CN101827833B - 来自糖类和醇类的糠醛和5-(烷氧基甲基)糠醛衍生物的混合物 - Google Patents
来自糖类和醇类的糠醛和5-(烷氧基甲基)糠醛衍生物的混合物 Download PDFInfo
- Publication number
- CN101827833B CN101827833B CN2008801060568A CN200880106056A CN101827833B CN 101827833 B CN101827833 B CN 101827833B CN 2008801060568 A CN2008801060568 A CN 2008801060568A CN 200880106056 A CN200880106056 A CN 200880106056A CN 101827833 B CN101827833 B CN 101827833B
- Authority
- CN
- China
- Prior art keywords
- furfural
- fuel
- mixture
- alcohol
- diesel oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 235000000346 sugar Nutrition 0.000 title description 7
- 150000001298 alcohols Chemical class 0.000 title description 2
- 150000008163 sugars Chemical class 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001299 aldehydes Chemical group 0.000 claims abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 7
- 125000004849 alkoxymethyl group Chemical group 0.000 claims abstract description 4
- 239000000446 fuel Substances 0.000 claims description 63
- 239000002283 diesel fuel Substances 0.000 claims description 57
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 29
- 229930091371 Fructose Natural products 0.000 claims description 25
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 25
- 239000005715 Fructose Substances 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 150000002402 hexoses Chemical class 0.000 claims description 16
- 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 claims description 15
- 239000008103 glucose Substances 0.000 claims description 15
- 150000002972 pentoses Chemical class 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical group O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 claims description 7
- 239000002551 biofuel Substances 0.000 claims description 7
- 229960003487 xylose Drugs 0.000 claims description 7
- 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 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002841 Lewis acid Substances 0.000 claims description 5
- 150000002240 furans Chemical class 0.000 claims description 5
- 150000007517 lewis acids Chemical class 0.000 claims description 5
- 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 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 239000003502 gasoline Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 239000003225 biodiesel Substances 0.000 claims description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007848 Bronsted acid Substances 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 238000006266 etherification reaction Methods 0.000 abstract description 2
- 239000003377 acid catalyst Substances 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 28
- 239000000047 product Substances 0.000 description 14
- -1 alkoxy methyl furfural Chemical compound 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000002028 Biomass Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000013618 particulate matter Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 238000007600 charging Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- LLYCMZGLHLKPPU-UHFFFAOYSA-M perbromate Chemical compound [O-]Br(=O)(=O)=O LLYCMZGLHLKPPU-UHFFFAOYSA-M 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 description 3
- BHGBNDNKYPEAAT-UHFFFAOYSA-N 2-(ethoxymethyl)furan Chemical class CCOCC1=CC=CO1 BHGBNDNKYPEAAT-UHFFFAOYSA-N 0.000 description 3
- 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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 150000002016 disaccharides Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-N laevulinic acid Natural products CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 3
