CN101809010B - 来自糖或hmf和混合醇的羟甲基糠醛醚 - Google Patents
来自糖或hmf和混合醇的羟甲基糠醛醚 Download PDFInfo
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- CN101809010B CN101809010B CN2008801059876A CN200880105987A CN101809010B CN 101809010 B CN101809010 B CN 101809010B CN 2008801059876 A CN2008801059876 A CN 2008801059876A CN 200880105987 A CN200880105987 A CN 200880105987A CN 101809010 B CN101809010 B CN 101809010B
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- Prior art keywords
- mixture
- alcohol
- fuel
- reaction
- hmf
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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 51
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 11
- -1 Hydroxymethylfurfural ethers Chemical class 0.000 title abstract description 20
- 150000001298 alcohols Chemical class 0.000 title abstract description 3
- 235000000346 sugar Nutrition 0.000 title description 6
- 150000008163 sugars Chemical class 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 64
- 239000000203 mixture Substances 0.000 claims abstract description 56
- 150000002402 hexoses Chemical class 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 72
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 57
- 239000000446 fuel Substances 0.000 claims description 48
- 239000003054 catalyst Substances 0.000 claims description 31
- 229930091371 Fructose Natural products 0.000 claims description 24
- 239000005715 Fructose Substances 0.000 claims description 24
- 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 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 20
- 239000002283 diesel fuel Substances 0.000 claims description 19
- 230000002378 acidificating effect Effects 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 14
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- 239000002028 Biomass Substances 0.000 claims description 13
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- 239000008103 glucose Substances 0.000 claims description 12
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
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- 239000003377 acid catalyst Substances 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 239000006241 High Modulus Furnace Substances 0.000 description 37
- 239000000758 substrate Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- 239000003921 oil Substances 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
