CN103539766A - Preparation method of furfural - Google Patents
Preparation method of furfural Download PDFInfo
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- CN103539766A CN103539766A CN201310522703.6A CN201310522703A CN103539766A CN 103539766 A CN103539766 A CN 103539766A CN 201310522703 A CN201310522703 A CN 201310522703A CN 103539766 A CN103539766 A CN 103539766A
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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
- C07D307/48—Furfural
Abstract
The invention discloses a preparation method of furfural. Particularly, the method comprises the following step of converting five-carbon sugar serving as a raw materail into furfural in the presence of a modified metal oxide serving as a catalyst in a mixture of water and an organic solvent at the temperature of 100-220 DEG C under the pressure of 0.1-10MPa. The method is high in product yield and simple in process routes, and has potential industrial application prospect; and moreover, products can be conveniently separated.
Description
Technical field
The present invention relates to the preparation method of chemical, relate in particular to a kind of preparation method of furfural.
Background technology
Furfural is a kind of biomass-based bulk chemical (280,000 tons of global annual production in 2005), and the derivative being transformed by furfural has potential application in fuel, polymer, medicine intermediate and chemistry of pesticide field.The more important thing is, from furfural, can obtain as a series of potential fuel dope molecules (as methyltetrahydrofuran, levulinate etc.) by catalyzed conversion.
Traditional catalysis wood sugar is mineral acid to the catalyzer of furfural, as sulfuric acid and hydrochloric acid (E.I.Fulmer, L.M.Christensen, R.M.Hixon, R.L.Foster, J Phys Chem.40 (1935) 133-141; H.D.Mansilla, J.Baeza, S.Urz ú a, G.Maturana, J.
, N.Dur á n, Bioresour Technol.66 (1998) 1189-193.).But these inorganic acid catalysts exist a series of problem, as environmental pollution, equipment corrosion, with product separation difficulty, exists a large amount of side reactions to make furfural productive rate low etc.
Reported that in recent years series of stable, efficient solid acid catalyst are for substituting traditional inorganic acid catalyst, as Sn-Beta, SO4
2-/ SnO
2, acidic ion exchange resin Amberlyst A70, loading type (the V.Choudhary V such as Suanphosphotungstate, layered zeolite, modified SBA-15, porous molecular screen, A.B.Pinar, S.I.Sandler, D.G.Vlachos, R.F.Lobo, ACS Catal.1 (2011) 1724-1728; P.L.Dhepe, R.Sahu, Green Chem.12 (2010) 2153-2156.).But there is the problems such as preparation is difficult, expensive, and stability is not high in the solid acid catalyst of above-mentioned report.
Summary of the invention
The problem existing in order to overcome above-mentioned mineral acid and solid acid catalyst, the invention provides a kind of method that carbohydrate is converted into furfural, utilizes water-organic solvent mixed system to prepare furfural under the catalysis of solid-phase catalyst modified metal-oxide.
The object of the invention is to be achieved through the following technical solutions:
The invention provides a kind of preparation method of furfural, it is characterized in that, under the pressure of the temperature of 100-220 ℃ and 0.1-10MPa, in the mixture of water and organic solvent, as the carbohydrate of raw material, under the modified metal-oxide as catalyzer exists, be converted into furfural, wherein said carbohydrate is to be selected from one or both in wood sugar and xylan.
In one embodiment, described modified metal-oxide is the niobium of phosphoric acid modification or one or both in tantalum pentoxide.Preferably, the described catalyzer of use and the mass ratio of described raw material are 1-200%.
In one embodiment, described organic solvent is to be selected from one or more in Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, isopropylcarbinol, methyl iso-butyl ketone (MIBK), methyl isobutyl carbinol, methyl tertiary butyl ether, Pentyl alcohol and primary isoamyl alcohol, and the water using and the volume ratio of organic solvent are 1: 0.25～1: 5.
In one embodiment, the described raw material of use and the mass ratio of water are 0.05～1.
In one embodiment, described temperature is that 140-200 ℃ and described pressure are 0.1-3MPa.
In one embodiment, described dehydration is carried out in batch reactor or continuous fixed bed type reactor.
In one embodiment, described dehydration is being carried out in fixed bed type reactor continuously, wherein first described catalyzer is packed in continuous fixed bed type reactor, then described reactor is heated to previous reaction temperature and under aforementioned pressure, the aqueous solution of described carbohydrate and organic solvent are mixed, then with 0.1～5h
-1liquid hourly space velocity the described aqueous solution and ORGANIC SOLVENT MIXTURES are pumped into the catalytic bed of described reactor.