- GPFLOAQVIYTABX-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;trifluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)F.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GPFLOAQVIYTABX-BTVCFUMJSA-N 0.000 description 2
- GANSPRKOWQQXPE-UHFFFAOYSA-N 2-(Methoxymethyl)furan Chemical compound COCC1=CC=CO1 GANSPRKOWQQXPE-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DLRVVLDZNNYCBX-UHFFFAOYSA-N Polydextrose Polymers OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(O)O1 DLRVVLDZNNYCBX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229940040102 levulinic acid Drugs 0.000 description 2
- 150000004730 levulinic acid derivatives Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- ZKLRYZNOOWOOMP-UHFFFAOYSA-N 2,2,2-trifluoroacetic acid;trifluoromethanesulfonic acid Chemical compound OC(=O)C(F)(F)F.OS(=O)(=O)C(F)(F)F ZKLRYZNOOWOOMP-UHFFFAOYSA-N 0.000 description 1
- GZCGUPFRVQAUEE-UHFFFAOYSA-N 2,3,4,5,6-pentahydroxyhexanal Chemical compound OCC(O)C(O)C(O)C(O)C=O GZCGUPFRVQAUEE-UHFFFAOYSA-N 0.000 description 1
- GXICAIPZEZBXCA-UHFFFAOYSA-N 2-(ethoxymethyl)-5-methylfuran Chemical compound CCOCC1=CC=C(C)O1 GXICAIPZEZBXCA-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 description 1
- ZAQJHHRNXZUBTE-NQXXGFSBSA-N D-ribulose Chemical compound OC[C@@H](O)[C@@H](O)C(=O)CO ZAQJHHRNXZUBTE-NQXXGFSBSA-N 0.000 description 1
- ZAQJHHRNXZUBTE-UHFFFAOYSA-N D-threo-2-Pentulose Natural products OCC(O)C(O)C(=O)CO ZAQJHHRNXZUBTE-UHFFFAOYSA-N 0.000 description 1
- ZAQJHHRNXZUBTE-WUJLRWPWSA-N D-xylulose Chemical compound OC[C@@H](O)[C@H](O)C(=O)CO ZAQJHHRNXZUBTE-WUJLRWPWSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001202 Inulin Polymers 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229920000377 Sinistrin Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 150000001320 aldopentoses Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-STGXQOJASA-N alpha-D-lyxopyranose Chemical compound O[C@@H]1CO[C@H](O)[C@@H](O)[C@H]1O SRBFZHDQGSBBOR-STGXQOJASA-N 0.000 description 1
- WQZGKKKJIJFFOK-PQMKYFCFSA-N alpha-D-mannose Chemical compound OC[C@H]1O[C@H](O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-PQMKYFCFSA-N 0.000 description 1
- SRBFZHDQGSBBOR-QMKXCQHVSA-N alpha-L-arabinopyranose Chemical compound O[C@H]1CO[C@@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-QMKXCQHVSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- HSNWZBCBUUSSQD-UHFFFAOYSA-N amyl nitrate Chemical compound CCCCCO[N+]([O-])=O HSNWZBCBUUSSQD-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- UNXNGGMLCSMSLH-UHFFFAOYSA-N dihydrogen phosphate;triethylazanium Chemical compound OP(O)(O)=O.CCN(CC)CC UNXNGGMLCSMSLH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 description 1
- 229950006191 gluconic acid Drugs 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 1
- 229940029339 inulin Drugs 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BJHIKXHVCXFQLS-PQLUHFTBSA-N keto-D-tagatose Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-PQLUHFTBSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002581 ketopentoses Chemical class 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 229910021644 lanthanide ion Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- IMFKDZCVWYKAAL-UHFFFAOYSA-N phosphoric acid pyridine Chemical compound P(=O)(O)(O)O.N1=CC=CC=C1.N1=CC=CC=C1 IMFKDZCVWYKAAL-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000001259 polydextrose Substances 0.000 description 1
- 229940035035 polydextrose Drugs 0.000 description 1
