CN103833694B - 一种从二甲亚砜溶液中分离2,5-呋喃二甲醛的方法 - Google Patents
一种从二甲亚砜溶液中分离2,5-呋喃二甲醛的方法 Download PDFInfo
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 238000001179 sorption measurement Methods 0.000 claims description 17
- 238000003795 desorption Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 10
- 244000060011 Cocos nucifera Species 0.000 claims description 10
- 239000003610 charcoal Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 235000009827 Prunus armeniaca Nutrition 0.000 claims description 3
- 244000018633 Prunus armeniaca Species 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 239000010903 husk Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000007667 floating Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 3
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 abstract 2
- 239000003463 adsorbent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
一种从二甲亚砜溶液中分离2,5-呋喃二甲醛的方法。以活性炭为吸附剂,糠醛为脱附剂,在常温下分离2,5-呋喃二甲醛。该分离方法条件温和,工艺步骤简单,能耗低,成本低,具有良好的应用前景。
Description
技术领域
本发明涉及一种从二甲亚砜溶液中分离2,5-呋喃二甲醛的方法。
背景技术
2,5-呋喃二甲醛(DFF)是一种重要的呋喃类衍生物,是一种多用途的有机合成中间体。它可以作为单体用于生产聚合物,也可以用来合成药物及其中间体、抗真菌剂、大环配体等。目前,DFF通常由5-羟甲基糠醛(HMF)氧化制得。然而,由于原料HMF价格比较昂贵而使得DFF无法实现工业化生产。CN103113327A采用果糖为原料,经由“一锅”脱水、氧化直接合成DFF,反应在具有脱水和稳定中间体功能的二甲亚砜(DMSO)溶剂中进行,副产物较多,另外DMSO沸点较高,若采用蒸馏的方法分离DFF,DFF会与副产物发生进一步反应而降低分离产率。如何从DMSO溶剂中分离出DFF成为限制其大规模生产的关键问题。
Halliday等人在Organic Letters5(2003)2003中报道了在DMSO溶剂中合成DFF及分离DFF的方法。首先,用环己烷索氏提纯反应液后,用硅胶过滤,最后将环己烷低温蒸干,从而达到分离提纯DFF的目的。
Yang等人在Green Chemistry14(2012)2986中首先将产物混合液过滤后加入一定量的水,再用乙酸乙酯萃取出DFF;其次,向乙酸乙酯层中加入5%的NaCl溶液移除残留的DMSO;最后,用MgSO4干燥剩余的溶液,通过低温蒸馏的方式提纯DFF。
采用以上几种方法提纯DFF,需加入多种有机溶剂和试剂,过程较为复杂,操作繁琐,能耗高。
发明内容
本发明旨在提供一种简便、低能耗的从DMSO溶液中分离DFF的方法,以克服已有技术中步骤长、能耗高、成本高的缺点。
发明要点:①市售活性炭用去离子水洗净、除浮炭、烘干后备用;②向玻璃小瓶中依次加入2mL含0.125mmol/L DFF的待分离的DMSO溶液、磁力搅拌子和活性炭,密封后,室温搅拌吸附2~14h,过滤出活性炭;③将滤出的活性炭烘干、冷却至室温后,加入α-糠醛,搅拌脱附1~5h,过滤出活性炭;④滤液用气相色谱定量分析。其中活性炭与DMSO的质量比为1:1.1~1:5.4,活性炭粒度为20~110目,活性炭与α-糠醛的质量比为1:4.1~1:29.0。
活性炭与DMSO的最佳质量比为1:1.2~1:1.6,活性炭的最佳粒度为40~80目,活性炭与α-糠醛的最佳质量比为1:6.5~1:12.4,吸附时间最佳为10~12h,脱附时间最佳为2~3h。
本发明所述的活性炭是椰壳、杏壳或煤质活性炭,其中最好的是椰壳活性炭。活性炭具有高度发达的孔隙结构、巨大的比表面积、良好的吸附性能、丰富的表面官能团,因而可作为吸附剂广泛地应用于化工、医疗和环保等众多领域。采用活性炭吸附的方法从DMSO溶液中分离提纯出DFF,不但操作步骤简单,而且节约资源,降低能耗,在经济上具有更加可观的潜在应用价值。
本发明所述的分离产率=吸附率×脱附率。
本发明的特点为:①分离在常温常压下进行,能耗低;②DFF的分离产率高;③活性炭廉价易得,性质稳定,无毒;④工艺步骤简单,操作安全,具有良好的应用前景。
具体实施方式
实施例1-7:
向玻璃小瓶中依次加入2mL含0.125mmol/L DFF的待分离的DMSO溶液、磁力搅拌子和粒度为40~80目的椰壳活性炭,活性炭与DMSO的质量比为1:5.4,密封后,室温搅拌吸附,过滤出活性炭,滤液采用气相色谱定量分析吸附率。采用不同的吸附时间进行吸附实验,结果列在表1中。
表1
实施例序号 | 吸附时间(h) | 吸附率(%) |
1 | 2 | 47 |
2 | 4 | 48 |
3 | 6 | 55 |
4 | 8 | 58 |
5 | 10 | 75 |
6 | 12 | 80 |
7 | 14 | 70 |
实施例8-10:
向玻璃小瓶中依次加入2mL含0.125mmol/L DFF的待分离的DMSO溶液、磁力搅拌子和粒度为40~80目的椰壳活性炭,活性炭与DMSO的质量比为1:1.8,密封后,室温搅拌吸附10h后,过滤出活性炭,将其烘干、冷却至室温后,加入α-糠醛与活性炭的质量比为9.7:1,搅拌脱附2h,过滤出活性炭。滤液采用气相色谱定量分析吸附率和脱附率,计算出分离产率,结果列在表2中。
表2
实施例序号 | 活性炭类型 | 吸附率(%) | 脱附率(%) | 分离产率(%) |
8 | 椰壳 | 82 | 84 | 69 |
9 | 杏壳 | 74 | 70 | 52 |
10 | 煤质 | 79 | 82 | 65 |
实施例11-12:
按照实施例8的方法,采用不同粒度的活性炭进行分离实验,结果列在表3中。
