CN118125999A - Preparation method of 5-hydroxymethylfurfural - Google Patents
Preparation method of 5-hydroxymethylfurfural Download PDFInfo
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- CN118125999A CN118125999A CN202211536074.8A CN202211536074A CN118125999A CN 118125999 A CN118125999 A CN 118125999A CN 202211536074 A CN202211536074 A CN 202211536074A CN 118125999 A CN118125999 A CN 118125999A
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- Prior art keywords
- hydroxymethylfurfural
- water
- molecular sieve
- adsorbent
- cellulose
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 102
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003463 adsorbent Substances 0.000 claims abstract description 44
- 239000001913 cellulose Substances 0.000 claims abstract description 33
- 229920002678 cellulose Polymers 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000012074 organic phase Substances 0.000 claims abstract description 31
- 239000003960 organic solvent Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims description 30
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000012621 metal-organic framework Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- -1 aluminum alkoxide Chemical class 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002734 clay mineral Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000003729 cation exchange resin Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 150000002194 fatty esters Chemical class 0.000 claims description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 239000011973 solid acid Substances 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- RFRMMZAKBNXNHE-UHFFFAOYSA-N 6-[4,6-dihydroxy-5-(2-hydroxyethoxy)-2-(hydroxymethyl)oxan-3-yl]oxy-2-(hydroxymethyl)-5-(2-hydroxypropoxy)oxane-3,4-diol Chemical compound CC(O)COC1C(O)C(O)C(CO)OC1OC1C(O)C(OCCO)C(O)OC1CO RFRMMZAKBNXNHE-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 229910021532 Calcite Inorganic materials 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 239000013177 MIL-101 Substances 0.000 claims description 2
- 239000013206 MIL-53 Substances 0.000 claims description 2
- HDJLSECJEQSPKW-UHFFFAOYSA-N Methyl 2-Furancarboxylate Chemical compound COC(=O)C1=CC=CO1 HDJLSECJEQSPKW-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229940023913 cation exchange resins Drugs 0.000 claims description 2
- 229920003086 cellulose ether Polymers 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229940049953 phenylacetate Drugs 0.000 claims description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 229940071182 stannate Drugs 0.000 claims description 2
- 125000005402 stannate group Chemical group 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 26
- 238000000605 extraction Methods 0.000 abstract description 11
- 239000008346 aqueous phase Substances 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 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 2
- 238000013019 agitation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 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
- 241001464837 Viridiplantae Species 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000004888 barrier function Effects 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
- 239000002551 biofuel Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 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
- C07D307/38—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
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The application discloses a preparation method of 5-hydroxymethylfurfural, and belongs to the field of preparation and synthesis of 5-hydroxymethylfurfural. The preparation method of the 5-hydroxymethylfurfural comprises the following steps: s1, mixing materials containing cellulose, a catalyst, water and an organic solvent and reacting to obtain a reaction solution containing 5-hydroxymethylfurfural; s2, the organic phase in the reaction liquid is communicated with an adsorbent, and 5-hydroxymethylfurfural is obtained through enrichment; the organic solvent is insoluble in water. The organic extraction phase is mixed with the aqueous phase reaction liquid, and the 5-hydroxymethylfurfural in the organic extraction phase is adsorbed by the adsorbent, so that side reactions can be effectively inhibited, the reaction selectivity is improved, and the energy consumption in the production process is reduced.
Description
Technical Field
The application relates to a preparation method of 5-hydroxymethylfurfural, and belongs to the field of preparation and synthesis of 5-hydroxymethylfurfural.
Background
Under the introduction of the 'double carbon target', the bio-based material is gradually becoming one of the new industrial directions of global technological innovation and economic development. Cellulose (cellulose) is macromolecular polysaccharide composed of glucose, is a natural macromolecular material with the greatest distribution and storage in nature and has the advantages of good biocompatibility, reproducibility, biodegradability and the like, and a large amount of cellulose exists in green plants and marine organisms. By photosynthesis, plants synthesize hundreds of millions of tons of cellulose each year. Biomass resources are abundant, renewable and easy to obtain, and have attracted considerable attention as potential substitutes for fossil resources. The main components of biomass are carbohydrates and various high value-added chemicals that can be converted into biofuels. Among them, 5-Hydroxymethylfurfural (HMF) is one of the most important bio-based platform compounds, its downstream derivatives are widely classified, and the end market covers the fields of high gas barrier coating materials, feed additives, surfactants, etc., with great industrial potential.