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- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 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 6
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- 229910052799 carbon Inorganic materials 0.000 description 5
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- 150000001875 compounds Chemical class 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000007869 Guerbet synthesis reaction Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006266 etherification reaction Methods 0.000 description 4
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 4
- 150000004676 glycans Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920001282 polysaccharide Polymers 0.000 description 4
- 239000005017 polysaccharide Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-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
- 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 3
- 150000001721 carbon Chemical group 0.000 description 3
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- 229940040102 levulinic acid Drugs 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 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
- 230000035484 reaction time Effects 0.000 description 3
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- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-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
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- 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
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
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- 238000005886 esterification reaction Methods 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
- 238000000105 evaporative light scattering detection Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
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- 235000013305 food Nutrition 0.000 description 1
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- 235000019322 gelatine Nutrition 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 229910001449 indium ion Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 229910021644 lanthanide ion Inorganic materials 0.000 description 1
- 150000004730 levulinic acid derivatives Chemical class 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry 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
- 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 150000002971 pentose derivatives Chemical class 0.000 description 1
- 150000002972 pentoses Chemical class 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
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000011949 solid catalyst Substances 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
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 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
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 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
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- 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
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Abstract
本发明提供了一种制备5-羟甲基糠醛醚混合物的方法,该方法通过在酸性催化剂存在下使含己糖的原料或HMF与混合醇反应。
Description
技术领域
本发明涉及一种由生物质制备5-羟甲基糠醛(5-(羟甲基)-2-糠醛,或HMF)醚混合物的方法。
背景技术
在石油化工行业使用的燃料、燃料添加剂和各种化学品是来自石油、天然气和煤炭,均为不可再生资源。另一方面,生物质被认为是可再生资源。生物质是指生物材料(包括可生物降解的废物),其可以用于制备燃料或用于工业上生产例如纤维、化学品或热。其不包括通过地质过程已变成如煤或石油的物质的有机物质。
生产用于非食品应用的生物质衍生品是一个发展中的行业。基于生物的燃料是一个引起人们强烈兴趣的应用实例。
生物质含有可转化为价值增值产品的糖(己糖和戊糖)。目前由糖制备的生物燃料的工作主要是集中在将葡萄糖或蔗糖发酵成为乙醇或通过合成气完全分解成合成液体燃料。EP 0641854描述了包含烃类和/或含有至少一种甘油醚的植物油衍生物的燃料组合物的应用,以减少颗粒物排放量。
最近,人们重新重视了果糖的酸催化反应,其生成具有巨大效益的中间体HMF。大多数被研究的方法的缺点在于:HMF在其形成所需的反应条件下不是很稳定。从含糖原料和酸性催化剂的水相中快速去除已被看作是解决这一问题的方案。美国威斯康星-麦迪逊大学的研究人员已经开发出一种由果糖制备HMF的方法。HMF可以转化成塑料的单体、石油或燃料填充剂,甚至可能转变成燃料本身。James Dumesic教授和同事的方法首先使用酸性催化剂(盐酸或酸性离子交换树脂)将果糖在水相中脱水。加入盐以使HMF盐析至萃取相。萃取相使用惰性有机溶剂,其有利于从水相萃取HMF。两相法在高果糖浓度(10~50重量%)下操作,达到高产量(在果糖转化率为90%下,HMF的选择性为80%),并将HMF送入易于分离的溶剂中(DUMESIC,James A等,“相改性剂促进由果糖高效地生产羟甲基糠醛(Phase modifiers promote efficient production of Hydroxymethylfurfural fromfructose)”.Science.30 juni 2006,vol.312,no.5782,p.1933-1937)。虽然由此法生产HMF很吸引人,由于相对复杂的工厂设计,且由于当将比果糖便宜的和活性低的己糖(如葡萄糖或蔗糖)用作原料时低于理想产率,多溶剂法具有成本劣势。HMF在室温下是固态的,其在随后的步骤中须转化为有用的产品。Dumesic报道了完整的氢解法步骤以将HMF转化为二甲基呋喃(DMF),其被认为是一个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小时内通过柱洗脱连续将果糖转化成5-乙氧基甲基糠醛(EMF)的方法。EMF的应用并没有被讨论。
在共同悬而未决的专利申请PCT/EP2007/002145中还描述了HMF醚的制备,包括这些醚作为燃料或燃料添加剂的应用。事实上,同时制备和测试了甲基醚和乙基醚(甲氧基甲基糠醛,或MMF;乙氧基乙基糠醛或EMF)。然而,该共同悬而未决的专利申请的发明仅限于伯脂肪醇的使用,优选为C1-C5的伯醇。其未提供混合醇的实施例,例如,在一种醇中含有至少5体积%的另一种醇的混合物。虽然MMF和EMF作为燃料或燃料添加剂是有用的,本发明人发现,醚类,尤其是以高浓度地与如汽油、煤油、柴油、生物柴油或绿色柴油的燃料混合时,仍有改进的余地。因此,本发明人着手克服这一不足。
出人意料的是,本发明人发现由醇混合物得到的HMF的醚与由单一醇醚类似物得到的醚相比具有优异的混合性能。
由含有己糖的原料或由HMF可以以适当的产率制得HMF与上述醇的醚,而减少副产物的形成,并以不需要繁琐的工艺步骤(如两相系统)或较长的工艺时间的方式。
发明内容
