CN103242269A - Preparation method of furfural - Google Patents
Preparation method of furfural Download PDFInfo
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- CN103242269A CN103242269A CN2013101868197A CN201310186819A CN103242269A CN 103242269 A CN103242269 A CN 103242269A CN 2013101868197 A CN2013101868197 A CN 2013101868197A CN 201310186819 A CN201310186819 A CN 201310186819A CN 103242269 A CN103242269 A CN 103242269A
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- furfural
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a preparation method of furfural, and belongs to the technical field of chemical synthesis. According to the method, furfural is obtained in 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) ionic liquid through a one-pot method by taking pentose and biomass as raw materials, taking a polymer-supported sulfonic acid (PEG (polyethylene glycol)-OSO3H, PS (polystyrene)-PEG-OSO3H) as a catalyst and taking manganese chloride as an additive. Therefore, the reaction process is greatly simplified, the production rate is improved, and the production cost is reduced; the catalyst is easy to recover and recycle, and the separation and post-treatment processes are simple; and adopted raw materials and various reagents are non-toxic, the production process is pollution-free, equipment is not corroded, and the method is environment-friendly.
Description
Technical field
The invention belongs to the organic chemical synthesis technical field, relate to a kind of preparation method of furfural, relating in particular to a kind of is the method for feedstock production furfural with biomass.
Background technology
Furfural has another name called and is 2 furan carboxyaldehyde, is the derivative that the hydrogen atom on 2 in the furans is replaced by aldehyde radical.Its English is abbreviated as FAL, and molecular formula is C
5H
4O
2Its chemical structural formula is:
Furfural is the most important derivative of furans ring system, be one important in the product that makes in the agricultural byproducts.Furfural is the raw materials for production of furfuryl alcohol, also is the main production raw material of furane resin.Furfural still prepares the raw material of multiple medicine and Industrial products.Traditional preparation process furfural method is, makes biomass by hydrolyzation form wood sugar with strong mineral acid example hydrochloric acid or sulfuric acid, then the wood sugar generation furfural that dewater under the effect of acid.But, adopt this method can only obtain 45 ~ 55% furfurals, not only productive rate is low, and the acid of using has strong corrodibility to production unit; Secondly, all there are very big problem in the recycling of mineral acid and product separation, so this method is greatly limited in the application of industrial circle.
Summary of the invention
The objective of the invention is at problems of the prior art, providing a kind of is the method for feedstock production furfural with pentose and biomass.
The preparation method of furfural of the present invention is to be raw material with pentose or biomass, is catalyzer with the sulfonic acid of polymkeric substance support, and Manganous chloride tetrahydrate is additive, at 1-butyl-3-Methylimidazole hexafluorophosphate ([BMIM] PF
6) in the ionic liquid, in 120 ℃～160 ℃ reaction 0.2 ~ 1 h down, after reaction finished, extraction separated and gets.Its reaction equation is as follows:
Described pentose is wood sugar, ribose or pectinose; Described biomass are maize straw, corncob cellulose, aspen, pine, withy fringe or straw;
The sulfonic acid of described polymerization catalyst thing support is PEG-OSO
3H or PS-PEG-OSO
3H, catalyst consumption is raw material pentose or biomass quality 3 ~ 4 times;
The mass volume ratio of described raw material pentose or biomass and ionic liquid 1-butyl-3-Methylimidazole hexafluorophosphate is 0.03 ~ 0.1g/m;
The consumption of described additive Manganous chloride tetrahydrate is raw material pentose or biomass quality 0.15 ~ 0.4 times;
For the further cost of saving, improve the yield of furfural, after extracted organic phase, in extracting mother liquid, continue to add pentose or biomass, reaction 0.2 ~ 1h under 120 ℃～160 ℃; After reaction finished, extraction merged organic phase, separates, and drying obtains furfural.
Above-mentioned synthetic product is through FTIR (KBr),
1H NMR,
13C NMR and HPLC detect, and its product is the pure product of furfural.