Typical routes to 5-hydroxymethylfurfural are acid-catalyzed dehydration of carbohydrates such as glucose, fructose, cellulose and sucrose. Various homogeneous or heterogeneous catalysts have been developed, including Lewis and Bronsted acids, which have been found to be effective in the synthesis of 5-hydroxymethylfurfural and which are widely used in processes for the production of 5-hydroxymethylfurfural. However, because the 5-hydroxymethylfurfural generated in the reaction process has higher reactivity, the 5-hydroxymethylfurfural can further react under the catalysis of the catalyst to generate high-molecular black rot through polymerization or generate acetoacetic acid through decomposition. The generation of these byproducts can lead to lower selectivity of the reaction, and can lead to corrosion and blockage of equipment, so that the reaction is difficult to carry out, the maintenance and use cost of the equipment is greatly increased, and the economic benefit is poor. Meanwhile, in the process of collecting the product 5-hydroxymethylfurfural, an organic solvent is usually required to be used for extraction, and then the organic solvent is recycled in a distillation mode, so that larger energy consumption is generated, and the production cost is greatly increased. The disadvantages of these aspects above limit the potential industrial applications of 5-hydroxymethylfurfural.
Disclosure of Invention
According to a first aspect of the present application there is provided a process for the preparation of 5-hydroxymethylfurfural which comprises mixing an aqueous solution comprising cellulose and a reaction catalyst with a water-insoluble organic phase, reacting under agitation, transferring the 5-hydroxymethylfurfural formed in the aqueous phase to the organic phase during agitation. In the process of preparing the 5-hydroxymethylfurfural, the organic phase is adsorbed and enriched through an adsorbent bed layer to obtain the 5-hydroxymethylfurfural, and the organic phase is recycled to continuously extract and extract the 5-hydroxymethylfurfural in the water phase. In the application, the organic extract phase directly mixed with the water phase can be dissolved in the organic phase at the initial stage of generating the 5-hydroxymethylfurfural, so that the 5-hydroxymethylfurfural is prevented from further generating side reaction in the water phase to form black rot. Meanwhile, the 5-hydroxymethylfurfural in the organic phase is enriched by an adsorption method, the organic phase is passed through an adsorbent bed, and the organic extract phase can be recycled without the normal pressure or reduced pressure distillation process which is commonly used for the organic extract phase in the traditional process. Effectively reduces the energy consumption. The 5-hydroxymethylfurfural can be desorbed from the adsorbent by flushing the adsorbent bed with water. The system for synthesizing the 5-hydroxymethylfurfural has the advantages of larger economic benefit, lower system cost, less environmental pollution, simple operation, easy repetition, low equipment maintenance cost and high-purity 5-hydroxymethylfurfural production.
The preparation method of the 5-hydroxymethylfurfural comprises the following steps:
S1, mixing materials containing cellulose, a catalyst, water and an organic solvent and reacting to obtain a reaction solution containing 5-hydroxymethylfurfural;
S2, the organic phase in the reaction liquid is communicated with an adsorbent, and 5-hydroxymethylfurfural is obtained through enrichment;
The organic solvent is insoluble in water.
Mixing an aqueous solution containing cellulose and an organic solvent insoluble in water, and reacting the aqueous phase under the catalysis of a catalyst to obtain the 5-hydroxymethylfurfural. Transferring the generated 5-hydroxymethylfurfural into an organic phase, and recycling the organic phase containing the 5-hydroxymethylfurfural to be continuously mixed with water after passing the organic phase through a bed layer containing an adsorbent. After the adsorbent is saturated, washing with water, desorbing the adsorbed 5-hydroxymethylfurfural to obtain a high-purity 5-hydroxymethylfurfural aqueous solution.
Alternatively, the reaction is carried out under stirring.