- 235000013856 polydextrose Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000004879 turbidimetry Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/44—Solvents
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- 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
- Y02P20/10—Process efficiency
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Furan Compounds (AREA)
- Catalysts (AREA)
Abstract
本发明提供了制备糠醛和5-(烷氧基甲基)糠醛衍生物的混合物的方法,该方法通过使含C5和C6糖的原料与醇在酸性催化剂的存在下反应,接着使糠醛和5-(烷氧基甲基)糠醛的混合物氢化和/或醚化以使5-(烷氧基甲基)糠醛和糠醛的醛官能团都转化为烷氧基甲基官能团或甲基官能团。
Description
技术领域
本发明涉及由同时含有戊糖(C5糖)和己糖(C6糖)的混合进料来制备糠醛和5-(烷氧基甲基)糠醛(RMF)衍生物的混合物的方法。
背景技术
从DE635783中获知使用葡萄糖或含葡萄糖的原料来制备烷氧基甲基糠醛和乙酰丙酸烷基酯。例如,已经使用了蔗糖、葡萄糖和果糖(均为C6糖)的二糖。所述反应主要提供了乙酰丙酸衍生物。
在石化工业中使用的燃料、燃料添加剂和多种化学品来源于石油、天然气和煤,其均为有限资源。然而,生物质(Biomass)被认为是可再生能源。生物质为生物材料(包括可生物降解的废料),其可用于制备燃料或用于如纤维、化学品或热能的工业生产中。生物质不包括已经通过地质作用转化为如煤或石油的有机物质。
用于非食物用途的生物质来源产品的制备为朝阳产业。生物基燃料为引起人们浓厚兴趣的用途的实例。
生物质包含可以转化为增值产品的糖(己糖和戊糖)。目前生物燃料源于糖的工作主要涉及将葡萄糖或果糖发酵为乙醇或通过完全分解经由合成气体成为合成液体燃料。EP 0641 854描述了包含碳氢化合物和/或含有至少一种甘油醚的植物油衍生物的燃料组合物用于降低颗粒物排放的用途。
近来,果糖的酸性催化反应,即生产作为具有重大利益的中间产物的HMF重新引起人们的关注。大部分被研究的方法具有这样的缺点:HMF在其形成所需的反应条件下非常不稳定。从包含糖原料和酸性催化剂的水相中快速除去被认为是解决该问题的方法。Wisconsin-Madison大学的研究人员已经开发了由果糖制备HMF的方法。HMF可以转化为用于塑料的单体、石油或燃料的补充剂,甚或转化为燃料本身。James Dumesic教授和同事的方法首先在水相中使用酸性催化剂(盐酸或酸性离子交换树脂)使果糖脱水。加入盐使HMF盐析(salt-out)进入萃取相。提取相使用有利于从水相中提取HMF的惰性有机溶剂。两相法在高果糖浓度(10-50wt%)下进行,实现高产率(在90%果糖转化率下,80%HMF选择性),并将HMF传递入易于分离的溶剂中(DUMESIC,James A,et al.″Phase modifiers promote efficient production ofHydroxymethylfurfural from fructose″.Science.30juni 2006,vol.312,no.5782,p.1933-1937)。尽管由该方法得到的HMF产率引人注目,但是当使用比果糖更便宜且活性更低的己糖如葡萄糖或蔗糖作为原料时,多溶剂法由于相对复杂的设备设计并且由于低于理想的产率,其具有成本方面的缺点。HMF在室温下为固体,其不得不在后续步骤中转化才能成为可用的产品。Dumesic已经报道了将HMF转化成二甲基呋喃(DMF)的完整的氢解法步骤,DMF被认为是令人感兴趣的汽油添加剂。
在WO 2006/063220中提供了使用酸性催化剂在60℃下在24小时内分批或者在17小时内通过柱淋洗连续将果糖转化为5-乙氧基甲基糠醛(EMF)的方法。而没有讨论EMF的应用。
在共同悬而未决专利申请PCT/EP2007/002145中也描述了HMF醚的制备,包括这类醚作为燃料或燃料添加剂的用途。实际上,同时制备和测试了甲醚和乙醚(甲氧基甲基糠醛或MMF;乙氧基乙基糠醛或EMF)。然而,该共同悬而未决专利申请的发明限于使用与优选C1-C5的伯醇混合的己糖原料。不考虑使用与仲和叔醇混合的己糖和戊糖原料,支化的伯醇是唯一考虑的例子。尽管5-烷氧基甲基糠醛衍生物可用作燃料或燃料添加剂,但本发明人发现该醚还有改进的空间,特别是当以高浓度与如汽油、煤油、柴油、生物柴油(biodiesel)或绿色柴油(green diesel)的燃料混合时。本发明人已经开发出了针对糠醛及其衍生物的醛官能度对燃料混合物性能的副作用的其他衍生路线,由于分别在醛到醇氢化/醚化或者醛到甲基氢化的过程中,由戊糖获得的难溶于燃料的糠醛同时转化成为更易溶的糠基醚或甲基呋喃,该路线现在也能以混合的戊糖/己糖进料开始。因此,不再需要从混合的戊糖/己糖生物质进料中除去戊糖。
令人惊讶地,本发明人已经发现5-烷氧基甲基糠醛的衍生物与糠醛的衍生物,优选与(5-烷氧基甲基糠醛)相应的糠醛的衍生物的组合,比单独的5-烷氧基甲基糠醛或5-烷氧基甲基糠醛与糠醛的混合物具有更好的混合性。
发明内容
因此,本发明提供了通过使含C5和C6糖的原料与醇在酸性催化剂的存在下反应,接着通过糠醛和5-(烷氧基甲基)糠醛的混合物的氢化和/或醚化将5-(烷氧基甲基)糠醛和糠醛的醛官能团均转化为烷氧基甲基官能团或甲基官能团来制备糠醛和5-(烷氧基甲基)糠醛衍生物的混合物的方法。
当将上述方法的反应产物用作后续转化成燃料、燃料添加剂的原料或作为燃料或燃料添加剂中间产物时,所述反应产物无需提纯。实际上,在从生物质制备燃料或燃料添加剂中,所述反应产物可以包含非干扰性组分(non-interfering component),例如乙酰丙酸衍生物等。然而,为了便于参考,以含戊糖/己糖的混合原料的反应来描述反应产物的,得到糠醛和5-(烷氧基甲基)糠醛的混合物。本发明还提供了根据本发明制备的反应产物作为燃料或作为燃料添加剂的用途。用于与本发明的产物混合的燃料包括但不限于汽油和汽油-乙醇混合物、煤油、柴油、生物柴油(指的是非石油类的柴油燃料,包括通过植物油的酯交换制备的短链烷基(甲基或乙基)酯,其可以(单独或与常规的石油柴油混合)使用)、费托液(Fischer-Tropsch liquid)(例如由GTL气体至液体/CTL煤至液体/BTL生物质至液体的方法获得)、柴油-生物柴油混合物和绿色柴油以及柴油和/或生物柴油与绿色柴油(绿色柴油为通过氢化处理生物质来源的油、脂肪、油酯或裂解油而得到的碳氢化合物;例如参见UOP的报告:OPPORTUNITIES FOR BIORENEWABLES IN OIL REFINERIESFINAL TECHNICAL REPORT,SUBMITTED TO:U.S.DEPARTMENT OFENERGY(DOE Award Number:DE-FG36-05GO15085)。该产物为不含硫且具有90-100的十六烷值的质优价高的柴油燃料)的混合物。与本发明的产物混合的燃料也可以包括一种或多种其它呋喃化合物(furanics),其中用呋喃化合物的表述来涵盖呋喃和四氢呋喃的所有衍生物。本发明还提供了包含如上所述的燃料成分(fuel element)的燃料组合物和根据本发明制备的反应产物。
具体实施方式
生物质资源已经广为人知。生物质中令人感兴趣的组分为能够释放己糖和至少5%戊糖的混合物的那些进料(在下文中称作含戊糖和己糖的混合原料)。在有机化学中,己糖是化学式为C6H12O6的具有6个碳原子的单糖。根据官能团将己糖分为在1位上具有醛基的己醛糖和在其位上具有酮基的己酮糖。合适的6-碳单糖包括但不限于果糖、葡萄糖、半乳糖、甘露糖及它们的氧化、还原、醚化、酯化和酰胺化的衍生物,例如,醛糖酸或糖醇,虽然葡萄糖的活性低于果糖,但由于葡萄糖最充足、最经济,因而是最优选的单糖。戊糖为化学式为C5H10O5的具有5个碳原子的单糖。它们或者在1位具有醛官能团(戊醛糖)或在2位具有酮官能团(戊酮糖)。合适的5-碳单糖包括但不限于阿拉伯糖、核糖、核酮糖、木糖、木酮糖、来苏糖及它们的氧化、还原、醚化、酯化和酰胺化的衍生物。