The present invention is relative, and prior art has the following advantages:
1, to adopt with pentose and biomass be raw material in the present invention, is catalyzer with the sulfonic acid of polymkeric substance support, at [BMIM] PF
6) in the ionic liquid, one kettle way has obtained furfural, has simplified reaction greatly, has effectively improved the productive rate of furfural;
2, equal inexpensive being easy to get of raw material of the present invention and all ingredients, cost is low; Reaction system recycle the further production cost that reduces furfural;
3, use the catalyzer of polyoxyethylene glycol load to have advantages of high catalytic activity, effectively improved production efficiency; And catalyzer is easy to reclaim and recycle, separate and aftertreatment technology simple;
4, raw material and all ingredients of the present invention's employing are nontoxic, and production process is pollution-free, and equipment is not had corrosion, environmental friendliness.
Embodiment
Be further described below by the synthetic method of specific examples to furfural of the present invention.
Embodiment 1, the synthetic furfural of wood sugar
Adding 0.5 mmol(0.075 g in 15 mL standard Schlenk Glass tubings) wood sugar, 0.3g PEG-OSO
3H, 0.03 g Manganous chloride tetrahydrate, and then add 2 mL [BMIM] PF
6, at 120 ℃ of following stirring reaction 18 min; After reaction is finished, cooling rapidly is with ether (3 * 2 mL) extraction, after extraction is finished, the wood sugar that adds 0.5 mmol in the mother liquor of extraction, under 120 ℃ condition, can continue to recycle, merge organic phase, remove ether with Rotary Evaporators under 40 ℃, vacuum-drying, spend the night, get furfural, yield 75%.
FTIR?(KBr)?(
ν,?cm
-1):?3388?(-OH),?1671?(-CHO),?1520?(C=C),?1020?(C-O-C),?2848,?2806?(-CH
2);
?1H-NMR?(400?MHz，?CDCl
3)?δ?＝?9.67?(s,?1H,?CHO),?δ?=?7.71?(d,?
J=4.0?Hz,?1H,?Furan-H-5),?δ?=?7.28?(d,?
J=6.0?Hz,?1H,?Furan-H-3),?δ?=?6.62?(t,?1H,
?J=4.0?Hz,?Furan-H-4);
?13C-NMR?(101?MHz,?CDCl
3)?δ:177.93,?153.06,?148.36,?121.55,?112.76。
Embodiment 2, the synthetic furfural of wood sugar
Add 0.2g PS-PEG-OSO
3H, other are identical with embodiment 1, the yield 82% of furfural, its each performance index or characterization data are with embodiment 1.
Embodiment 3, the synthetic furfural of ribose
Adding 0.5 mmol(0.075 g in 15 mL standard Schlenk Glass tubings) ribose, 0.3g PEG-OSO
3H, 0.03 g Manganous chloride tetrahydrate, and then add 2 mL [BMIM] PF
6, stirring reaction 20 min under 120 ℃ condition; After reaction is finished, cooling rapidly, with ether (3 * 2 mL) extraction, after extraction was finished, the ribose that adds 0.5 mmol in the mother liquor of extraction can continue to recycle under 120 ℃ condition, merge organic phase, remove ether with Rotary Evaporators under 40 ℃, vacuum-drying is spent the night, get furfural, yield 67%.Its each performance index or characterization data are with embodiment 1.
Embodiment 4, the synthetic furfural of ribose
Add 0.2g PS-PEG-OSO
3H, other are identical with embodiment 3, the yield 70% of furfural, its each performance index or characterization data are with embodiment 1.
Embodiment 5, the synthetic furfural of pectinose
The pectinose that in 15 mL standard Schlenk Glass tubings, adds 0.5 mmol (0.075 g), 0.3g PEG-OSO
3H, 0.03 g Manganous chloride tetrahydrate, and then add 2 mL [BMIM] PF
6, stirring reaction 20 min under 120 ℃ condition; After reaction is finished, cooling rapidly, with ether (3 * 2 mL) extraction, after extraction was finished, the pectinose that adds 0.5 mmol in the mother liquor of extraction can continue to recycle under 120 ℃ condition, merge organic phase, remove ether with Rotary Evaporators under 40 ℃, vacuum-drying is spent the night, get furfural, yield 72%.Its each performance index or characterization data are with embodiment 1.
Embodiment 6, the synthetic furfural of pectinose
Add 0.2g PS-PEG-OSO
3H, other are identical with embodiment 5, the yield 77% of furfural, its each performance index or characterization data are with embodiment 1.