Optionally, in step S2, the adsorbent is rinsed with water, and 5-hydroxymethylfurfural is desorbed from the adsorbent.
Optionally, the mass ratio of the water to the adsorbent is 1-10: 1.
Optionally, the cellulose is at least one selected from cellulose ether, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose.
Optionally, the catalyst is selected from at least one of water-soluble acid, solid acid catalyst, aluminum alkoxide, aluminum phenoxy, tetrabutyl stannate, titanium alkoxide, zirconium alkoxide, ethyl antimonite, and butyl antimonite.
Optionally, the water-soluble acid is selected from at least one of phosphoric acid, hydrochloric acid, sulfuric acid, boric acid, and p-toluenesulfonic acid.
Optionally, the hydrochloric acid is a 35.0wt% to 40.0wt% hydrochloric acid solution.
Optionally, the sulfuric acid is concentrated sulfuric acid of 95.0wt% to 99.0 wt%.
Optionally, the solid acid catalyst is selected from at least one of cation exchange resins, molecular sieves with acidic sites, sulfides, natural clay minerals, amorphous oxides, metal organic framework materials.
Optionally, the cation exchange resin comprises a sulfonic acid resin.
Optionally, the natural clay mineral comprises kaolin.
Optionally, the molecular sieve with acid sites is selected from at least one of ZSM-5 molecular sieve, TS-1 molecular sieve, 13X molecular sieve and Y molecular sieve.
Optionally, the metal-organic framework material comprises metal-organic framework material MILs-125.
Optionally, the organic solvent is at least one selected from tetrahydrofuran, 2-methyl furan, fatty esters, aromatic esters, cyclic esters, and ketones.
Optionally, the fatty esters are selected from ethyl acetate and/or dimethyl carbonate.
Alternatively, the aromatic esters are selected from phenyl acetate.
Alternatively, the cyclic esters are selected from methyl furoate.
Optionally, the ketone is selected from at least one of methyl isobutyl ketone, cyclohexanone and isophorone.
Optionally, the adsorbent is selected from at least one of activated carbon, molecular sieves, natural clay minerals, amorphous oxides, metal organic framework materials.
Optionally, the activated carbon is at least one selected from coal-based carbon, coconut shell carbon and wood-based carbon.
Optionally, the molecular sieve is at least one selected from a Y-type molecular sieve, an A-type molecular sieve, a ZSM-5 molecular sieve, a 13X molecular sieve, an MWW molecular sieve and an MOR molecular sieve.
Optionally, the natural clay mineral is selected from at least one of bentonite, montmorillonite, kaolin and calcite.
Optionally, the amorphous oxide is selected from at least one of amorphous silica, amorphous alumina, amorphous aluminosilicate.
Optionally, the metal organic framework material is selected from at least one of metal organic framework materials MIL-125, MIL-101, SIFSIX and MIL-53.
Optionally, the mass ratio of the cellulose to the water is 0.5-10: 1 to 20.
Optionally, the mass ratio of the cellulose to the water is 5-10: 5 to 20.
Optionally, the mass ratio of the cellulose to the water is 8-10: 6-20.
Optionally, the mass ratio of the cellulose to the water is 5-10: 10 to 20.
Optionally, the mass ratio of cellulose to water is 10: 15-20.
Optionally, the mass ratio of cellulose to water is 1:0.8 to 10.
Alternatively, the mass ratio of cellulose to water is independently selected from 1:0.8, 1:1. 1: 2. 1: 3. 1:0.8, 1: 4. 1: 5. 1: 6. 1: 7. 1: 8. 1: 9. 1:10 or a range of values between any of the two.
Optionally, the mass ratio of the cellulose to the catalyst is 0.5-10: 0.01 to 1.
Optionally, the mass ratio of the cellulose to the catalyst is 8-10: 0.01 to 1.
Optionally, the mass ratio of the cellulose to the catalyst is 10:0.01 to 1.
Alternatively, the mass ratio of cellulose to catalyst is independently selected from 10:0.01, 10:0.05, 10:0.1, 10:0.2, 10:0.5, 10:0.7, 10:0.9, 10:1 or a range value between any two.