另一方面,本发明人也已经成功地转化蔗糖,其也可大量利用。可以使用的其它二糖包括麦芽糖、纤维二糖和乳糖。可以使用的多糖包括纤维素、菊粉(多聚果糖)、淀粉(聚葡萄糖)和半纤维素。在制备5-HMF醚的过程中,所述多糖和二糖转化为其单糖组分并被脱水。
在本发明的方法中使用的醇优选具有单个羟基,其可以在伯、仲、甚至叔位置上。所述醇可以包含1至20个碳原子,优选1至8个碳原子,由此具有4个以上碳原子的醇优选具有支化的碳主链。
在本发明的方法中使用的优选的醇包括甲醇、乙醇、1-丙醇、2-丙醇、异丁醇、叔丁醇、异戊醇、异辛醇。也可以使用醇的混合物,例如异丁醇和叔丁醇的混合物。
在制备本发明的HMF醚的过程中使用的醇的量优选至少与原料的己糖含量等摩尔,但是通常过量使用。实际上,所述醇(例如叔丁醇)可以用作溶剂或助溶剂。在这种情况下,存在足够量的醇以形成HMF醚。
在本发明的方法中的酸性催化剂可以选自(卤化的)有机酸、无机酸、路易斯酸、离子交换树脂和沸石中,或为其组合和/或混合物。其可以为均相催化剂,但是考虑到纯化的原因,优选多相催化剂(指的是固体催化剂)。HMF醚可以用质子酸、布朗斯台德酸,或,可选地,路易斯酸或者用具有一个以上这些酸性官能度的催化剂来制备。
所述质子酸可以为有机或无机酸。例如,所述有机酸可以选自草酸、乙酰丙酸、马来酸、三氟醋酸(triflic acid)、甲磺酸或对甲苯磺酸中。或者,所述有机酸可以选自(多)磷酸、硫酸、盐酸、氢溴酸、硝酸、氢碘酸中,其可以原位产生。
某些盐可以用作催化剂,其中,所述盐可以为(NH4)2SO4/SO3、磷酸铵、吡啶氯化物、磷酸三乙胺、吡啶盐、磷酸吡啶、吡啶盐酸盐(pyridiniumhydrochloride)/氢溴酸盐(hydrobromide)/过溴酸盐(perbromate)、DMAP、铝盐、Th和Zr离子、磷酸锆、为醋酸盐或三氟醋酸盐(三氟甲基磺酸盐)的Sc和如Sm的镧系元素离子以及Y、Cr-离子、Al-离子、Ti-离子、Ca-离子、In-离子、ZrOCl2、VO(SO4)2、TiO2、V-紫菜碱、Zr-紫菜碱、Cr-紫菜碱、Ti-紫菜碱中的任意一种或多种。
选作脱水催化剂的路易斯酸可以为ZnCl2、AlCl3、BF3中的任一种。
离子交换树脂可以为合适的脱水催化剂。实例包括AmberliteTM和AmberlystTM、DiaionTM和LevatitTM。其它可以使用的固体催化剂包括天然粘土材料、沸石、负载酸(例如用无机酸浸渍的二氧化硅)、热处理的木炭、金属氧化物、金属硫化物、金属盐和混合氧化物,及其混合物。如果使用升高的反应温度,如在下文中所定义,那么所述催化剂在这些温度下应该是稳定的。
可以在由Lewkowski先生撰写的“Synthesis,chemistry and applications of5-hydroxymethylfurfural and its derivatives”Arkivoc.2001,p.17-54的综述论文的表1中找到可以用于本发明的方法中的催化剂的概况。催化剂的量可以根据选择的催化剂或催化剂混合物而变化。例如,基于进料的己糖含量,可以向反应混合物中加入催化剂的量从0.01至40mole%,优选从0.1至30mole%,更优选从1至20mole%变化。
在优选的实施方式中,所述催化剂为多相催化剂。
反应进行的温度可以变化,但是一般而言,优选的是在50至300摄氏度,优选125至250摄氏度,更优选150至225摄氏度的温度下进行反应。一般而言,高于300的温度是不优选的,因为反应的选择性降低,并且出现许多副产物,特别是糖的焦糖化。因为反应速率低,低于最低温度进行反应也是不优选的。如果在水的沸腾温度以上进行反应,那么反应优选在加压,例如10巴以上的氮气下进行。
通常将混合的戊糖/己糖原料溶于或悬浮在溶剂中以促进反应,该溶剂也可以为醇反应体。所述溶剂体系可以为选自水;亚砜,优选DMSO;酮,优选甲乙酮、甲基异丁基酮和丙酮;乙二醇醚,优选二乙二醇二甲醚(二甘醇二甲醚),或反应醇(reactant alcohol)中的一种或多种。也可以使用所谓的离子液体。后者指的是具有低熔点的一类惰性离子化合物,因而其可以用作溶剂。其实例包括,例如,在“Dehydration of fructose and sucrose into5-hydroxymethylfurfural in the presence of 1-H-3-methyl imidazolium chlorideacting both as solvent and catalyst”,Claude Moreau et al,Journal of MolecularCatalysis A:Chemical 253(2006)165-169中所讨论的氯化1-H-3-甲基咪唑鎓(1-H-3-methyl imidazolium chloride)。
溶剂的量优选以充分溶解或悬浮原料并足以限制不需要的副反应的量存在。
本发明的方法可以按分批法或连续法进行,具有或不具有(部分)产物流的循环以控制反应温度(通过热交换器循环)。例如,本发明的方法可以按连续流动法进行。在这种方法中,可以使用均相催化剂,并且反应物在流动法中的停留时间为0.1秒至10小时,优选为1秒至1小时,更优选为5秒至20分钟。
或者,连续流动法可以为使用多相酸性催化剂的固定床连续流动法或反应性(催化)蒸馏法。为了引发或再生多相酸性催化剂或提高性能,可以将无机酸或有机酸中加入到固定床或反应性蒸馏连续流动法的进料中。在固定床法中,液体时空速(LHSV)可以为1至1000,优选5至500,更优选为10至250,并且最优选为25至100min-1。
上述方法得到稳定的HMF醚与糠醛的混合物,接着该混合物可以在用作燃料或燃料添加剂之前转化为其他衍生物。
本发明还涉及5-(烷氧基甲基)糠醛和糠醛的混合物在氢化/醚化过程中将5-(烷氧基甲基)糠醛和糠醛的醛官能团都转化为烷氧基甲基官能团以将所得的产物用作燃料或燃料组分的用途。本发明还涉及使用5-(烷氧基甲基)糠醛和糠醛的混合物在氢化过程中优选同时将5-(烷氧基甲基)糠醛和糠醛的醛官能团转化为CH3官能团以用作燃料和/或燃料组分的用途。特别令人感兴趣的是所述醚在柴油、生物柴油或“绿色柴油”中的用途,其在上述燃料中的溶解度(大大)高于乙醇。除了上述燃料组分外,在本发明的燃料组分中可存在用于柴油燃料的常规添加剂和掺合剂。例如,本发明的燃料可以包含常规量的常规添加剂,例如十六烷改进剂、摩擦改性剂、除污剂、抗氧化剂和热稳定剂。本发明特别优选的柴油燃料的成分包括如上所述的碳氢化合物和HMF醚以及过氧化或硝酸酯十六烷改进剂,例如二叔丁基过氧化物、硝酸戊酯和硝酸乙基己酯。
向柴油燃料中加入本发明的醚类得到类似的NOx数且CO排放轻微增加;然而,利用加入足量的十六烷改进剂能够使NOx和CO的排放降低至远低于主要成分的标准燃料(base reference fuel)。
实施例
所附实施例用来说明本发明的方法以及使用该方法制备的产物作为燃料的适合性。这些实施例并非意欲限制本发明的范围。
使用如下的缩写:
F=糠醛
HMF=5-(羟甲基)糠醛
MMF=5-(甲氧基甲基)糠醛
EMF=5-(乙氧基甲基)糠醛
nBuMF=5-正(丁氧基甲基)糠醛
FME=糠基甲基醚
FEE=糠基乙基醚
DMMF=二(甲氧基甲基)呋喃
DEMF=二(乙氧基甲基)呋喃
根据下面的公式计算底物转化率和选择性以及产率:
转化率=100*[n0(底物)-nt(底物)]/n0底物
选择性=100*nt(产物)/[n0(底物)-nt(底物)]
产率=100*nt(产物)/n0底物,
其中:
n0-起始摩尔值
nt-在“t”时刻化合物的摩尔数。
实施例1
在典型的实验中,将32.5mg的木糖、32.5mg的葡萄糖或果糖,以及0.8ml的乙醇加入到内部涂覆特氟龙(Teflon)的反应器中。该混合物在固体酸性催化剂(6.5mg)存在下在氮气(12.5巴)中在150℃下反应1小时。在UV图谱上观察到的3个主峰确认为糠醛(F)、5-(羟甲基)糠醛(HMF)和5-(乙氧基甲基)糠醛EMF。
表1
木糖和 | 催化剂 | YF(%) | Y HMF(%) | Y EMF(%) |
葡萄糖 | CrCl2 | 23.2 | 4.8 | 11.5 |
葡萄糖 | 沸石HY 5 | 7.9 | 2.1 | 5.7 |
葡萄糖 | 三氟甲基磺酸铝(III) | 24.6 | 0.3 | 4.3 |
果糖 | CrCl2 | 20.7 | 5.7 | 14.8 |
果糖 | 沸石HY 5 | 8.0 | 4.2 | 14.6 |