因此,本发明提供了一种通过使含己糖的原料或HMF与混合醇在酸性催化剂的存在下反应以制备5-羟甲基糠醛醚混合物的方法。
当上述方法的反应产物直接使用或当其用作随后转化的中间体时,该反应的选择性优选较高,且产物优选较纯净。然而,当上述方法的反应产物被用作燃料、燃料添加剂或作为燃料或燃料添加剂中间体时,反应产物不一定需要纯净。事实上,在由生物质到燃料和燃料添加剂的制备过程中,生物质本身就是各种单糖、双糖和多糖的混合物,反应产物可能包含无扰组分,如乙酰丙酸衍生物和/或戊糖衍生物等。但是,为便于参考,以含己糖的原料的反应得到HMF醚的方式描述了方法和反应产物。由于HMF被认为是由含己糖的原料制备的中间体,所以HMF与支链醇的反应也在本发明范围内。
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应用。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燃料,煤油,柴油,生物柴油(指由植物油的酯交换反应制备,由短链烷基(甲基或乙基)酯组成的非石油类柴油燃料,可单独或与常规石油柴油混合使用),费-托液体(例如由GTL、CTL或BTL天然气液化合成油/煤液化合成油/生物质液化合成油工艺),柴油-生物柴油混合物,绿色柴油,和柴油和/或生物柴油与绿色柴油(绿色柴油是由源于生物质的油、脂肪、油脂或热解油通过加氢处理得到的烃;见,例如,UOP报告“生物可再生在炼油中的机遇的最终技术报告(OPPORTUNITIES FOR BIORENEWABLES INOIL REFINERIES FINAL TECHNICAL REPORT)”,提交给:美国能源部(DOE授予号:DE-FG36-05GO15085)的混合物。该产品是不含硫且具有90~100的十六烷值的优质柴油燃料)。用于与本发明的产品混合的燃料还可能包括一种或多种其他呋喃类化合物(furanics),其中术语“呋喃类化合物”用于指包括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和根据本发明制备的反应产物的燃料组合物。
具体实施方式
生物质资源是众所周知的。在生物质中关心的组分是单糖、二糖或多糖(以下称含糖原料)。合适的6碳单糖包括但不限于,果糖、葡萄糖、半乳糖、甘露糖及其氧化、还原、醚化、酯化和酰胺化衍生物(amidatedderivatives),如醛糖酸或糖醇,葡萄糖是最丰富、最经济、并因此最优选的单糖,即使其反应性低于果糖。另一方面,本发明人还成功地转化蔗糖,这也是大量地存在的。其他可用的二糖包括麦芽糖、纤维二糖和乳糖。可用的多糖包括纤维素、菊糖(一种多果聚糖)、淀粉(一种多葡聚糖)和半纤维素。多糖和二糖被转化成其单糖组分并在5-HMF醚的制备过程中脱水。
在本发明的方法中使用的醇的混合物通常是两种或两种以上具有伯、仲或叔羟基的单醇的混合物。合适的醇有1~20个碳原子,优选1~8个碳原子,并可以选自甲醇、乙醇和丙醇到辛醇的任何异构体中。特别重要的是第二种醇的存在,同样有1~20个碳原子,但与第一种醇不同。需要的该第二种醇的量至少为5体积%、优选10体积%、更优选至少15体积%,从而扰乱反应产物的结晶。因此,合适的混合物包括以体积比5∶95~95∶5,优选10∶90~90∶10,更优选15∶85~85∶15的甲醇和乙醇。这意味着,可以使用“污染”的乙醇用于生产在效果上甚至优于EMF的产品。也可使用合成的醇,例如,通过格尔贝特反应(Guerbet reaction)制备的醇(如,由丁醇制备的2-乙基己醇,“由正丁醇通过使用基于铜或钯前体和丁醇钠的双功能催化剂通过格尔贝特反应选择性合成2-乙基-1-己醇”(″Selective synthesis of2-ethyl-1-hexanol from n-butanol through the Guerbet reaction by usingbifunctional catalysts based on copper or palladium precursors and sodiumbutoxide″),Carlo Carlini,Journal of Molecular Catalysis A:Chemical 212(2004)65-70),因此其通常包括与低级醇(原料)结合的高级醇。
显然,也可以使用三种或更多的醇混合物,只要第二种和其他醇的总含量在醇混合物中至少5体积%。
在HMF醚的制备中使用的醇混合物的量优选与给料的己糖含量等摩尔,但通常以较大过量使用。事实上,可使用醇混合物(如50/50的丁醇/乙醇)作为溶剂或共溶剂。在这种情况下,有足量的醇存在以形成HMF醚。由于醇在醚化反应中具有不同反应性,醚产品比例不一定等于混合醇的给料比例。
在本发明方法中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或其组合和/或混合物。其可以是均相催化剂,但因为纯化的原因优选为多相催化剂(意为固体)。HMF醚可以采用质子酸,布朗斯特酸(Bronsted acid)或者路易斯酸,或由具有这些酸性功能的一种以上的催化剂来制备。
质子酸可以是有机酸或无机酸。例如,所述有机酸可以选自草酸,乙酰丙酸,马来酸,三氟乙酸,甲烷磺酸或对甲苯磺酸中。此外,所述无机酸可以选自(多)磷酸、硫酸、盐酸、氢溴酸、硝酸、氢碘酸中,非必须地原位生成。
某些盐可用作催化剂,其中,所述盐可以是,(NH4)2SO4/SO3、磷酸铵、氯化吡啶(pyridinium chloride)、磷酸三乙胺、吡啶盐、磷酸吡啶、吡啶盐酸盐/氢溴酸盐/过溴酸盐、DMAP、铝盐、钍和锆离子、磷酸锆、钪和镧系元素离子如钐和钇的乙酸盐或三氟乙酸盐、铬离子、铝离子、钛离子、钙离子、铟离子、ZrOCl2、VO(SO4)2、TiO2、钒-卟啉(V-porphyrine)、锆-卟啉、铬-卟啉、钛-卟啉中的任何一种或多种。
