5-羟甲基糠醛制备研究
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摘要
5-羟甲基糠醛(5-HMF)具有高活性的呋喃环、芳醇、芳醛结构,其衍生物被广泛的用作真菌剂、腐蚀抑制剂、香料,也可以代替由石油加工得到的苯系化合物作为合成高分子材料的原料;因而,以生物质资源的糖类化合物为原料合成精细化工产品5-HMF的研究备受关注。
本课题主要研究了不同反应器型式、催化剂、溶剂、原料对合成5-HM F反应的影响。通过改变反应时间、反应温度、原料浓度、溶剂比例、催化剂类型及用量来考察六碳糖脱水反应合成5-HMF的产品收率和反应选择性。在高温高压条件下,果糖更容易脱水生成5-HMF。通过设计正交试验确定了用葡萄糖做原料生成5-HMF的最优条件:反应温度为130℃,反应时间为120 min,反应物料配比为葡萄糖∶离子液体∶催化剂B∶助催化剂C=10∶1∶2.4%∶2.4%(摩尔比)。得到的结果:产品收率达60.50%,选择性达71.17%。另外,还初步探索了5-HMF的分离提纯方法,即先用丙酮萃取,再蒸馏,萃取收率达到50.76%,蒸馏收率为44.82%。
5-hydroxymethyl furfural (5-HMF) is one of important fine chemical products,of which the derivatives were widely used as fungi, corrosion inhibitors and flavors, as well as the substituent of petroleum-based benzyene hydrocarbons to synthesize polymers, owing to its active furan ring and the frame of arylalcohol and arylalde- hydes. Therefore, it has attracted lots of attentions to study the synthesis of 5-HMF using biomass-based carbohydrates as the raw materials.
In this thesis we studied the effects of reaction equipments, catalysis, solvents and raw materials on the product of 5-HMF. We studied the yield and selectivity of 5-HMF under different reaction time, reaction temperature, concentrations of raw material, solvents, the type and dosage of catalysts. It is indicated that fructose is easier to synthesis 5-HMF than glucose at the high temperature and pressure. By designing orthogonal experiments, the optimal conditions were obtained: the temperature=130℃, reaction time=120 min, glucose∶BMIMCl∶catalyzer B∶secondary catalyzer C=10∶1∶2.4%∶2.4%(mol ratio). The yield of 5-HMF was 60.50%, the selectivity was about 71.17%. In addition, the separation method of 5-HMF was investigated, i.e., 5-HMF was purified though extraction by acetone followed by distillation. The yield of extraction reached to 50.76%, the yield of distillation was 44.82%.
本课题主要研究了不同反应器型式、催化剂、溶剂、原料对合成5-HM F反应的影响。通过改变反应时间、反应温度、原料浓度、溶剂比例、催化剂类型及用量来考察六碳糖脱水反应合成5-HMF的产品收率和反应选择性。在高温高压条件下,果糖更容易脱水生成5-HMF。通过设计正交试验确定了用葡萄糖做原料生成5-HMF的最优条件:反应温度为130℃,反应时间为120 min,反应物料配比为葡萄糖∶离子液体∶催化剂B∶助催化剂C=10∶1∶2.4%∶2.4%(摩尔比)。得到的结果:产品收率达60.50%,选择性达71.17%。另外,还初步探索了5-HMF的分离提纯方法,即先用丙酮萃取,再蒸馏,萃取收率达到50.76%,蒸馏收率为44.82%。
5-hydroxymethyl furfural (5-HMF) is one of important fine chemical products,of which the derivatives were widely used as fungi, corrosion inhibitors and flavors, as well as the substituent of petroleum-based benzyene hydrocarbons to synthesize polymers, owing to its active furan ring and the frame of arylalcohol and arylalde- hydes. Therefore, it has attracted lots of attentions to study the synthesis of 5-HMF using biomass-based carbohydrates as the raw materials.
In this thesis we studied the effects of reaction equipments, catalysis, solvents and raw materials on the product of 5-HMF. We studied the yield and selectivity of 5-HMF under different reaction time, reaction temperature, concentrations of raw material, solvents, the type and dosage of catalysts. It is indicated that fructose is easier to synthesis 5-HMF than glucose at the high temperature and pressure. By designing orthogonal experiments, the optimal conditions were obtained: the temperature=130℃, reaction time=120 min, glucose∶BMIMCl∶catalyzer B∶secondary catalyzer C=10∶1∶2.4%∶2.4%(mol ratio). The yield of 5-HMF was 60.50%, the selectivity was about 71.17%. In addition, the separation method of 5-HMF was investigated, i.e., 5-HMF was purified though extraction by acetone followed by distillation. The yield of extraction reached to 50.76%, the yield of distillation was 44.82%.