Optionally, the mass ratio of the water to the organic solvent is 0.5-10: 1 to 50.
Optionally, the mass ratio of the water to the organic solvent is 0.5-10: 1 to 20.
Optionally, the mass ratio of the water to the organic solvent is 5-10: 5 to 50.
Optionally, the mass ratio of the water to the organic solvent is 8-10: 15-50.
Optionally, the mass ratio of the water to the organic solvent is 8-10: 30-50.
Optionally, the mass ratio of the water to the organic solvent is 1:1 to 100.
Alternatively, the mass ratio of water to organic solvent is independently selected from 1:1. 1: 5. 1: 10. 1: 20. 1: 50. 1: 70. 1:100 or a range of values therebetween.
Optionally, the mass ratio of the adsorbent to the organic phase is 0.5-10: 1 to 50.
Optionally, the mass ratio of the adsorbent to the organic phase is 5-10: 20 to 50.
Optionally, the mass ratio of the adsorbent to the organic phase is 8-10: 35 to 50.
Optionally, the mass ratio of the adsorbent to the organic phase is 1:1 to 50.
Alternatively, the mass ratio of the adsorbent and the organic phase is independently selected from 1: 1. 1: 5. 1: 10. 1: 20. 1: 30. 1: 40. 1:50 or a range of values therebetween.
Alternatively, the reaction conditions are as follows:
The temperature is 30-180 ℃;
The time is 2-10 h.
Alternatively, the temperature is independently selected from any value or range of values between any two points of 30 ℃, 40 ℃, 50 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 175 ℃,180 ℃.
Alternatively, the time is independently selected from any value or range of values between any two points of 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10 h.
The pressure of the reaction is not particularly limited, and may be normal pressure.
Optionally, the organic phase is in communication with a bed of adsorbent;
Recycling the organic solvent.
After the organic phase is passed through the adsorbent, the adsorbent is enriched in 5-hydroxymethylfurfural in the organic phase, after which the aqueous solution of 5-hydroxymethylfurfural of higher purity can be obtained by desorption with water.
Optionally, the mass ratio of the water to the adsorbent is 1-10: 1.
Optionally, the mass ratio of the water to the adsorbent is 5-10: 1.
Optionally, the mass ratio of the water to the adsorbent is 8-10: 1.
Alternatively, the mass ratio of the water and the adsorbent is independently selected from 1: 1.2:1. 3: 1. 4: 1. 5: 1. 6: 1. 7: 1. 8: 1. 9: 1. 10:1 or a range value between any two.
Alternatively, the yield of 5-hydroxymethylfurfural is greater than 80%.
Optionally, the yield of 5-hydroxymethylfurfural is 80% -95%.
And after the reaction is finished, a certain amount of reaction liquid is taken, deionized water is added to mix and fix the volume, and the detection of the yield of the 5-hydroxymethylfurfural is carried out.
The detection method is high performance liquid chromatography: obtaining a liquid chromatography peak area by configuring the content of 5-hydroxymethylfurfural in a standard solution, and obtaining a standard curve by taking the peak area as an abscissa and the concentration of 5-hydroxymethylfurfural as an ordinate; further, the concentration of 5-hydroxymethylfurfural in the reaction liquid after the reaction can be calculated, and the yield of 5-hydroxymethylfurfural is calculated through the concentration.
The application discloses a preparation method of 5-hydroxymethylfurfural, which comprises the following steps: an aqueous solution containing cellulose and a water-insoluble organic solvent are mixed. The 5-hydroxymethylfurfural is obtained by the reaction in the water phase under the catalysis of a catalyst, the generated 5-hydroxymethylfurfural is transferred to an organic phase, the organic phase containing the 5-hydroxymethylfurfural is recycled and continuously mixed with the water phase after passing through a bed layer containing an adsorbent, the adsorbent is saturated and then washed with water, and the adsorbed 5-hydroxymethylfurfural is desorbed to obtain a 5-hydroxymethylfurfural water solution with higher purity.