Embodiment of the present invention, by take carbohydrate as raw material, obtains furfural by catalysis of solid catalyst by carbohydrate in water-organic solvent mixed system, and the method product separation is convenient, and technique is simple, has potential using value.
Embodiment
A kind of method that embodiment of the present invention provides carbohydrate to be converted into furfural obtains furfural by catalysis of solid catalyst by carbohydrate in water-organic solvent mixed system.
More specifically, the invention provides a kind of method that carbohydrate is converted into furfural, the method comprises: under the pressure of the temperature of 100-220 ℃ and 0.1-10MPa, wood sugar or xylan, in the mixed system of water and organic solvent, obtain furfural under the effect of the modified metal-oxide as catalyzer.
The carbohydrate using in described method comprises any or the arbitrarily several combination in wood sugar or xylan and their optical isomer.
Metal in described modified metal-oxide is one or both in niobium or tantalum, preferably uses phosphoric acid modification, and more preferably its consumption is 1-200% with raw materials quality ratio.
In water-ORGANIC SOLVENT MIXTURES in described method, organic solvent comprises one or more in Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, isopropylcarbinol, methyl iso-butyl ketone (MIBK), methyl isobutyl carbinol, methyl tertiary butyl ether, Pentyl alcohol and primary isoamyl alcohol, and the water using and the volume ratio of organic solvent are 1: 0.25～1: 5.。
Carbohydrate in described method and the mass ratio of water are 0.05～1.
In described method, preferable reaction temperature is 140-200 ℃, and preferred reaction pressure is 0.1-3MPa.
Described method is carried out on batch reactor or continuous fixed reaction bed.In fixed bed type reactor, carrying out continuously, wherein first described solid catalyst is packed in continuous fixed bed type reactor, then described reactor is heated to previous reaction temperature and under aforementioned pressure, the aqueous solution of described carbohydrate and organic solvent are mixed, and the liquid hourly space velocity (LHSV) of then take is 0.1～5h
-1flow velocity the described aqueous solution and ORGANIC SOLVENT MIXTURES are pumped into described reactor catalysis bed.
Below in conjunction with specific embodiment, the invention process process is described further.The following stated is only preferably embodiment of the present invention, but protection scope of the present invention is not limited to this.
Catalyzer Preparation Example
The preparation method of solid catalyst modified metal-oxide used (the modified oxidized tantalum (TA-p) of take is example) with reference to existing document (for example, referring to Fengli Yang, Qishun Liu, Min Yue, Xuefang Bai and Yuguang Du, Chem.Commun., 2011,47,4469-4471).Concrete preparation method is as follows:
By the commercially available tantalum hydroxide (HKXC of 100g, China), join the phosphate aqueous solution (v/v of 1.5L 10%, 100mL strong phosphoric acid joins in 1.4L water) in, room temperature mechanical stirring reaction 52h, room temperature ageing 12h after completion of the reaction, suction filtration, filter cake deionized water wash 5 times, no acidic to washings.65 ℃ of dried overnight, be warming up to 110 ℃ of vacuum-drying 2h again.Afterwards, will after its grinding powder, in 300 ℃ of retort furnaces, calcine 3h, obtain modified oxidized tantalum (TA-p) catalyzer of white powder solid (75g), standby.
The preparation of modified oxidized niobium catalytic and above-mentioned modified oxidized tantalum catalyzer are similar.
The Preparation Example of furfural
Following examples 1-10 realizes in batch reactor (autoclave):
Embodiment 1
In 25mL autoclave, add 0.4g wood sugar, 400mg TA-p catalyzer, 4mL water and 6mL1-butanols (1-BO).After airtight, be filled with nitrogen to 2MPa, and be heated to 140 ℃, stir speed (S.S.) 800r/min, stirring reaction 3h.After having reacted, be cooled to room temperature, sampling dilution, measures furfural content by high performance liquid chromatography (HPLC).High performance liquid chromatography testing conditions: Hitachi L2000 HPLC System, Alltech C18 column, moving phase CH
3oH: H
2o=20: 80, flow velocity: 1.0mL/min, column temperature: 30 ℃, detector: DAD, detects wavelength: 277nm.By HPLC, determine that product is furfural, and the yield of furfural is 39.33%.Wood sugar transformation efficiency is measured by HPLC equally.