引文
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[4]P.T.阿纳斯塔斯等,绿色化学理论与应用,科学出版社,第一版,2002
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[7]Akerlof G C, Oshry H I, The dielectric constant of water at high temperatures and in equilibrium with its vapor, Journal of the American Chemical Society, 1950, 72: 2844-2847
[8]Haar L, Gallagher J S, Kell G S, NBS/NRC SeamTables, Hemisphere, N Y, 1984
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[10]汪利平,纤维素水热降解制备5-羟甲基糠醛的实验研究,天津:天津大学化工学院, 2006
[11]李林,魏海峰,张兰等, 5-羟甲基糠醛类用于制备神经系统用药的用途,中国专利1565438, 2005-01-19
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[29]Leshkov Y R, Chheda J N, Dumesic J A, Phase modifiers promot eeffieient production of hydroxylmethylfurfural from fructose. Science, 2006, 312(30): 1933-1937
[30]Lewkowski J, Synthesis, chemistry and applications of 5-hydroxymethylfurfural and its deri- vatives, Arkivoc, 2001, (Ⅰ): 17-54
[31]Lew B W, Method of producting dehydromucic acid, US3326944, 1967-06-20
[32]Fang S W, Photocrosslinkable polymers bearing pendant conjugated heterrocycliic chromoph- ores, Polymer, 2002, 43(12): 505-510
[33]Lasseuguette E, Synthesis, characterization and photocross-linking of copylymers of furan and aliphatic hydroxyethylesters prepared by transesterification, Polymer, 2005, 46(15): 5476- 5483
[34]Storbeek R, Ballauff M, Synthesis and properties of polyesters based on Z, 5-furan-diear boxylieacidandl, 4:3,6-dianhydrohexitols, Polymer, 1993, 34(23): 5003-5005
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[41]Moore J A, Kelly J E, Polyesters derived from furan and tetrahydrofuran nuclin, Macromole- cules, 1978, 11(3): 568-573
[42]YuriyR, Juben N C, James A D, Phase modifiers promot eeffieient production of hydroxylmet- hylfurfural from fructose, Science, 2006, 312(30): 1933-1937
[43]Cottier L, Descotes G, 5-(hydroxymethyl) furfural synthesis and chemical transformations, Trend in Heterocyclic Chemistry, 1991, 2: 233-248
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[46]Fitzoatick H D, Process for carrying out reactions involving sugars and their derivatives with readents therefore, GB, 1019512, 1966
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[48]Mednick M L, The acid-base-catalyzed conversion of aldohexose into 5-(hydroxymethyl)-2- furfural, Journal of Organic Chemistry, 1962, 27(2): 398-403
[49]Brown D W, Floyd A J, Kinsman R G, et al, Dehydration reactions of fructose in non-aqueous media, Journal of Chemical Technology and Biotechnology, 1982, 32(7-12): 920-924
[50]Seri K, Sakaki T, Catalytic activity of Lanthanoide(Ⅲ) ions for dehydration of D-glucose to 5-( hydroxymethyl ) furfural[J], Journal of Molecular Catalysis A: Chemical, 1996, 112(2): 163-L165
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[52]Seri K, Sakaki T, Lanthanoide(Ⅲ)-catalyzed degradation of cellulose at 250℃, Bioresource Technology, 2002, 81(3): 257-260
[53]Carlini C, Giuttari M, Selective Saccharides dehydration to 5-hydroxymethyl-2-furaldehyde by heterogeneous niobium catalysts, Applied Catalysis A: General, 1999, 183 (2): 295-302
[54]Benvenuti F, Carlini C, Heterogeneous zirconium and titanium catalysts for the selective syn- thesis of 5-hydroxymethyl-2-furaldehyde from carbonhydrates, Applied Catalysis A: General, 2000, 193(1/2): 147-153
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[57]Moreau C, Durand R, Hydrolysis of sucrose in the presence of H-form zeolites, Industrial Crops and Products, 2000, 11(2-3): 237-242
[58]Bicker M, Hirth J, Vogel H, Dehydration of fructose to 5-hydroxymethylfurfural in sub- and supercritical acetone, Green Chemistry, 2003, 5: 280-284