As a specific embodiment, the method comprises the following steps:
(1) The raw materials containing cellulose aqueous solution are dehydrated under the catalysis of a catalyst to obtain reaction liquid containing 5-hydroxymethylfurfural, the reaction liquid is mixed with an organic extraction phase insoluble in water, and the 5-hydroxymethylfurfural generated in the aqueous phase of the reaction liquid is transferred into the organic extraction phase.
(2) In the production process, the 5-hydroxymethylfurfural in the organic extraction phase is adsorbed and enriched by using an adsorbent, the organic extraction phase after adsorbing the 5-hydroxymethylfurfural is recycled into the reaction liquid, the 5-hydroxymethylfurfural is continuously extracted, and the adsorbent is then washed by water to desorb the adsorbed 5-hydroxymethylfurfural.
Specifically, the method comprises the following steps:
a) Mixing cellulose, water, a catalyst and an organic solvent extract, and reacting in a stirring state at a reaction temperature of 30-180 ℃ for 2-10 hours;
b) And c) adsorbing the organic solvent extract phase in the reaction of the step a) through an adsorbent, recycling the organic solvent extract phase to the reaction of the step a) after adsorption, and then flushing and desorbing the 5-hydroxymethylfurfural in the adsorbent by using water to obtain an aqueous solution of the product 5-hydroxymethylfurfural.
The preparation route of the application is to utilize cellulose, catalyst and organic extraction solvent to mix, and the organic phase of 5-hydroxymethyl furfural extracted in the reaction process is adsorbed by adsorbent to produce 5-hydroxymethyl furfural, thus realizing the recycling of the organic extraction phase and carrying out the method of catalyzing the conversion of cellulose into 5-hydroxymethyl furfural. The added organic phase effectively inhibits the further side reaction of the 5-hydroxymethylfurfural, no other impurities or black rot are generated after the reaction, the adsorbent is used for adsorbing the 5-hydroxymethylfurfural product in the organic phase after the reaction, the organic phase is not required to be distilled, the organic phase can be recycled to realize the recovery and separation of the extraction solvent and the product, the side reaction is difficult to control in the traditional preparation process of the 5-hydroxymethylfurfural, and the generated black rot is extremely easy to cause equipment corrosion and blockage. Compared with the traditional simple aqueous phase reaction system, the application can effectively avoid side reaction of the 5-hydroxymethylfurfural, the reaction liquid after reaction is clear and transparent, has higher conversion rate and selectivity, and compared with the normal pressure or reduced pressure distillation process required by the traditional organic solvent, the use of the adsorbent can effectively reduce the energy consumption of the recycling process, is environment-friendly, has lower economic cost, is beneficial to industrial production and amplification, has low equipment maintenance cost, and can efficiently produce the high-purity 5-hydroxymethylfurfural.
The application has the beneficial effects that:
1) Compared with the traditional method, the preparation method of the 5-hydroxymethylfurfural provided by the application has the advantages that cellulose which is low in cost and wide in acquisition range is used as a raw material in the preparation process, meanwhile, the water phase and the organic solvent extraction phase are directly mixed to generate a synergistic effect, and the product is transferred from the water phase to the organic phase, so that the occurrence of side reaction can be effectively controlled, the occurrence of black rot is avoided, the selectivity of the reaction is improved, and the equipment maintenance and labor cost is greatly reduced.
2) The preparation method of the 5-hydroxymethylfurfural provided by the application adopts an adsorbent adsorption method to recycle the organic extraction phase, has larger economic benefit, does not need a traditional normal pressure or reduced pressure distillation system with higher energy consumption, has lower system cost, has little environmental pollution, is simple to operate, is easy to repeat, has low equipment maintenance cost, and can efficiently produce the high-purity 5-hydroxymethylfurfural.
Drawings
FIG. 1 is a hydrogen nuclear magnetic resonance spectrum of the product synthesized in example 1 of the present application.
FIG. 2 is a hydrogen nuclear magnetic spectrum of a 5-hydroxymethylfurfural standard.
FIG. 3 is a carbon nuclear magnetic spectrum of the product synthesized in example 1 of the present application.
FIG. 4 is a carbon nuclear magnetic spectrum of a 5-hydroxymethylfurfural standard.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
The starting materials and catalysts in the examples of the present application were purchased commercially, unless otherwise specified.