Embodiment 2
Concrete reaction process is identical with embodiment 1 with detection method, just organic solvent is changed to 2-butanols (2-BO).As a result of products therefrom is furfural, and yield is 22.61%.
Embodiment 3
Concrete reaction process is identical with embodiment 1 with detection method, just organic solvent is changed to methyl iso-butyl ketone (MIBK) (MIBK).As a result of products therefrom is furfural, and yield is 38.21%.
Embodiment 4
Concrete reaction process is identical with embodiment 1 with detection method, just organic solvent is changed to primary isoamyl alcohol (i-AO).As a result of products therefrom is furfural, and yield is 33.23%.
Reaction conditions and the result of case study on implementation 1-4 are as shown in table 1:
Table 1
From embodiment 1-4, can find out, although the kind of organic solvent has a certain impact to furaldehyde yield, by method of the present invention, can obtain product furfural.
Embodiment 5
Concrete reaction process is identical with embodiment 2 with detection method, just temperature of reaction is adjusted into 160 ℃.As a result of products therefrom is furfural, and yield is 42.75%.
Embodiment 6
Concrete reaction process is identical with embodiment 2 with detection method, just temperature of reaction is adjusted into 180 ℃.As a result of products therefrom is furfural, and yield is 46.15%.
Embodiment 7
Concrete reaction process is identical with embodiment 3 with detection method, just temperature of reaction is adjusted into 160 ℃.As a result of products therefrom is furfural, and yield is 42.52%.
Embodiment 8
Concrete reaction process is identical with embodiment 3 with detection method, just temperature of reaction is adjusted into 180 ℃.As a result of products therefrom is furfural, and yield is 45.33%.
Reaction conditions and the result of case study on implementation 5-8 are as shown in table 2:
Table 2
From embodiment 5-8, can find out, temperature has a certain impact to furaldehyde yield, and in the methods of the invention, the suitableeest temperature of reaction is approximately 180 ℃.
Embodiment 9
Concrete reaction process is identical with embodiment 1 with detection method, just temperature of reaction is adjusted into 180 ℃, and water and organic phase ratio are adjusted into 1: 1.As a result of products therefrom is furfural, and yield is 50.81%.
Embodiment 10
Concrete reaction process is identical with embodiment 9 with detection method, just water and organic phase ratio is adjusted into 1: 1.5.As a result of products therefrom is furfural, and yield is 55.74%.
Embodiment 11
Concrete reaction process is identical with embodiment 9 with detection method, just water and organic phase ratio is adjusted into 1: 2.As a result of products therefrom is furfural, and yield is 48.64%.
Embodiment 12
Concrete reaction process is identical with embodiment 9 with detection method, just water and organic phase ratio is adjusted into 1: 3.As a result of products therefrom is furfural, and yield is 43.52%.
Reaction conditions and the result of case study on implementation 9-12 are as shown in table 3:
Table 3
From embodiment 9-12, can find out, water and organic phase ratio have a certain impact to furaldehyde yield, and in the methods of the invention, the suitableeest water and organic phase ratio are about 1: 1.5.
Embodiment 13
Concrete reaction process is identical with embodiment 6 with detection method, just saccharide raw material is adjusted into xylan.As a result of products therefrom is furfural, and yield is 23.12%.
Embodiment 14
Concrete reaction process is identical with embodiment 6 with detection method, just solid catalyst is adjusted into modified oxidized niobium.As a result of products therefrom is furfural, and yield is 43.35%.
From embodiment 13-14, can find out, in the methods of the invention, the saccharide raw material of use can be also xylan, and the catalyzer of use can be also modified oxidized niobium.