选作为脱水催化剂的路易斯酸可以是ZnCl2、AlCl3、BF3的任意一种。
离子交换树脂可以是适当的脱水催化剂。其例子包括AmberliteTM和AmberlystTM,DiaionTM和LevatitTM。其他可用的固体催化剂包括天然粘土矿物、沸石、负载的酸如用无机酸浸渍的二氧化硅、经热处理的碳、金属氧化物、金属硫化物、金属盐和其混合氧化物和混合物。如果使用如在下文中定义的较高的反应温度,那么催化剂在这些温度下应保持稳定。
本发明的方法中可使用的催化剂的概述可以在由Lewkowski先生的综述论文“5-羟甲基糠醛及其衍生物的合成、化学性质和应用”(″Synthesis,chemistry and applications of 5-hydroxymethylfurfural and itsderivatives″)Arkivoc.2001,p.17-54,的表1中找到。
催化剂的量可能会不同,这取决于选择的催化剂或催化剂混合物。例如,催化剂可以以不同地,相对于生物质资源的己糖含量的0.01~40摩尔%、优选0.1~30摩尔%、更优选1~20摩尔%的量加入到反应混合物中。
在优选的实施方式中,所述催化剂是多相催化剂。
反应进行的温度可变化,但总体来说反应优选在50~300摄氏度,更优选在125~250摄氏度,更优选在150~225摄氏度下进行。一般来说,由于其反应选择性的降低和出现许多副产品,特别是糖的焦糖化作用,高于300的温度是不优选的。由于低反应速率,在最低温度以下进行反应也是不优选的。如果反应在水的沸点温度以上进行,则反应优选在压力,如10bar氮气或更高的压力下进行。
含己糖的原料通常是溶解或悬浮在溶剂中从而促进反应,所述溶剂可以是混合的醇反应物。该溶剂体系可以为选自水,亚砜、优选为二甲基亚砜,酮、优选为甲乙酮、甲基异丁基酮和丙酮,乙二醇醚、优选为二甘醇二甲醚(diglyme)中的一种或多种。也可以使用所谓的离子液体。后者指的是熔点低的一类惰性离子化合物,因此其可用作溶剂。其例子包括:例如,在Claude Moreau等在Journal of Molecular Catalysis A:Chemical 253(2006)165-169,“果糖和蔗糖在氯化(1-H-3-甲基咪唑)同时作为溶剂和催化剂的存在下脱水为5-羟甲基糠醛”(″Dehydration of fructose and sucrose into5-hydroxymethylfurfural in the presence of 1-H-3-methyl imidazolium chlorideacting both as solvent and catalyst″)一文中论述的氯化(1-H-3-甲基咪唑)。
优选存在足量的溶剂以溶解或悬浮原料并限制不想要的副反应。
本发明的方法可以以批量法或连续法进行,回收或不回收(部分)产品流,以控制反应温度(通过换热器回收)。因此,本发明的方法可以在连续流动法下进行。在这种方法中,可以使用均相催化剂,且在流动法中反应物的停留时间为0.1秒~10小时,优选为1秒~1小时,更优选为5秒~20分钟。
或者,连续的流动法可以是用多相酸性催化剂的固定床连续流动法或反应(催化)蒸馏法。要启动或再生多相酸性催化剂或提高性能,可以将无机或有机酸加入到固定床或反应蒸馏连续流动法的进料中。在固定床法中,液体时空速(LHSV)可为1~1000,优选为5~500,更优选为10~250,且最优选为25~100min-1。
上述方法产生了稳定的HMF醚,其可以直接使用或在作为燃料和/或作为燃料添加剂之前进一步转化为衍生物。本发明人认为由本发明的方法制备的一些产品实际上是新的。因此,由混合醇制备的混合醚,是新的,并且是优异的燃料组份或燃料添加剂。由于这些醇可以从生物质制备,这可能开启一类完全由生物质衍生的产品。因此,也要求了保护这些新醚。
本发明的混合HMF醚也可用于或可转化成某化合物,该化合物可用作溶剂,用作在聚合反应中的单体(如2,5-呋喃二羧酸或FDCA),用作精细化工和医药中间体,或其他用途。使用适当的催化剂在适当的条件下氧化混合HMF醚,如在Adv.Synth.Catal.2001,343,220-225中描述的用NHPI/Co(OAc)2/Mn(OAc)2催化体系对于对二甲苯、或如在EP 0356703中描述的在pH<8下用Pt/C催化体系对于HMF、或如在FR 2669634中描述的在pH>7下用Pt/C催化体系对于HMF,其全部以空气作为氧化剂,从而形成了2,5-呋喃二羧酸(FDCA)。
本发明还涉及根据本发明的方法制备的混合HMF醚作为燃料或作为燃料添加剂的应用。特别令人感兴趣的是,混合醚在柴油、生物柴油或“绿色柴油”中的使用,因为该混合醚在这些油中的溶解度比乙醇大(得多)。除了上述燃料组份,本发明的燃料组合物中也可存在柴油燃料的常规添加剂和掺和剂。例如,本发明的燃料可包含常规量的常规添加剂,如十六烷值改进剂、摩擦改性剂、脱垢剂、抗氧化剂和热稳定剂。本发明特别优选的柴油燃料配方包括上述柴油燃料烃和HMF醚,以及过氧化物或硝酸酯十六烷改进剂,如二叔丁基过氧化物、硝酸戊酯和硝酸乙基己酯。
附上实施例以说明本发明的方法和由此制备的产品作为燃料的适用性。这些实施例并非意图限制本发明的范围。
实施例
实施例1.批次实验制备混合醚
