
| MAX A. MELLMER，ET AL.: "Selective Production of Levulinic Acid from Furfuryl Alcohol in THF Solvent Systems over H‑ZSM‑5", 《ACS CATALYSIS》 * |
| 吴静 等: "糠醛加氢催化剂的研究进展", 《现代化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548330A (en) * | 2020-04-29 | 2020-08-18 | 南京工业大学 | Method for preparing 2, 5-furan dicarbaldehyde by selective oxidation of 5-hydroxymethylfurfural on manganese-based spinel catalyst |
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