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[2]闵恩泽等,绿色化学技术,江西科学技术出版社,第一版, 2001
[3]闵恩泽,吴巍等,绿色化学与化工,化学工业出版社,第一版, 2000
[4]P.T.阿纳斯塔斯等,绿色化学理论与应用,科学出版社,第一版,2002
[5]蔡磊,吕秀阳,何龙等,新平台化合物乙酰丙酸化学与应用,化工时刊, 2004, 18 (7): 1-4
[6]Marshall W L, Frank E U, Ion product of water subatances, 0-1000℃, 1-10,000 bars, new international formulation and its background, Journal of Physical and Chemical Reference Data, 1981, 10: 295-304
[7]Akerlof G C, Oshry H I, The dielectric constant of water at high temperatures and in equilibrium with its vapor, Journal of the American Chemical Society, 1950, 72: 2844-2847
[8]Haar L, Gallagher J S, Kell G S, NBS/NRC SeamTables, Hemisphere, N Y, 1984
[9]Connolly J F, Solubility of hydrocarbons in water near the critical solution temperatures, Journal of Chemical & Engineering Data, 1966, 11(10): 13-16
[10]汪利平,纤维素水热降解制备5-羟甲基糠醛的实验研究,天津:天津大学化工学院, 2006
[11]李林,魏海峰,张兰等, 5-羟甲基糠醛类用于制备神经系统用药的用途,中国专利1565438, 2005-01-19
[12]李林,张兰,楚晋等, 5-羟甲基糠醛在制备防治神经退行性疾和认知损害的药品和保健品中的用途,中国专利1504188, 2004-06-16
[13]严永清,朱丹妮,陈婷等, 5-羟甲基-2-糠醛的医药用途,中国专利1182589, 1998-05-27
[14]杜莹,潘柯,严孝强等, 5-羟甲基-2-糠醛及其衍生物、类似物的医药用途,中国专利, 1589784, 2005-03-09
[15]晋文英, 5-羟甲基糠醛的药物用途,中国专利1704050, 2005-07-07
[16]Leshkov Y R, Chheda J N, Dumesic J A, Phase modifiers promot eeffieient production of hydroxylmethylfurfural from fructose, Science, 2006, 312 (30): 1933-1937
[17]薛福连,乙酰丙酸生产应用与开发前景,化工生产与技术, 2000,10 (5): 27
[18]Fitzpatrick S W, Production of levulinic acid from carbohydrate containing materials: US5608105, 1997-03-04
[19]张欢欢,陈丰秋,环境友好催化剂催化葡萄糖水解的研究,工业催化, 2006, 14(5): 27-29
[20]Lewkowski J, Synthesis, chemistry and applications of 5-hydroxymethylfurfural and its derivatives, Arkivoc, 2001, (Ⅰ): 17-54
[21]Reijendam J W,Heeres G J,Janssen M J, Polyenyl-substituted furans and thiophenes,A study of the electronic spectra (Ⅰ) , Tetrahedron, 1970, 26(6): 1219-1302
[22]Reijendam J W,Heeres G J,Janssen M J, Polyenyl-substituted furans and thiophenes,A study of the electronic spectra (Ⅱ) , Tetrahedron, 1970, 26(6): 1303-1310
[23]Morikawa S, Synthesis of hydroxymethyfurfural and 2,5-furandicarboxaldehyde, Noguchi Ke nkyusho Jiho, 1978, 21: 25-33
[24]Morikawa S,Teratake S, 2,5-Furandicarboxaldehyde, JP54009260, 1979-01-24
[25]Morikawa S, Synthesis of hydroxymethyfurfural from 5-hydroxymethylfurfural, Noguchi Ken kyusho Jiho, 1979, 22: 20-27
[26]EI Hajj T,Martin J C,Descotes G, et al, Oxidation of 5-hydroxymethylfurfural under sonochemical conditions, Polish Journal of Chemistry, 1983, 20(1): 233-235
[27]Cottier L,Descotes G,Lewkowski J, et al, Oxidation of 5-hydroxymethylfurfural under sono chemical conditions, Polish Journal of Chemistry, 1994, 68(4): 693-698
[28]Cottier L,Descotes G,Lewkowski J, et al, Ultrasonically accelerated syntheses of furan-2,5- dicarbaldehyde from 5-hydroxymethyl-2-furfural, Organic Preparations and Procedures Inter -national, 1995, 27(5): 564-566
[29]Leshkov Y R, Chheda J N, Dumesic J A, Phase modifiers promot eeffieient production of hydroxylmethylfurfural from fructose. Science, 2006, 312(30): 1933-1937
[30]Lewkowski J, Synthesis, chemistry and applications of 5-hydroxymethylfurfural and its deri- vatives, Arkivoc, 2001, (Ⅰ): 17-54
[31]Lew B W, Method of producting dehydromucic acid, US3326944, 1967-06-20
[32]Fang S W, Photocrosslinkable polymers bearing pendant conjugated heterrocycliic chromoph- ores, Polymer, 2002, 43(12): 505-510
[33]Lasseuguette E, Synthesis, characterization and photocross-linking of copylymers of furan and aliphatic hydroxyethylesters prepared by transesterification, Polymer, 2005, 46(15): 5476- 5483