在7.5ml间歇反应器中,0.053mmol果糖在体积比为23/45/23/9的甲醇/乙醇/正丁醇/水中在150摄氏度的温度下在9mg的酸性催化剂下反应1小时。在紫外光谱中观察到四个呋喃峰。这些产物经质谱鉴定为HMF、甲氧基甲基糠醛(MMF)、乙氧基甲基糠醛(EMF)和正丁氧基甲基糠醛(nBMF)。还发现了乙酰丙酸(LA)。本实施例使用的催化剂的选择性和转化率列于下表中。
根据下列公式计算底物的转化率,呋喃衍生物的选择性和产率:
X=100*mr底物/m0底物
X 转化率(%)
mr底物 反应的底物的量(mg)
m0底物 进料的底物的量(mg)
S化合物=100*nr底物/n0底物
S化合物 化合物的选择性(%)
nr底物 反应的底物的摩尔数
n0底物 供料的底物的摩尔数
产率=100*n产物/n0底物
产率 产率(%)
n产物 生成的产物的摩尔数
表1.批次实验中在混合醇的存在下果糖脱水的转化率和选择性。
实施例2.由果糖(或葡萄糖)和混合醇-连续流动实验形成混合醚
在体积比为23/45/23/9的甲醇/乙醇/正丁醇/水中的1.25wt%的糖(果糖或葡萄糖)溶液在190℃催化剂下流过固定床(200μl)。选择流动速率以达到0.25或0.5min-1的空速,即,2或4分钟的接触时间。
在所有情况下tBMF是在外排流中通过HPLC检测并通过LC-MS(Cl)确认的。使用与批次反应相同的方法计算底物的转化率,呋喃衍生物的选择性和产率。
表2.流动实验中在混合醇的存在下果糖脱水的转化率和选择性。
实施例3
在批次实验中,将0.36mmol底物(葡萄糖、果糖或HMF)和6.5mg的固体酸性催化剂在内层涂覆了Teflon的反应器中混合。加入0.8ml的醇混合物(体积比为1/2/1的甲醇,乙醇和正丁醇)并用氮气中加压至12.5bar。在不同温度下进行反应不同的反应时间。四个主峰在紫外光谱中被观察到,并被确认为HMF、5-乙氧基甲基糠醛(EMF)、5-甲氧基甲基糠醛(MMF)和5-丁氧基甲基糠醛(nBuMF)。在此实验中和在实施例4的实验中,选择性的计算略有不同,其根据以下公式:
选择性=100*nt(产物)/[n0(底物)-nt(底物)]
其中:
n0-最初的摩尔数
nt-在″t″时刻化合物的摩尔数
其结果列于表3。
表3.在1小时、150℃下在不同的固体酸性催化剂的存在下葡萄糖或果糖的转化率(Conv.)和呋喃化合物的选择性(S)。
实施例4
在批次实验中,将0.36mmol底物(葡萄糖、果糖或HMF)和6.5mg的固体酸性催化剂在内层涂覆了Teflon的反应器中混合。加入0.8ml的醇混合物(体积比为4/2/1的乙醇,异丁醇和正己醇)并用氮气(12.5bar)加压至12.5bar。醚化作用在不同温度进行醚化作用不同的反应时间。四个主峰在紫外光谱中被观察到,并被确认为HMF、5-乙氧基甲基糠醛(EMF)、5-异丁氧基甲基糠醛(iBuMF)和5-己氧基甲基糠醛(nHexMF)。其结果列于表4。
表4.在3小时的反应时间、100℃下在不同的固体酸性催化剂的存在下HMF的转化率(Conv.)和5-烷氧基甲基糠醛的选择性(S)。
催化剂 | 转化率(%) | SEMF[%] | SiBuMF[%] | SnHexMF[%] |
Amberlyst 70 | 81.2 | 48.8 | 24.4 | 2.8 |
Dowex Dr-2030 | 94.9 | 57.9 | 21.2 | 1.9 |
Lewatit K-2629,H+Form | 90.7 | 61.0 | 21.8 | 2.1 |
高岭土K 5 | 88.5 | 55.9 | 31.3 | 3.3 |
Nafion | 98.7 | 49.7 | 32.3 | 4.6 |
Amberlyst36Wet | 82.3 | 54.4 | 22.0 | 2.3 |
沸石H-USY SAR15 | 79.6 | 51.8 | 29.2 | 4.6 |
分析方法
反应产物以内标(糖精,Sigma Aldrich)借助于HPLC-分析量化。使用了配备有UV和ELSD探测器的Agilent 1100系列色谱仪。固定相,为反相C18(Sunfire 3.5μm,4.6x100mm,Waters)柱。按照以下图表在40℃温度下并以0.6ml/min的恒速进行梯度洗脱。
实施例5.柴油燃料的应用
燃料溶解度
燃料溶解度是柴油燃料应用的主要问题。并非所有的高极性含氧化合物在目前的市售柴油燃料中具有良好的溶解度。结果表明,根据本发明的方法由混合醇的醚化作用得到的总HMF醚,在其与混合物的5体积%、25体积%和40体积%与市售柴油混合,两种液体混合物组份均可完全混溶。在对比的一组实验中表明,乙氧基甲基糠醛(EMF)在与市售柴油以5体积%混合时完全混溶,但在EMF与柴油以25体积%和40体积%混合时发生了相分离。
参考文献
·DUMESIC,James A等,″Phase modifiers promote efficient productionof Hydroxymethylfurfural from fructose″,Science,30 June 2006,vol.312,no.5782,p.1933-1937.
·WO 2006/063220
·Advanced Organic Chemistry,第15章,Jerry March著,且特别在反应5-4中(第三版,1985年,John Wiley&Sons,pp.684-685)。
·LEWKOWSKI,Jaroslaw,Synthesis,chemistry and applications of5-hydroxymethylfurfural and its derivatives,Arkivoc.,2001,p.17-54.