果糖 | 三氟甲基磺酸铝(III) | 20.6 | 0.0 | 0.4 |
实施例2
在典型的实验中,将32.5mg的木糖、32.5mg的葡萄糖或果糖,以及0.8ml的甲醇加入到内部涂覆特氟龙(Teflon)的反应器中。该混合物在固体酸性催化剂(6.5mg)的存在下在氮气(12.5巴)中在150℃下反应1小时。在UV图谱上观察到的3个主峰确认为糠醛(F)、5-(羟甲基)糠醛(HMF)和5-(甲氧基甲基)糠醛(MMF)。
表2
木糖和 | 催化剂 | Y F(% | Y HMF(%) | Y MMF(%) |
葡萄糖 | CrCl2 | 11.0 | 0.9 | 11.3 |
葡萄糖 | 三氟甲基磺酸Al(III) | 17.8 | 0.1 | 2.1 |
果糖 | CrCl2 | 9.6 | 2.2 | 18.9 |
果糖 | 三氟甲基磺酸Al(III) | 18.4 | 0.0 | 1.5 |
果糖 | 蒙脱土K 5 | 4.0 | 1.0 | 8.1 |
实施例3
在典型的实验中,将65mg的木糖、葡萄糖与果糖(1∶1∶1,重量比)的混合物和6.5mg的固体酸性催化剂在内部涂覆特氟龙的反应器中混合。加入0.8ml的醇混合物(甲醇、乙醇和正丁醇,体积比1/2/1),并用氮气增压至12.5巴。混合物在150℃下反应1小时。在UV图谱上观察到的主峰确认为F、HMF、EMF、MMF和nBuMF。
表3
催化剂 | Y F(%) | Y HMF(%) | Y EMF(%) | Y MMF(%) | YnBuMF(%) |
CrCl2 | 11.8 | 6.9 | 7.5 | 7.6 | 2.6 |
沸石HY 5 | 5.1 | 5.4 | 4.2 | 5.1 | 0.8 |
沸石HY 15 | 5.6 | 1.6 | 5.3 | 5.2 | 1.5 |
蒙脱土K 5 | 5.3 | 1.3 | 6.2 | 6.1 | 2.0 |
蒙脱土K 10 | 4.4 | 1.9 | 5.1 | 5.0 | 1.6 |
Amberlyst36Wet | 3.3 | 2.1 | 6.2 | 6.4 | 1.7 |
沸石β | 9.8 | 0.3 | 5.5 | 5.3 | 1.9 |
实施例4
相分离/不同呋喃化合物的结晶温度(℃)/柴油混合物的相分离/柴油混合物
将合成的呋喃化合物及其混合物与通常的柴油燃料以1∶1的体积比混合。在由Avantium Technologies,Amsterdam开发的多反应器体系Crystal 16TM中测定混合物的混溶性。因此,在用磁力搅拌棒以700rpm的持续搅拌下,以0.375℃/min的速度冷却样品。通过浊度测量记录相分离和/或结晶。糠醛(F)和乙氧基甲基糠醛(EMF)不能与柴油以1/1的比率混溶。加入低于40%的DMMF,在室温下完全混溶。与单独使用二醚相比,C-5相关的单醚的存在改善了混溶性,特别是当甲醇用作酯化试剂时。
表4:不同的呋喃化合物与普通的柴油的混溶性
燃料组分 | 组分比(v/v) | 相分离/结晶温度(℃) | |
1 | 柴油 | -12 | |
2 | 柴油+DMMF | 1∶1 | >25 |
3 | 柴油+FME | 1∶1 | -7 |
4 | 柴油+DMMF+FME | 2∶1∶1 | 14 |
5 | 柴油+DEMF | 1∶1 | -8 |
6 | 柴油+FEE | 1∶1 | -11 |
7 | 柴油+DEMF+FEE | 2∶1∶1 | -11 |
8 | 柴油+EMF | 1∶1 | >25 |
9 | 柴油+F | 1∶1 | >25 |
10 | 柴油+EMF+F | 2∶1∶1 | >25 |
实施例5
用柴油、FEE和DEMF测试发动机排放
在Citroen Berlingo测试车的D9B柴油发动机中,用普通的市售柴油燃料(实验1)和其中分别加入25vol.%FEE(实验2)或25vol%DEMF(实验3)的相同的市售柴油进行比较测试。FEE和DEMF以液体的形式加入,并且以使用的混合比不会产生任何混合或絮问题。开始用普通的柴油使发动机运行稳定,之后将供给燃料分别换为25vol%FEE-柴油混合物和25vol%DEMF-柴油混合物。
在使用市售柴油燃料以及使用25vol%FEE和25%DEMF混合物的稳定运行期间,进行如下测试:总颗粒物、体积、O2、CO、CO2、NOx(NO+NO2)和总碳氢化合物。
根据NEN-EN 13284-1取样总颗粒物;
根据VDI 2066-5取样粒径分布;
根据ISO 10780测量体积;
根据ISO 10396取样气体;
根据NEN-ISO 12039分析O2、CO和CO2;
根据NEN-ISO 10849分析NOx(NO+NO2);
根据NEN-EN 13526分析总碳氢化合物。
表5:100%市售柴油燃料的气体分析结果
表6:100%市售柴油燃料的颗粒物结果
表7:市售柴油与25vol%FEE的混合物的气体分析结果
表8:市售柴油与25vol%FEE的混合物的颗粒物结果
表9:市售柴油与25vol%DEMF的混合物的气体分析结果
表10:市售柴油与25vol%DEMF的混合物的颗粒物结果
实施例6
用柴油、FME和DMMF测试发动机排放
以与实施例5相似的方式,在Citroen Berlingo测试车的D9B柴油发动机中,用普通的市售柴油燃料(实验4)和其中分别加入25vol.%FME(实验5)或12.5vol%DMMF(实验6)的相同的市售柴油进行比较测试。FME和DMMF以液体的形式加入,并且以使用的混合比不产生任何混合或絮凝问题。起初用普通的柴油稳定地运行发动机,其后将燃料供给分别转换为25vol%FME-柴油混合物和12.5vol%DMMF-柴油混合物。
测量的结果示于表11-15中。
表11:100%市售柴油燃料的气体分析结果
表12:100%市售柴油燃料的颗粒物结果
表13:市售柴油与25vol%FME的混合物的气体分析结果
表14:市售柴油与25vol%FME的混合物的颗粒物结果
表15:市售柴油与12.5vol%DMMF的混合物的气体分析结果
表16:市售柴油与12.5vol%DMMF的混合物的颗粒物结果
实施例7
燃料可溶性
燃料的可溶性是柴油燃料应用的主要关注点。并不是所有的高极性氧化剂(oxygenate)在目前的市售柴油燃料中都具有良好的可溶性。结果显示:2,5-二(乙氧基甲基)呋喃和2-(乙氧基甲基)呋喃(由混合C6/C5原料制备的醚化产物)与市售柴油的混合物以及5-(乙氧基甲基)-2-甲基呋喃和2-甲基呋喃(由混合的C6/C5原料制备的氢化产物)与市售柴油的混合物可以以任意比率完全混溶。在比较组实验中显示乙氧基甲基糠醛(EMF)(由C6原料制备)以5vol%能与市售柴油完全混溶,但是以25vol%和40vol%的EMF与柴油混合发生相分离。用EMF/糠醛混合物的结果比单独用EMF的结果差。
参考文献
·DE 635783
·DUMESIC,James A,et al.″Phase modifiers promote efficient productionof Hydroxymethylfurfural from fructose″.Science.30June 2006,vol.312,no.5782,p.1933-1937.
·WO 2006/063220
·Chapter 15of Advanced Organic Chemistry,by Jerry March,and inparticular under reaction 5-4.(3rd ed.,1985by John Wiley & Sons,pp.684-685).
·LEWKOWSKI,Jaroslaw.Synthesis,chemistry and applications of 5-hydroxymethylfurfural and its derivatives.Arkivoc.2001,p.17-54.
·MOREAU,Claude,et al.″Dehydration of fructose and sucrose into 5-hydroxymethylfurfural in the presence of 1-H-3-methyl imidazolium chlorideacting both as solvent and catalyst″,Journal of Molecular Catalysis A:Chemical253(2006)p.165-169.