Embodiment 7, the synthetic furfural of biomass
The biomass that in 15 mL standard Schlenk Glass tubings, add 0.2 g, 0.3 g PEG-OSO
3H, 0.03 g Manganous chloride tetrahydrate, and then add 2 mL [BMIM] PF
6, stirring reaction 0.5～1 h under 120 ℃～160 ℃ condition; After reaction was finished, cooling was rapidly filtered, with ether (3 * 2 mL) extraction, after extraction is finished, add biomass in the mother liquor of extraction and under 120 ℃ condition, can continue to recycle, merge organic phase, remove ether with Rotary Evaporators under 40 ℃, vacuum-drying is spent the night, and gets furfural.Its each performance index or characterization data are with embodiment 1.The yield that different biomass prepare furfural sees the following form:
Embodiment 8, the synthetic furfural of biomass
Add 0.2g PS-PEG-OSO
3H, other are identical with embodiment 7.Obtain each performance index of furfural or characterization data with embodiment 1.The yield that different biomass prepare furfural sees the following form:
Claims (7)
1. the preparation method of a furfural is to be raw material with pentose or biomass, is catalyzer with the sulfonic acid of polymkeric substance support, and Manganous chloride tetrahydrate is additive, in ionic liquid 1-butyl-3-Methylimidazole hexafluorophosphate, in 120 ℃～160 ℃ reaction 0.2～1h down; After reaction finished, extraction separated, and is dry and get.
2. the preparation method of furfural according to claim 1 is characterized in that: after extraction is finished, add pentose or biomass in extracting mother liquid, in 120 ℃～160 ℃ reaction 0.2～1h down; After reaction finished, extraction merged organic phase, separates, and drying obtains furfural.
3. the preparation method of furfural as claimed in claim 1 or 2, it is characterized in that: described pentose is wood sugar, ribose or pectinose.
4. the preparation method of furfural as claimed in claim 1 or 2, it is characterized in that: described biomass are maize straw, corn cob, aspen, pine, withy fringe or straw.
5. the preparation method of furfural as claimed in claim 1 or 2, it is characterized in that: the sulfonic acid of described polymerization catalyst thing support is PEG-OSO
3H or PS-PEG-OSO
3H, its consumption are raw material pentose or biomass quality 2～4 times.
6. the preparation method of furfural as claimed in claim 1 or 2, it is characterized in that: the consumption of described additive Manganous chloride tetrahydrate is raw material pentose or biomass quality 0.15～0.4 times.
7. the preparation method of furfural as claimed in claim 1 or 2, it is characterized in that: the mass volume ratio of described raw material pentose or biomass and ionic liquid 1-butyl-3-Methylimidazole hexafluorophosphate is 0.03～0.1g/mL.
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Cited By (4)
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|---|---|---|---|---|
| CN104193704A (en) * | 2014-07-31 | 2014-12-10 | 华南理工大学 | Method for preparing furfural by catalyzing xylose by using acid catalyst |
| CN105315243A (en) * | 2015-09-16 | 2016-02-10 | 安庆市宜秀区永兴农机农艺综合发展专业合作社 | Method for preparing furfural through agricultural waste |
| CN107324994A (en) * | 2017-07-10 | 2017-11-07 | 济南大学 | The method that deoxyribose prepares ethyl levulinate |
| WO2018121329A1 (en) * | 2016-12-29 | 2018-07-05 | 江南大学 | Magnetic metal oxide crosslinked acidic poly(ionic liquid) and use thereof |
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| CN102993140A (en) * | 2012-12-13 | 2013-03-27 | 浙江大学 | Method for preparing 5-hydroxymethyl furfural by catalyzing biomass conversion |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193704A (en) * | 2014-07-31 | 2014-12-10 | 华南理工大学 | Method for preparing furfural by catalyzing xylose by using acid catalyst |
| CN105315243A (en) * | 2015-09-16 | 2016-02-10 | 安庆市宜秀区永兴农机农艺综合发展专业合作社 | Method for preparing furfural through agricultural waste |
| WO2018121329A1 (en) * | 2016-12-29 | 2018-07-05 | 江南大学 | Magnetic metal oxide crosslinked acidic poly(ionic liquid) and use thereof |
| US10898888B2 (en) | 2016-12-29 | 2021-01-26 | Jiangnan University | Preparation and application of magnetic metallic oxide cross-linked acidic polyionic liquid |
| CN107324994A (en) * | 2017-07-10 | 2017-11-07 | 济南大学 | The method that deoxyribose prepares ethyl levulinate |
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