Following examples 15-26 realizes in flow reactor
Embodiment 15
In fixed-bed reactor, carrying out continuously, fixed-bed reactor adopt the zirconium material reaction tubes that internal diameter is 8mm, and reaction tubes two ends are loaded quartz sand and filled silica wool.Catalyst loading quality is 3g, admission space 3mL, and carrier gas is nitrogen, system pressure 2.0MPa, system pressure is controlled (Swagelok) by back pressure valve, and reaction bed temperature is surveyed (K type thermopair) by temperature sensor, and temperature regulator is controlled (Yudian518P).Upper feeding mode.Material pumps into reaction system by two SSI efficient liquid-phase chromatographic pumps.Reaction mixture is cooling by water cooler after beds with certain flow rate, collects reaction solution in gas-liquid separator, and the furfural content in organic phase and water is detected by HPLC respectively.Under the nitrogen pressure of 2MPa, the wood sugar aqueous solution of 10wt% and n-butyl alcohol are pumped in the mixing tank before reactor with certain flow rate, after on-line mixing, enter in the reactor that catalyzer TA-p is housed, by condenser condenses, enter gas-liquid separator with catalyzer contact reacts at a certain temperature.Collect reaction solution, after water and n-butyl alcohol phase separatory, wood sugar and furfural content are measured by HPLC respectively.Liquid hourly space velocity (LHSV)=(the water volume+organic phase volume pumping in fixed bed per hour)/catalyst volume.The liquid hourly space velocity of reaction is 1h
-1, the volume ratio of water and organic phase propyl carbinol is 1: 1, and temperature of reaction is 100 ℃, and it is 1.41% that HPLC measures furaldehyde yield.
Embodiment 16
Concrete reaction process is identical with embodiment 15 with detection method, just temperature of reaction is adjusted into 120 ℃.As a result of products therefrom is furfural, and yield is 7.35%.
Embodiment 17
Concrete reaction process is identical with embodiment 15 with detection method, just temperature of reaction is adjusted into 140 ℃.As a result of products therefrom is furfural, and yield is 24.48%.
Embodiment 18
Concrete reaction process is identical with embodiment 15 with detection method, just temperature of reaction is adjusted into 160 ℃.As a result of products therefrom is furfural, and yield is 44.90%.
Embodiment 19
Concrete reaction process is identical with embodiment 15 with detection method, just temperature of reaction is adjusted into 180 ℃.As a result of products therefrom is furfural, and yield is 55.95%.
Embodiment 20
Concrete reaction process is identical with embodiment 15 with detection method, just temperature of reaction is adjusted into 200 ℃.As a result of products therefrom is furfural, and yield is 47.55%.
Reaction conditions and the result of case study on implementation 15-20 are as shown in table 4:
Table 4
From case study on implementation 15-20, can find out, in flow reactor, temperature is influential to furaldehyde yield.From reaction result, temperature of reaction has a significant impact productive rate.Since 100 ℃, with the rising of temperature of reaction, the transformation efficiency of wood sugar rises gradually, and when temperature of reaction surpasses 180 ℃, wood sugar almost completely transforms.Furfural productive rate presents with downward trend after first rising of temperature rising.When temperature of reaction is during lower than 160 ℃, wood sugar transformation efficiency is not high, and furfural productive rate is lower.When temperature is 180 ℃, the maximum output of furfural is 55.95%, highly selective 61.81%.Continue rising temperature, wood sugar approaches completely and transforms, but furfural productive rate declines to some extent.
Embodiment 21
The present embodiment specific operation process is identical with embodiment 19, just liquid hourly space velocity is adjusted into 0.25h
-1, as a result of products therefrom is furfural, and yield is 58.67%.
Embodiment 22
The present embodiment specific operation process is identical with embodiment 19, just liquid hourly space velocity is adjusted into 0.5h
-1, as a result of products therefrom is furfural, and yield is 57.06%.
Embodiment 23
The present embodiment specific operation process is identical with embodiment 19, just liquid air speed per hour is adjusted into 0.75h
-1, as a result of products therefrom is furfural, and yield is 56.51%.
Reaction conditions and the result of case study on implementation 21-23 are as shown in table 5:
Table 5
From embodiment 19 and 21-23, can find out, liquid hourly space velocity LHSV is from 0.25h
-1to 1h
-1process in, the transformation efficiency of wood sugar and the productive rate of furfural decline gradually.Illustrate that LHSV has obvious impact to reaction process.LHSV is less than 1h
-1, wood sugar transformation efficiency surpasses 90%, and furaldehyde yield is greater than 55%.Along with the increase of LHSV, the transformation efficiency of wood sugar and the productive rate of furfural obviously decline.
Embodiment 24
The present embodiment specific operation process is identical with embodiment 19, just water and organic phase ratio is adjusted into 1: 1.5, and as a result of products therefrom is furfural, and yield is 59.66%.
Embodiment 25
The present embodiment specific operation process is identical with embodiment 19, just water and organic phase ratio is adjusted into 1: 2, and as a result of products therefrom is furfural, and yield is 50.63%.
Embodiment 26
The present embodiment specific operation process is identical with embodiment 19, just water and organic phase ratio is adjusted into 1: 3, and as a result of products therefrom is furfural, and yield is 48.71%.