·EP 0641 854
·UOP report OPPORTUNITIES FOR BIORENEWABLES IN OILREFINERIES FINAL TECHNICAL REPORT,SUBMITTED TO:U.S.DEPARTMENT OF ENERGY(DOE Award Number:DE-FG36-05GO15085))
·Adv.Synth.Catal.2001,343,220-225
·EP 0 356 703
·FR 2 669 634
Claims (8)
1.一种制备糠醛和5-烷氧基甲基糠醛衍生物的混合物的方法,其是通过使含己糖和戊糖的原料与脂肪族的C1-C8的醇在酸性催化剂的存在下反应,得到糠醛与5-(烷氧基甲基)糠醛的混合物,接着使糠醛和5-烷氧基甲基糠醛的混合物氢化,并将氢化的产物醚化以将5-(烷氧基甲基)糠醛和糠醛的醛官能团都转化为烷氧基甲基官能团,
所述脂肪族的C1–C8的醇选自甲醇、乙醇、1-丙醇、2-丙醇、正丁醇、异丁醇、叔丁醇、异戊醇、异辛醇及其混合物,
其中,所述含己糖的原料选自葡萄糖、果糖和蔗糖,
以及所述含戊糖的原料为木糖。
2.根据权利要求1所述的方法,其中,所述酸性催化剂选自固体有机酸、无机酸、盐、路易斯酸、离子交换树脂、沸石和其组合。
3.根据权利要求2所述的方法,其中,所述酸性催化剂为固体布朗斯台德酸。
4.根据权利要求2所述的方法,其中,所述酸性催化剂为固体路易斯酸。
5.根据权利要求1所述的方法,其中,所述反应在50至300摄氏度的温度下进行。
6.根据权利要求1所述的方法,其中,所述方法以连续流动法进行。
7.通过权利要求1所述的方法制备的醚作为燃料或燃料添加剂的用途。
8.一种燃料组合物,其包含通过权利要求1所述的方法制备的醚作为燃料组分,该燃料组分非必须地与汽油和汽油-乙醇混合物、煤油、柴油、生物柴油、费托液、柴油-生物柴油混合物和绿色柴油以及柴油和/或生物柴油与绿色柴油的混合物,以及呋喃和四氢呋喃的其它衍生物中的一种或多种混合。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07017572 | 2007-09-07 | ||
EP07017572.4 | 2007-09-07 | ||
PCT/EP2008/007428 WO2009030511A1 (en) | 2007-09-07 | 2008-09-05 | Mixture of furfural and 5-(alkoxymethyl)furfural derivatives from sugars and alcohols |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101827833A CN101827833A (zh) | 2010-09-08 |
CN101827833B true CN101827833B (zh) | 2013-07-10 |
Family
ID=38776292
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2008801060568A Expired - Fee Related CN101827833B (zh) | 2007-09-07 | 2008-09-05 | 来自糖类和醇类的糠醛和5-(烷氧基甲基)糠醛衍生物的混合物 |
Country Status (15)
Country | Link |
---|---|
US (1) | US8277521B2 (zh) |
EP (1) | EP2195306B1 (zh) |
JP (1) | JP5950321B2 (zh) |
KR (1) | KR20100072013A (zh) |
CN (1) | CN101827833B (zh) |
AP (1) | AP2010005179A0 (zh) |
AU (1) | AU2008295006B2 (zh) |
BR (1) | BRPI0815436B1 (zh) |
CA (1) | CA2697802C (zh) |
EA (2) | EA018486B1 (zh) |
MX (1) | MX2010002603A (zh) |
MY (1) | MY148864A (zh) |
UA (1) | UA98002C2 (zh) |
WO (1) | WO2009030511A1 (zh) |
ZA (1) | ZA201001902B (zh) |
Families Citing this family (53)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2128226A1 (en) * | 2008-05-19 | 2009-12-02 | Furanix Technologies B.V | Fuel component |
WO2010131844A2 (ko) * | 2009-05-11 | 2010-11-18 | 한국생산기술연구원 | 해조류 유래 갈락탄을 이용한 바이오연료의 제조방법 |
KR101116392B1 (ko) | 2009-08-12 | 2012-03-09 | 한국생산기술연구원 | 해조류 유래 갈락탄을 이용한 바이오 연료의 제조방법 |
US8236973B2 (en) | 2009-11-05 | 2012-08-07 | Battelle Memorial Institute | Adsorption separation processes for ionic liquid catalytic processes |
US8871957B2 (en) * | 2010-04-15 | 2014-10-28 | Korea Institute Of Industrial Technology | Metal catalyst composition for producing furfural derivatives from raw materials of lignocellulosic biomass, and method for producing furfural derivatives using the composition |
US8324409B2 (en) | 2010-04-23 | 2012-12-04 | The Board Of Trustees Of The University Of Illinois | Efficient method for preparing 2,5-dimethylfuran |
CN102260229A (zh) * | 2010-05-28 | 2011-11-30 | 中国科学院大连化学物理研究所 | 一种制备5-羟甲基糠醛及5-烷氧基甲基糠醛的方法 |
ES2862178T3 (es) | 2010-06-26 | 2021-10-07 | Virdia Llc | Métodos de producción de mezclas de azúcares |
IL206678A0 (en) | 2010-06-28 | 2010-12-30 | Hcl Cleantech Ltd | A method for the production of fermentable sugars |
IT1401427B1 (it) | 2010-08-11 | 2013-07-26 | Nuova Pignone S R L | Metodi e dispositivi usati per controllare automaticamente la velocita di un espansore |
IL207945A0 (en) | 2010-09-02 | 2010-12-30 | Robert Jansen | Method for the production of carbohydrates |
CN102453559A (zh) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | 一种用于发动机节能减排的燃油添加剂及应用 |
WO2012088208A2 (en) | 2010-12-21 | 2012-06-28 | E. I. Du Pont De Nemours And Company | Methods for furfural production from branched non-fermentable sugars in stillage or syrup |
EP2674421B1 (en) * | 2011-01-28 | 2016-07-13 | Mitsubishi Chemical Corporation | Method for producing 2-furaldehyde |
CN102206198A (zh) * | 2011-03-31 | 2011-10-05 | 中国科学院青岛生物能源与过程研究所 | 一种微波合成5-(烷氧甲基)糠醛的方法 |
WO2012137201A1 (en) | 2011-04-07 | 2012-10-11 | Hcl Cleantech Ltd. | Lignocellulose conversion processes and products |
KR101924414B1 (ko) * | 2011-06-09 | 2018-12-03 | 마이크로마이다스, 인코포레이티드 | 치환된 푸란을 제조하기 위한 바이오매스의 변환을 위한 다상 반응기의 이용 |
US8952186B2 (en) * | 2011-06-22 | 2015-02-10 | Basf Se | Method for dehydrating a carbohydrate-comprising |
JP2014528407A (ja) * | 2011-09-29 | 2014-10-27 | エスケー ケミカルズ カンパニー リミテッド | 有機溶媒の下でイオン交換樹脂を用いる5−ヒドロキシメチル−2−フルフラールまたはそのアルキルエーテル誘導体の製造方法 |
US9617608B2 (en) | 2011-10-10 | 2017-04-11 | Virdia, Inc. | Sugar compositions |
CN102442982B (zh) * | 2011-12-06 | 2014-03-19 | 中国科学院青岛生物能源与过程研究所 | 一种由糖制备呋喃二甲醇二烷基醚的方法 |
WO2013102002A1 (en) | 2011-12-28 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Processes for making furfurals |
US9181211B2 (en) | 2011-12-28 | 2015-11-10 | E I Du Pont De Nemours And Company | Process for the production of furfural |