In the examples of the present application, the concentrations of concentrated sulfuric acid and hydrochloric acid used are described below:
concentrated sulfuric acid: h SO is 98.0wt%;
Hydrochloric acid: HCl was 37.0wt%.
The analytical methods in the examples of the application are as follows:
the reaction solution was dissolved in deuteration reagent by using liquid nuclear magnetic resonance spectrometer model AVANCE II 400M manufactured by Bruce company to analyze nuclear magnetic resonance chart of carbon and hydrogen.
High performance liquid chromatography was carried out using water as mobile phase under the conditions of model 7890A from vortical corporation, using uv-vis and differential refraction detector.
The yield and selectivity of 5-hydroxymethylfurfural in the examples of the application were calculated as follows:
yield of 5-hydroxymethylfurfural = moles of 5-hydroxymethylfurfural produced/moles of reaction substrate added
Selectivity of 5-hydroxymethylfurfural = moles of 5-hydroxymethylfurfural produced/moles of reaction substrate participating in the reaction
The method comprises the steps of obtaining a liquid chromatography peak area by configuring the content of 5-hydroxymethylfurfural in a standard solution, and obtaining a standard curve by taking the peak area as an abscissa and the concentration of 5-hydroxymethylfurfural as an ordinate; further, the concentration of 5-hydroxymethylfurfural in the reaction liquid after the reaction can be calculated, and the yield of 5-hydroxymethylfurfural is calculated through the concentration.
Example 1
5G of cellulose, 16.84g of dimethyl carbonate and 5g of water are added into a batch kettle reactor, 0.12g of concentrated sulfuric acid is added dropwise as a catalyst under stirring, the temperature is raised to 100 ℃, the reaction time is 6 hours, and the color of the aqueous phase reaction solution and the color of the organic extract phase are gradually increased. The organic extract phase was passed through 5g of coconut activated carbon, followed by flushing the adsorbent with 6g of water to give an aqueous solution of 5-hydroxymethylfurfural. A small amount of flushing liquid is taken for high performance liquid chromatography analysis, and the result shows that the yield of the 5-hydroxymethylfurfural is 85% and the selectivity is 98%.
Example 2
8G of cellulose, 30g of ethyl acetate and 6g of water are added into a batch kettle reactor, 0.1g of ZSM-5 molecular sieve is added as a catalyst under stirring, the temperature is raised to 150 ℃, the reaction time is 5 hours, and the colors of the aqueous phase reaction solution and the organic extract phase are gradually deepened. The organic extract phase was passed through 8g of molecular sieve type X, after which the adsorbent was washed with 12g of water to give an aqueous solution of 5-hydroxymethylfurfural. A small amount of flushing liquid is taken for high performance liquid chromatography analysis, and the result shows that the yield of the 5-hydroxymethylfurfural is 90% and the selectivity is 98%.
Examples 3 to 11
The specific ingredients, materials and reaction conditions are shown in Table 1, and the other operations in the synthesis process are the same as in example 1.
TABLE 1 raw material composition, ratio and adsorption separation conditions for examples 3 to 11
Example 12 liquid Nuclear magnetic resonance analysis
Liquid nuclear magnetic resonance analysis was performed on the 5-hydroxymethylfurfural prepared in examples 1 to 11, and typical examples are shown in fig. 1 and 3, and fig. 2 and 4 are standard spectra of 5-hydroxymethylfurfural. Fig. 1 corresponds to the hydrogen nuclear magnetic resonance spectrum of 5-hydroxymethylfurfural prepared in example 1, and it can be seen from a comparison of fig. 1 and fig. 2 that the 5-hydroxymethylfurfural prepared in example 1 has a typical standard hydrogen nuclear magnetic spectrum of 5-hydroxymethylfurfural.
FIG. 3 corresponds to the carbon nuclear magnetic resonance spectrum of 5-hydroxymethylfurfural prepared in example 1. As can be seen from a comparison of FIGS. 3 and 4, the carbon nuclear magnetic spectrum of 5-hydroxymethylfurfural prepared in example 1 has typical standard 5-hydroxymethylfurfural.