·MOREAU,Claude等,″Dehydration of fructose and sucrose into5-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 0641854
·UOP 报告“OPPORTUNITIES FOR BIORENEWABLES IN OILREFINERIES FINAL TECHNICAL REPORT”,提交给:美国能源部(DOE授予号:DE-FG36-05GO15085)。
·Adv.Synth.Catal.2001,343,220-225
·EP 0356703
·FR 2669634
Claims (19)
1.制备5-羟甲基糠醛醚混合物的方法,通过在酸性催化剂的存在下,使HMF或选自含葡萄糖的二糖、葡萄糖或果糖中的含己糖的原料与至少两种不同醇的混合物反应,其中,组成所述混合物的醇为C1~C8醇,第二种醇在醇混合物中的含量为至少5体积%。
2.根据权利要求1所述的方法,其中,所述醇为由费-托醇合成法得到的混合物。
3.根据权利要求1所述的方法,其中,所述醇为由格尔贝特醇合成法得到的混合物。
4.根据权利要求1所述的方法,其中,所述酸性催化剂选自均相催化剂或多相催化剂中,该均相催化剂或多相催化剂选自固体有机酸、无机酸、盐、路易斯酸、离子交换树脂、沸石或其混合物和/或其组合之中。
5.根据权利要求1所述的方法,其中,所述酸性催化剂为固体布朗斯特酸。
6.根据权利要求1所述的方法,其中,所述酸性催化剂为固体路易斯酸。
7.根据权利要求1所述的方法,其中,所述反应在50~300摄氏度的温度下进行。
8.根据权利要求1所述的方法,其中,所述原料为5-(羟甲基)糠醛。
9.根据权利要求1所述的方法,其中,所述原料包括:葡萄糖、果糖或其混合物。
10.根据权利要求1所述的方法,该方法在溶剂的存在下进行,其中,所述溶剂选自如下:水;亚砜;酮;离子液体;醚;以及它们的混合物。
11.根据权利要求1所述的方法,其中,所述方法采用连续流动法进行。
12.根据权利要求11所述的方法,其中,在流动法中的停留时间为0.1秒~10小时。
13.根据权利要求12所述的方法,其中,所述连续流动法为固定床连续流动法。
14.根据权利要求13所述的方法,其中,所述固定床包含多相酸性催化剂。
15.根据权利要求14所述的方法,其中,所述连续流动法为反应蒸馏或催化蒸馏法。
16.根据权利要求14所述的方法,其中,除了多相酸性催化剂,将无机或有机酸性催化剂加入到固定床连续流动法的进料中。
17.根据权利要求13所述的方法,其中,液体时空速为1~1000。
18.根据权利要求1~17中任意一项所述的方法制备的醚混合物作为燃料或燃料添加剂的应用。
19.一种燃料组合物,其包含:根据权利要求1~17中任意一项所述的方法制备的醚混合物作为燃料组份,该醚混合物非必须地与汽油和汽油-乙醇混合物;煤油;柴油;生物柴油,即,由植物油的酯交换反应制备,由短链烷基酯组成的非石油类柴油燃料;费-托液体;柴油-生物柴油混合物;绿色柴油,即,由源于生物质的油、脂肪、油脂或热解油通过加氢处理得到的烃;柴油和/或生物柴油与绿色柴油的混合物以及其他的呋喃和四氢呋喃的衍生物中的一种或多种混合。
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Families Citing this family (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MY159836A (en) * | 2009-10-07 | 2017-02-15 | Furanix Technologies Bv | Method for the preparation of 2,5-furandicarboxylic acid and esters thereof |
US8236973B2 (en) | 2009-11-05 | 2012-08-07 | Battelle Memorial Institute | Adsorption separation processes for ionic liquid catalytic processes |
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 |
KR101306277B1 (ko) | 2011-03-23 | 2013-09-09 | 서울대학교산학협력단 | 이온성 액체를 용매로 이용한 푸르푸라놀계 화합물과 2-푸란카르복시산계 화합물의 제조방법 |
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 |
US8796477B2 (en) | 2011-05-24 | 2014-08-05 | Eastman Chemical Company | Oxidation process to produce a crude and/or purified carboxylic acid product |
US8791278B2 (en) | 2011-05-24 | 2014-07-29 | Eastman Chemical Company | Oxidation process to produce a crude and/or purified carboxylic acid product |
US9199958B2 (en) | 2011-05-24 | 2015-12-01 | Eastman Chemical Company | Oxidation process to produce a crude and/or purified carboxylic acid product |
US9573120B2 (en) | 2014-05-08 | 2017-02-21 | Eastman Chemical Company | Furan-2,5-dicarboxylic acid purge process |
US8791277B2 (en) | 2011-05-24 | 2014-07-29 | Eastman Chemical Company | Oxidation process to produce a crude and/or purified carboxylic acid product |
US8846960B2 (en) | 2011-05-24 | 2014-09-30 | Eastman Chemical Company | Oxidation process to produce a crude and/or purified carboxylic acid product |
WO2012175584A1 (en) * | 2011-06-22 | 2012-12-27 | Basf Se | Method for dehydrating a carbohydrate-comprising composition |
CN103842349B (zh) * | 2011-09-29 | 2015-09-30 | 韩国生产技术研究院 | 在有机溶剂的存在下、使用离子交换树脂生产5-羟甲基-2-呋喃甲醛或其烷基醚衍生物的方法 |
WO2013102015A1 (en) | 2011-12-28 | 2013-07-04 | 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 |
US9181210B2 (en) | 2011-12-28 | 2015-11-10 | E I Du Pont De Nemours And Company | Processes for making furfurals |
WO2013102027A1 (en) | 2011-12-28 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Process for the production of furfural |
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 |