WO2013101999A1 (en) * | 2011-12-28 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Process for the production of furfural |
CN104039772B (zh) * | 2011-12-28 | 2016-06-29 | 纳幕尔杜邦公司 | 用于制备糠醛的方法 |
CN103183653A (zh) * | 2011-12-29 | 2013-07-03 | 广西科学院 | 一种制备5-羟甲基糠醛的绿色方法 |
JP6374861B2 (ja) | 2012-05-03 | 2018-08-15 | ヴァーディア, インコーポレイテッド | リグノセルロース材料の処理のための方法 |
CN103467418B (zh) * | 2012-06-07 | 2016-01-20 | 中国科学院大连化学物理研究所 | 一种果糖基生物质催化转化制呋喃衍生物的方法 |
WO2014009522A1 (en) * | 2012-07-13 | 2014-01-16 | Dsm Ip Assets B.V. | Process to produce furfural |
US9388151B2 (en) | 2012-10-26 | 2016-07-12 | Micromidas, Inc. | Methods for producing 5-(halomethyl) furfural |
CN103073526B (zh) * | 2012-12-26 | 2014-12-03 | 中国科学院宁波材料技术与工程研究所 | 一种2,5-二取代的四氢呋喃类混合物的制备方法 |
MY196287A (en) | 2013-03-14 | 2023-03-24 | Micromidas Inc | Methods For Purifying 5-(Halomethyl)Furfural |
JP2016512548A (ja) | 2013-03-14 | 2016-04-28 | マイクロマイダス,インコーポレイテッド | 固体形態の5−(ハロメチル)フルフラールおよびその製造方法 |
WO2014197195A2 (en) | 2013-06-06 | 2014-12-11 | California Institute Of Technology | Diels-alder reactions catalyzed by lewis acid containing solids: renewable production of bio-plastics |
CN111662253A (zh) | 2013-09-20 | 2020-09-15 | 微麦德斯公司 | 生产5-(卤甲基)糠醛的方法 |
EP3071556A1 (en) * | 2013-11-21 | 2016-09-28 | Lali, Arvind Mallinath | A process for synthesis of furan derivative using an acid catalyst and preparation thereof |
US9388351B2 (en) | 2014-06-18 | 2016-07-12 | Phillips 66 Company | Furfural to fuel |
EP3242871B1 (en) | 2015-01-07 | 2019-11-06 | Virdia, Inc. | Methods for extracting and converting hemicellulose sugars |
EP3256513B1 (en) | 2015-02-10 | 2021-10-27 | Furanix Technologies B.V. | Fuel composition comprising humins |
KR101767182B1 (ko) * | 2015-04-15 | 2017-08-11 | 한국화학연구원 | 바이오매스로부터 퓨란계 유도체의 제조방법 |
US11091815B2 (en) | 2015-05-27 | 2021-08-17 | Virdia, Llc | Integrated methods for treating lignocellulosic material |
CN105085448B (zh) * | 2015-08-21 | 2017-12-29 | 中国科学院上海高等研究院 | 一种以微藻为原料制备5‑羟甲基糠醛的方法 |
JP2018538361A (ja) * | 2015-11-04 | 2018-12-27 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | フラン−2,5−ジカルボン酸を調製する方法 |
EP3387038A1 (en) | 2015-12-11 | 2018-10-17 | Societe Anonyme des Eaux Minerales d'Evian Et en Abrege "S.A.E.M.E" | Pet polymer with an anti-crystallization comonomer that can be bio-sourced |
CN108779088B (zh) | 2016-01-13 | 2021-10-08 | 斯道拉恩索公司 | 2,5-呋喃二甲酸及其中间体和衍生物的制备方法 |
CN106336923B (zh) * | 2016-11-10 | 2018-03-16 | 黑龙江省能源环境研究院 | 乳化柴油复合添加剂及其制备方法 |
CN107324994A (zh) * | 2017-07-10 | 2017-11-07 | 济南大学 | 脱氧核糖制备乙酰丙酸乙酯的方法 |
AU2018301662B2 (en) | 2017-07-12 | 2022-06-30 | Stora Enso Oyj | Purified 2,5-furandicarboxylic acid pathway products |
KR102278268B1 (ko) * | 2019-11-22 | 2021-07-16 | 한국화학연구원 | 5-알콕시메틸퍼퓨랄로부터 2,5-퓨란디카르복실산 제조방법 |
WO2020190043A1 (ko) * | 2019-03-21 | 2020-09-24 | 한국화학연구원 | 프룩토스로부터 5-알콕시메틸퍼퓨랄 및 2,5-퓨란디카르복실산의 제조방법 |
CN111057594B (zh) * | 2019-12-30 | 2021-10-29 | 李旭 | 一种醇基燃料添加剂的制备方法 |
RU2736717C1 (ru) * | 2019-12-30 | 2020-11-19 | Акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" (АО "ВНИИ НП") | Смазывающая добавка к дизельным топливам, представляющая собой ацетали фурфурола, и топливная композиция, ее содержащая |
CN114345376A (zh) * | 2022-01-07 | 2022-04-15 | 浙江华康药业股份有限公司 | 一种酸性离子缓冲液催化剂及其制备方法以及使用该催化剂制备糠醛的系统和方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE635783C (de) * | 1934-06-03 | 1936-09-28 | Borys Korotkyj Dr | Verfahren zur Herstellung von Alkoxymethylfurfurolen und Laevulinsaeurealkylestern |
DE3621517A1 (de) * | 1986-06-27 | 1988-01-07 | Klaus Dipl Chem Dr Garves | Darstellung von alkoxymethylfurfuralen und alkyllevulinaten aus cellulose oder lignocellulosen oder staerke und alkoholen |
WO1999067409A1 (en) * | 1998-06-23 | 1999-12-29 | The Regents Of The University Of California | Method of treating biomass material |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3095882A (en) * | 1961-08-04 | 1963-07-02 | Philip Morris Inc | Tobacco flavorants |
FR2462433A1 (fr) * | 1979-08-03 | 1981-02-13 | Bertin & Cie | Perfectionnements apportes aux procedes et aux appareillages pour l'obtention de furfural a partir de matieres vegetales |
JPS6210078A (ja) * | 1985-01-11 | 1987-01-19 | コフインパ−ル・ソシエテ・アノニム | キシロ−ス水溶液、好ましくは製紙用パルプ、織布用パルプ製造時の残留黒液からフルフラ−ルを製造する方法およびプラント |
DE3826073A1 (de) | 1988-07-30 | 1990-02-01 | Hoechst Ag | Verfahren zur oxidation von 5-hydroxymethylfurfural |
JPH02108682A (ja) * | 1988-10-14 | 1990-04-20 | Agency Of Ind Science & Technol | フルフラールの製造および濃縮方法 |
FR2669634B1 (fr) | 1990-11-22 | 1994-06-10 | Furchim | Procede de fabrication d'acide 2-5-furane dicarboxylique. |
US5308365A (en) | 1993-08-31 | 1994-05-03 | Arco Chemical Technology, L.P. | Diesel fuel |