[34]Storbeek R, Ballauff M, Synthesis and properties of polyesters based on Z, 5-furan-diear boxylieacidandl, 4:3,6-dianhydrohexitols, Polymer, 1993, 34(23): 5003-5005
[35]Van Dam H E, Kieboom A P G, Van Bekkum H, The convertion of fructose and glucose in acidic media: formation of hydroxymethylfurfural, Starch/Starke, 1986, 38: 95-101
[36]Antal M J, Mok W S L, Mechanism of formation of 5-(hydroxymethyl)-2-furaldehyde fromD-fructose and sucrose, Carbohydrate Research, 1990, 199: 91-109
[37]Krishna R, Kallury M R, Ambidge C, et al, Rapid Hydrothermolysis of cellulose and related carbohydrates, Carbohydrate Research, 1986, 158:253-261
[38]Nelson D A, Molton P M, Landsman S D, Formation, during liquefaction of cellulose, of 2,5-dimethyl-1,4-benzenediol via aldol addition and a reduction-oxidation pathway, Carbo- hydrate Research, 1984, 128: 356-360
[39]Haworth W N, Jones W G M, Convertion of sucrose into furan compounds: 5-hydroxylmethyl furfural and some derivatives, Journal of the Chemical Society, 1944, 667-670
[40]Kuster M. Manufacture of 5- hydroxylmethylfurfural, Starch/Starke 1990, 42: 314-321
[41]Moore J A, Kelly J E, Polyesters derived from furan and tetrahydrofuran nuclin, Macromole- cules, 1978, 11(3): 568-573
[42]YuriyR, Juben N C, James A D, Phase modifiers promot eeffieient production of hydroxylmet- hylfurfural from fructose, Science, 2006, 312(30): 1933-1937
[43]Cottier L, Descotes G, 5-(hydroxymethyl) furfural synthesis and chemical transformations, Trend in Heterocyclic Chemistry, 1991, 2: 233-248
[44]Fayet, Gelas J, A new method for the preparation of 5- hydroxymethyl-2- furaldehyde by the reaction of monium or immonium salts with mono-, oligo- and polysaccharides, Direct access to 5- hydroxymethyl-2- furaldehyde, Carbohydrate Research, 1990, 199: 91-109
[45]Ralph A H, west C P, John W, Preparation of hydroxymethyl furfural, US3071599, 1963
[46]Fitzoatick H D, Process for carrying out reactions involving sugars and their derivatives with readents therefore, GB, 1019512, 1966
[47]Peniston Q P, Manufacture of 5-hydroxymethyl-2-furfural, US2750394, 1956-05-22
[48]Mednick M L, The acid-base-catalyzed conversion of aldohexose into 5-(hydroxymethyl)-2- furfural, Journal of Organic Chemistry, 1962, 27(2): 398-403
[49]Brown D W, Floyd A J, Kinsman R G, et al, Dehydration reactions of fructose in non-aqueous media, Journal of Chemical Technology and Biotechnology, 1982, 32(7-12): 920-924
[50]Seri K, Sakaki T, Catalytic activity of Lanthanoide(Ⅲ) ions for dehydration of D-glucose to 5-( hydroxymethyl ) furfural[J], Journal of Molecular Catalysis A: Chemical, 1996, 112(2): 163-L165
[51] Seri K, Inoue Y, Ishida H, Catalytic acivity of Lanthanoide(Ⅲ) ions for dehydration of D- glucose to 5- ( hydroxymethyl )-2-furaldehyde in water, Bulletin of Chemical Society of Japan, 2001, 74(6): 1145-1150
[52]Seri K, Sakaki T, Lanthanoide(Ⅲ)-catalyzed degradation of cellulose at 250℃, Bioresource Technology, 2002, 81(3): 257-260
[53]Carlini C, Giuttari M, Selective Saccharides dehydration to 5-hydroxymethyl-2-furaldehyde by heterogeneous niobium catalysts, Applied Catalysis A: General, 1999, 183 (2): 295-302
[54]Benvenuti F, Carlini C, Heterogeneous zirconium and titanium catalysts for the selective syn- thesis of 5-hydroxymethyl-2-furaldehyde from carbonhydrates, Applied Catalysis A: General, 2000, 193(1/2): 147-153
[55]Peniston Q P, Manufacture of 5-hydroxymethyl-2-furfural, US2750394, 1956-05-22
[56]Moreau C, Durand R, Dehydration of fructose to 5-hydroxymethylfurfural over H-mordenites, Applied Catalysis A: General, 1996, 145(1-2): 211-224
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