US8969404B2 (en) | 2012-06-22 | 2015-03-03 | Eastman Chemical Company | Purifying crude furan 2,5-dicarboxylic acid by hydrogenation |
US8748479B2 (en) | 2012-06-22 | 2014-06-10 | Eastman Chemical Company | Process for purifying crude furan 2,5-dicarboxylic acid using hydrogenation |
US9029580B2 (en) | 2012-07-20 | 2015-05-12 | Eastman Chemical Company | Oxidation process to produce a purified carboxylic acid product via solvent displacement and post oxidation |
US8809556B2 (en) | 2012-07-20 | 2014-08-19 | Eastman Chemical Company | Oxidation process to produce a purified carboxylic acid product via solvent displacement and post oxidation |
US8772513B2 (en) | 2012-08-30 | 2014-07-08 | Eastman Chemical Company | Oxidation process to produce a crude dry carboxylic acid product |
US8916719B2 (en) | 2012-11-20 | 2014-12-23 | Eastman Chemical Company | Process for producing dry purified furan-2,5-dicarboxylic acid with oxidation off-gas treatment |
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US8916720B2 (en) | 2012-11-20 | 2014-12-23 | Eastman Chemical Company | Process for producing dry purified furan-2,5-dicarboxylic acid with oxidation off-gas treatment |
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BR112015019100A2 (pt) | 2013-04-26 | 2017-07-18 | Shell Int Research | processo para a preparação de monoetileno glicol a partir de sacarose, e, processo para a conversão de sacarose em frutose e/ou derivados de frutose |
US9943834B2 (en) | 2014-05-08 | 2018-04-17 | Eastman Chemical Company | Furan-2,5-dicarboxylic acid purge process |
KR101767182B1 (ko) | 2015-04-15 | 2017-08-11 | 한국화학연구원 | 바이오매스로부터 퓨란계 유도체의 제조방법 |
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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 |
EP3402787A4 (en) | 2016-01-13 | 2019-11-27 | Stora Enso Oyj | PROCESSES FOR PREPARING 2,5-FURANDICARBOXYLIC ACID AND INTERMEDIATES AND DERIVATIVES THEREOF |
WO2018035083A1 (en) * | 2016-08-17 | 2018-02-22 | Basudeb Saha | An integrated process for direct saccharification and dehydration of intact biomass to furfurals |
SG11201913469PA (en) | 2017-07-12 | 2020-01-30 | Stora Enso Oyj | Purified 2,5-furandicarboxylic acid pathway products |
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KR102347177B1 (ko) | 2020-02-13 | 2022-01-04 | 한국화학연구원 | 5-알콕시메틸퍼퓨랄 제조방법 |
CN113912576A (zh) * | 2021-10-21 | 2022-01-11 | 中国科学技术大学 | 双-(4-甲酰基糠醛)醚的制备方法、化合物及其应用 |
CN114105915A (zh) * | 2021-12-08 | 2022-03-01 | 浙江工业大学 | 一种利用5-羟甲基糠醛制备5-乙氧甲基糠醛的方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
WO2006063287A2 (en) * | 2004-12-10 | 2006-06-15 | Archer-Daniels-Midland Company | Conversion of 2,5-(hydroxymethyl) furaldehyde to 2,5-bis (hydroxymethyl) tetrahydofuran, purification and industrial uses of the product |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7317116B2 (en) * | 2004-12-10 | 2008-01-08 | Archer-Daniels-Midland-Company | Processes for the preparation and purification of hydroxymethylfuraldehyde and derivatives |
EP1834950A1 (en) * | 2006-03-10 | 2007-09-19 | Avantium International B.V. | Method for the synthesis of 5-alkoxymethylfurfural ethers and their use |
-
2008
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
WO2006063287A2 (en) * | 2004-12-10 | 2006-06-15 | Archer-Daniels-Midland Company | Conversion of 2,5-(hydroxymethyl) furaldehyde to 2,5-bis (hydroxymethyl) tetrahydofuran, purification and industrial uses of the product |
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