RU2203279C1 (ru) | 2001-10-22 | 2003-04-27 | Институт химии и химической технологии СО РАН | Способ получения простых эфиров 5-гидроксиметилфурфурола |
SE526429C2 (sv) * | 2003-10-24 | 2005-09-13 | Swedish Biofuels Ab | Metod för att framställa syreinnehållande föreningar utgående från biomassa |
US7393963B2 (en) | 2004-12-10 | 2008-07-01 | Archer-Daniels-Midland Company | Conversion of 2,5-(hydroxymethyl)furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor |
JP5101821B2 (ja) * | 2006-01-28 | 2012-12-19 | 公立大学法人大阪府立大学 | 不均一系リン酸ジルコニウム触媒、脱水反応方法、5−ヒドロキシメチルフルフラール製造方法、セルロース分解方法、及び不均一系リン酸ジルコニウム触媒の再生方法 |
US7520905B1 (en) * | 2006-02-06 | 2009-04-21 | Gene E Lightner | Additives derived from biomass extracted by biodiesel fuel oil |
EP1834950A1 (en) | 2006-03-10 | 2007-09-19 | Avantium International B.V. | Method for the synthesis of 5-alkoxymethylfurfural ethers and their use |
US7880049B2 (en) * | 2006-06-06 | 2011-02-01 | Wisconsin Alumni Research Foundation | Production of liquid alkanes in the jet fuel range (C8-C15) from biomass-derived carbohydrates |
EP2032550B1 (en) * | 2006-06-06 | 2013-11-20 | Wisconsin Alumni Research Foundation | Catalytic process for producing furan derivatives from carbohydrates in a biphasic reactor |
-
2008
- 2008-05-09 UA UAA201004053A patent/UA98002C2/uk unknown
- 2008-09-05 WO PCT/EP2008/007428 patent/WO2009030511A1/en active Application Filing
- 2008-09-05 AP AP2010005179A patent/AP2010005179A0/xx unknown
- 2008-09-05 BR BRPI0815436A patent/BRPI0815436B1/pt not_active IP Right Cessation
- 2008-09-05 US US12/446,489 patent/US8277521B2/en not_active Expired - Fee Related
- 2008-09-05 AU AU2008295006A patent/AU2008295006B2/en not_active Ceased
- 2008-09-05 EA EA201070345A patent/EA018486B1/ru not_active IP Right Cessation
- 2008-09-05 CA CA2697802A patent/CA2697802C/en not_active Expired - Fee Related
- 2008-09-05 JP JP2010523345A patent/JP5950321B2/ja not_active Expired - Fee Related
- 2008-09-05 MY MYPI2010000980A patent/MY148864A/en unknown
- 2008-09-05 MX MX2010002603A patent/MX2010002603A/es active IP Right Grant
- 2008-09-05 KR KR1020107007493A patent/KR20100072013A/ko not_active Application Discontinuation
- 2008-09-05 CN CN2008801060568A patent/CN101827833B/zh not_active Expired - Fee Related
- 2008-09-05 EP EP08785855.1A patent/EP2195306B1/en not_active Not-in-force
- 2008-09-05 EA EA201101606A patent/EA201101606A1/xx unknown
-
2010
- 2010-03-17 ZA ZA2010/01902A patent/ZA201001902B/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE635783C (de) * | 1934-06-03 | 1936-09-28 | Borys Korotkyj Dr | Verfahren zur Herstellung von Alkoxymethylfurfurolen und Laevulinsaeurealkylestern |
DE3621517A1 (de) * | 1986-06-27 | 1988-01-07 | Klaus Dipl Chem Dr Garves | Darstellung von alkoxymethylfurfuralen und alkyllevulinaten aus cellulose oder lignocellulosen oder staerke und alkoholen |
WO1999067409A1 (en) * | 1998-06-23 | 1999-12-29 | The Regents Of The University Of California | Method of treating biomass material |
Also Published As
Publication number | Publication date |
---|---|
WO2009030511A1 (en) | 2009-03-12 |
EP2195306B1 (en) | 2017-05-17 |
EA201070345A1 (ru) | 2010-08-30 |
ZA201001902B (en) | 2010-12-29 |
AU2008295006B2 (en) | 2012-11-08 |
UA98002C2 (uk) | 2012-04-10 |
KR20100072013A (ko) | 2010-06-29 |
BRPI0815436B1 (pt) | 2019-02-05 |
JP2010538033A (ja) | 2010-12-09 |
CN101827833A (zh) | 2010-09-08 |
AP2010005179A0 (en) | 2010-04-30 |
EA018486B1 (ru) | 2013-08-30 |
US8277521B2 (en) | 2012-10-02 |
US20100083565A1 (en) | 2010-04-08 |
AU2008295006A1 (en) | 2009-03-12 |
BRPI0815436A2 (pt) | 2017-05-23 |
MY148864A (en) | 2013-06-14 |
EA201101606A1 (ru) | 2012-08-30 |
JP5950321B2 (ja) | 2016-07-13 |
CA2697802A1 (en) | 2009-03-12 |
CA2697802C (en) | 2018-04-03 |
EP2195306A1 (en) | 2010-06-16 |
MX2010002603A (es) | 2010-04-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101827833B (zh) | 来自糖类和醇类的糠醛和5-(烷氧基甲基)糠醛衍生物的混合物 | |
EP2197868B1 (en) | Hydroxymethylfurfural ethers from sugars or hmf and mixed alcohols | |
EP2197867B1 (en) | Hydroxymethylfurfural ethers from sugars or hmf and branched alcohols | |
EP2197866B1 (en) | Hydroxymethylfurfural ethers from sugars and higher alcohols | |
EP2183236B1 (en) | Hydroxymethylfurfural ethers and esters prepared in ionic liquids | |
EP2197865B1 (en) | Hydroxymethylfurfural ethers from hmf and olefins | |
AU2008295004B2 (en) | 5-substituted 2-(alkoxymethyl)furans | |
EP2033958A1 (en) | Hydroxymethylfurfural ethers from sugars and di- and triols | |
US20100299991A1 (en) | Hydroxymethylfurfural Ethers from Sugars and Olefins | |
EP2034005A1 (en) | Fuel additive concentrate derived from a biomass resource |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130710 Termination date: 20200905 |