Reaction conditions and the result of case study on implementation 24-26 are as shown in table 6:
Table 6
From embodiment 19 and embodiment 24-26, can find out, the ratio of water and organic phase (n-butyl alcohol) is from rising at 1: 1 the process of 1: 3, the phenomenon declining to some extent after first rising all appears in the transformation efficiency of wood sugar and the productive rate of furfural.The ratio of water and organic phase (n-butyl alcohol) is 1: 1.5 o'clock, wood sugar peak rate of conversion 96.86%, the highest yield 59.66% of furfural.
Below the present invention be have been described in detail, but the present invention is not limited to embodiment described herein.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, can make other changes and distortion.Scope of the present invention is defined by the following claims.
Claims (8)
1. the preparation method of a furfural, it is characterized in that, under the pressure of the temperature of 100-220 ℃ and 0.1-10MPa, in the mixture of water and organic solvent, as the five-carbon sugar class of raw material, under the modified metal-oxide as catalyzer exists, be converted into furfural, wherein said carbohydrate is to be selected from one or both in wood sugar and xylan.
2. the preparation method of furfural according to claim 1, is characterized in that, described modified metal-oxide is the niobium of phosphoric acid modification or one or both in tantalum pentoxide.
3. the preparation method of furfural according to claim 1, is characterized in that, the described catalyzer of use and the mass ratio of described raw material are 1-200%.
4. the preparation method of furfural according to claim 1, it is characterized in that, described organic solvent is to be selected from one or more in Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, isopropylcarbinol, methyl iso-butyl ketone (MIBK), methyl isobutyl carbinol, methyl tertiary butyl ether, Pentyl alcohol and primary isoamyl alcohol, and the water using and the volume ratio of organic solvent are 1: 0.25～1: 5.
5. the preparation method of furfural according to claim 1, is characterized in that, the described raw material of use and the mass ratio of water are 0.05～1.
6. the preparation method of furfural according to claim 1, is characterized in that, described temperature is that 140-200 ℃ and described pressure are 0.1-3MPa.
7. the preparation method of furfural according to claim 1, is characterized in that, described dehydration is carried out in batch reactor or continuous fixed bed type reactor.
8. the preparation method of furfural according to claim 7, it is characterized in that, described dehydration is being carried out in fixed bed type reactor continuously, wherein first described solid catalyst is packed in continuous fixed bed type reactor, then described reactor is heated to previous reaction temperature and under aforementioned pressure, the aqueous solution of described carbohydrate and organic solvent are mixed, then with 0.1～5h
-1liquid hourly space velocity the described aqueous solution and ORGANIC SOLVENT MIXTURES are pumped into the catalytic bed of described reactor.
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| CN104072450A (en) * | 2014-07-14 | 2014-10-01 | 南京林业大学 | Novel method for preparing 5-hydroxymethylfurfural and furfural by adopting biomass raw material |
| CN108727311A (en) * | 2018-05-14 | 2018-11-02 | 安徽理工大学 | A kind of furfural production new process of environmental protection |
| CN109704995A (en) * | 2019-01-25 | 2019-05-03 | 吉林凯莱英制药有限公司 | Fushan reduction reaction continuous device and serialization Fushan restoring method |
| CN111518060A (en) * | 2020-06-04 | 2020-08-11 | 中国科学技术大学 | Method for preparing furfural from fructose |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104072450A (en) * | 2014-07-14 | 2014-10-01 | 南京林业大学 | Novel method for preparing 5-hydroxymethylfurfural and furfural by adopting biomass raw material |
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| CN108727311A (en) * | 2018-05-14 | 2018-11-02 | 安徽理工大学 | A kind of furfural production new process of environmental protection |
| CN109704995A (en) * | 2019-01-25 | 2019-05-03 | 吉林凯莱英制药有限公司 | Fushan reduction reaction continuous device and serialization Fushan restoring method |
| CN109704995B (en) * | 2019-01-25 | 2024-01-23 | 吉林凯莱英制药有限公司 | Serialization device for Fushan reduction reaction and serialization Fushan reduction method |
| CN111518060A (en) * | 2020-06-04 | 2020-08-11 | 中国科学技术大学 | Method for preparing furfural from fructose |
| CN111518060B (en) * | 2020-06-04 | 2022-07-15 | 中国科学技术大学 | Method for preparing furfural from fructose |
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Application publication date: 20140129 |