表3
实施例序号 | 椰壳活性炭粒度(目) | 吸附率(%) | 脱附率(%) | 分离产率(%) |
11 | 20-40 | 82 | 72 | 59 |
12 | 80-110 | 84 | 63 | 53 |
实施例13-18:
按照实施例8的方法,吸附时间为12h,采用不同用量的活性炭进行吸附分离实验,结果列在表4中。
表4
实施例序号 | m活性炭:mDMSO | 吸附率(%) | 脱附率(%) | 分离产率(%) |
13 | 1:2.7 | 73 | 70 | 51 |
14 | 1:2.2 | 78 | 71 | 55 |
15 | 1:1.8 | 84 | 80 | 67 |
16 | 1:1.6 | 90 | 86 | 77 |
17 | 1:1.2 | 91 | 82 | 75 |
18 | 1:1.1 | 92 | 77 | 71 |
注:m活性炭:mDMSO为活性炭与DMSO的质量比。
实施例19-22:
粒度为40~80目的椰壳活性炭与DMSO和α-糠醛的质量比分别为1:1.6和1:8.3,吸附时间为12h,按照实施例8的方法,采用不同的脱附时间,结果列在表5中。
表5
实施例23-25:
粒度为40~80目的椰壳活性炭与DMSO的质量比为1:1.6,吸附时间为12h,按照实施例8的方法,采用不同的α-糠醛用量进行吸附分离实验,结果列在表6中。
表6
注:m活性炭:mα-糠醛为活性炭与α-糠醛的质量比。
实施例26
将本分离DFF的方法应用于已公开的中国发明专利CN103113327A反应后的混合液,反应条件为:450mg果糖,25mg PMo11V1,10mL DMSO,160℃反应3h,获得DFF收率为52%。按照实施例16的方法进行分离实验,获得DFF的分离产率为75%。
Claims (7)
1.一种从二甲亚砜溶液中分离2,5-呋喃二甲醛的方法,其特征在于:①市售的椰壳、杏壳或煤质活性炭用去离子水洗净、除浮炭、烘干后备用;②向玻璃小瓶中依次加入2mL含0.125mmol/L DFF的待分离的DMSO溶液、磁力搅拌子和①中备用活性炭,密封后,室温搅拌吸附2~14h,过滤出活性炭;③将滤出的活性炭烘干,冷却至室温后,加入α-糠醛,搅拌脱附1~5h, 过滤出活性炭;④滤液用气相色谱定量分析;其中活性炭与DMSO的质量比为1:1.1~1:5.4,活性炭粒度为20~110目,活性炭与α-糠醛的质量比为1:4.1~1:29.0。
2.根据权利要求1所述的方法,其特征在于活性炭为椰壳活性炭。
3.根据权利要求1所述的方法,其特征在于活性炭与DMSO的质量比为1:1.2~1:1.6。
4.根据权利要求1所述的方法,其特征在于活性炭粒度为40~80目。
5.根据权利要求1所述的方法,其特征在于活性炭与α-糠醛的质量比为1:6.5~1:12.4。
6.根据权利要求1所述的方法,其特征在于吸附时间为10~12h。
7.根据权利要求1所述的方法,其特征在于脱附时间为2~3h。
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WO2003024947A1 (en) * | 2001-09-17 | 2003-03-27 | E.I. Du Pont De Nemours And Company | Process for preparing 2,5-diformylfuran from carbohydrates |
CN102731448A (zh) * | 2012-06-27 | 2012-10-17 | 北京大学 | 一种2,5-呋喃二甲醛的制备方法 |
CN103113327A (zh) * | 2013-01-24 | 2013-05-22 | 四川大学 | 一种由碳水化合物一步催化合成2,5-呋喃二甲醛的方法 |
WO2013177056A1 (en) * | 2012-05-23 | 2013-11-28 | Orochem Technologies, Inc. | Process and adsorbent for separating ethanol and associated oxygenates from a biofermentation system |
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Patent Citations (4)
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WO2003024947A1 (en) * | 2001-09-17 | 2003-03-27 | E.I. Du Pont De Nemours And Company | Process for preparing 2,5-diformylfuran from carbohydrates |
WO2013177056A1 (en) * | 2012-05-23 | 2013-11-28 | Orochem Technologies, Inc. | Process and adsorbent for separating ethanol and associated oxygenates from a biofermentation system |
CN102731448A (zh) * | 2012-06-27 | 2012-10-17 | 北京大学 | 一种2,5-呋喃二甲醛的制备方法 |
CN103113327A (zh) * | 2013-01-24 | 2013-05-22 | 四川大学 | 一种由碳水化合物一步催化合成2,5-呋喃二甲醛的方法 |
Non-Patent Citations (2)
Title |
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High yield production and purification of 5-hydroxymethylfurfural;Jianjian Wang等;《AIChE Journal》;20130128;第59卷(第7期);2558-2566 * |
Selective oxidation of 5-hydroxymethyl-2-furfural into 2,5-diformylfuran over VO2+ and Cu2+ ions immobilized on sulfonated carbon catalysts;Ngoc-Thuc Le等;《Applied Catalysis, A: General》;20130610;第464-465卷;305-312 * |
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