The test results for 5-hydroxymethylfurfural in other examples were similar to those described above, and standard 5-hydroxymethylfurfural was obtained by the present invention.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (10)
1. The preparation method of the 5-hydroxymethylfurfural is characterized by comprising the following steps of:
S1, mixing materials containing cellulose, a catalyst, water and an organic solvent and reacting to obtain a reaction solution containing 5-hydroxymethylfurfural;
S2, the organic phase in the reaction liquid is communicated with an adsorbent, and 5-hydroxymethylfurfural is obtained through enrichment;
The organic solvent is insoluble in water.
2. The method according to claim 1, wherein in step S2, the adsorbent is rinsed with water to desorb 5-hydroxymethylfurfural from the adsorbent.
3. The preparation method according to claim 2, wherein the mass ratio of the water to the adsorbent is 1 to 10:1.
4. The method according to claim 1, wherein the cellulose is at least one selected from the group consisting of cellulose ether, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose.
5. The method according to claim 1, wherein the catalyst is at least one selected from the group consisting of a water-soluble acid, a solid acid catalyst, an aluminum alkoxide, an aluminum phenoxy, a tetrabutyl stannate, a titanium alkoxide, a zirconium alkoxide, an ethyl antimonite, and a butyl antimonite;
preferably, the water-soluble acid is selected from at least one of phosphoric acid, hydrochloric acid, sulfuric acid, boric acid, and p-toluenesulfonic acid;
preferably, the solid acid catalyst is selected from at least one of cation exchange resins, molecular sieves with acidic sites, sulfides, natural clay minerals, amorphous oxides, metal organic framework materials;
preferably, the cation exchange resin comprises a sulfonic acid resin;
preferably, the natural clay mineral comprises kaolin clay;
preferably, the molecular sieve with acid position is selected from at least one of ZSM-5 molecular sieve, TS-1 molecular sieve, 13X molecular sieve and Y molecular sieve;
Preferably, the metal-organic framework material comprises metal-organic framework material MILs-125.
6. The method according to claim 1, wherein the organic solvent is at least one selected from tetrahydrofuran, 2-methylfuran, fatty esters, aromatic esters, cyclic esters, and ketones;
preferably, the fatty esters are selected from ethyl acetate and/or dimethyl carbonate;
preferably, the aromatic esters are selected from phenyl acetate;
preferably, the cyclic esters are selected from methyl furoate;
preferably, the ketone is selected from at least one of methyl isobutyl ketone, cyclohexanone and isophorone.
7. The method according to claim 1, wherein the adsorbent is at least one selected from the group consisting of activated carbon, molecular sieves, natural clay minerals, amorphous oxides, and metal organic framework materials;
preferably, the activated carbon is at least one selected from coal-based carbon, coconut shell carbon and wood carbon;
preferably, the molecular sieve is selected from at least one of a Y-type molecular sieve, an A-type molecular sieve, a ZSM-5 molecular sieve, a 13X molecular sieve, an MWW molecular sieve and an MOR molecular sieve;
preferably, the natural clay mineral is at least one selected from bentonite, montmorillonite, kaolin and calcite;
Preferably, the amorphous oxide is at least one selected from amorphous silica, amorphous alumina, amorphous aluminosilicate;
preferably, the metal organic framework material is selected from at least one of metal organic framework materials MIL-125, MIL-101, SIFSIX and MIL-53.
8. The preparation method according to claim 1, wherein the mass ratio of the cellulose to the water is 0.5 to 10: 1-20;
Preferably, the mass ratio of the cellulose to the catalyst is 0.5-10: 0.01 to 1;
preferably, the mass ratio of the water to the organic solvent is 0.5-10: 1 to 50;
preferably, the mass ratio of the adsorbent to the organic phase is 0.5-10: 1 to 50.
9. The preparation method according to claim 1, wherein the reaction conditions are as follows:
The temperature is 30-180 ℃;
The time is 2-10 h.
10. The method of claim 1, wherein the organic phase passes through a bed of adsorbent;
Recycling the organic solvent.
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