CN102399203A - Method for preparing 5-hydroxymethylfurfural by degrading carbonhydrate through ionic liquid - Google Patents
Method for preparing 5-hydroxymethylfurfural by degrading carbonhydrate through ionic liquid Download PDFInfo
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Abstract
The invention discloses a method for preparing 5-hydroxymethylfurfural (HMF) by degrading carbonhydrate through ionic liquid. The method comprises the following steps of: adding the carbonhydrate, the ionic liquid and a cocatalyst into a reactor, introducing an entrainer, continuously vacuumizing a reaction system to make the vacuum degree kept between 100 and 500Pa, and performing catalysis reaction at the temperature of between 120 and 180DEG C for 10 to 60 minutes; and during reaction, putting a separator connected with a product outlet of the reactor into an ice bath for collecting a product, wherein the separator is communicated with the product outlet of the reactor through a heat insulating connecting tube, and the separator has the same vacuum degree as the reactor. The catalysis reaction and product separation are coupled, and high vacuum distillation is adopted and the entrainer is introduced in the reaction process to make the generated water and 5-HMF leave the reaction system, so that the aim of enhancing the generation of the 5-HMF and the product separation is fulfilled and a problem that the 5-HMF is hard to separate is effectively solved.
Description
Technical field
The invention belongs to the biomass resource utilization field, be specifically related to the method that a kind of ionic liquid degradable carbon hydrate prepares 5 hydroxymethyl furfural.
Background technology
In recent years, because the petering out of fossil energy, obtained extensive concern by the biomass research that synthetic chemical substitutes gasoline and chemical intermediate of setting out.These by biomass synthetic chemical substance in, the 5 hydroxymethyl furfural that obtains through carbohydrate degradation is an important hardware and software platform compound.For example; Through oxidation, catalytic hydrogenation, hydrogenolysis or aldol reaction etc.; 5 hydroxymethyl furfural can be used for Synthetic 2,5-furans diacid, 2,5-furans glycol, 2; 5-dihydroxymethyl THF, dimethyl furan, and liquid alkane etc. (like patent: US2009124839, US2009156841 etc.).And these synthetic products all possibly be important high molecular polymer monomer or important fuel materials.
Because high molecular carbohydrate generally is that glucose or fructose polycondensation form.By glucose 1, the polycondensation of 4-β glycosidic link obtains like Mierocrystalline cellulose, and starch is by glucose 1,4-α and 1, and the polycondensation of 6-α glycosidic link obtains, and glycogen and synanthrin are by fructose polycondensation acquisition or the like.Therefore, tending to select glucose and fructose is the model substance of 5 hydroxymethyl furfural as the research carbohydrate degradation.
Through making thorough investigation and study and our breadboard research to document; Think in carbohydrate degradation to be that the research field of 5-hydroxymethylfurfural has following three clear conclusions: (1) DeR is generally carried out under acid catalysis; The Louis acid catalysis effect often is superior to bronsted acid, and this is because the proton in the bronsted acid can quicken the coking of sugar; (2) water medium is unfavorable for the generation of 5 hydroxymethyl furfural, and tends to cause 5 hydroxymethyl furfural further to be degraded to levulinic acid and formic acid etc.; (3) it is relatively easy that fructose is degraded to 5 hydroxymethyl furfural, but conversion of glucose be 5 hydroxymethyl furfural reaction very the difficulty.Glucose can turn to fructose by first isomery before being degraded to 5 hydroxymethyl furfural.
Up to now, ionic liquid, especially imidazolyl ionic liquid, being considered to is that the catalyzed carbon hydrate is degraded to the most effectively one of catalyzer of 5 hydroxymethyl furfural.As: (Zhao et al such as Zhao; Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural.Science; 2007,316 (5831): 1597-1600), application number is the U.S. Patent application of US20100317879) adopt CrCl first
2-[EMIM] Cl catalystsystem catalysis glucose degradation is a 5 hydroxymethyl furfural, has obtained unprecedented high yield 69%; Application number is that the U.S. Patent application of US20090313889 adopts the metal composite synergic ion liquid of N-heterocyclic carbene (N-heterocyclic carbene) to come the catalyzed carbon hydrate; At 70 ℃; Acquisition fructose and conversion of glucose are that the yield of 5 hydroxymethyl furfural is respectively 96% and 82%, and catalystsystem can recycle through boiling off low-boiling point material.People such as Hu (Hu et al, Efficient conversion of glucose into 5-hydroxymethylfurfural catalyzed by a common Lewis acid SnCl
4In an ionic liquid.Green Chem, 2009,11 (11): 1746-1749) adopt SnCl
4/ [EMIM] BF
4Catalysis glucose and the degraded that contains the sugar of glucose unit have also obtained to surpass 60% 5-HMF yield.
Glucose is the most effectively catalyst/solvent of 5 hydroxymethyl furfural although the imidazolyl ionic liquid is considered to degrade; But; How from the ionic liquid reaction medium, to isolate product-hydroxymethylfurfural product but few people mention that this also is one of major reason that hinders its suitability for industrialized production.There is bibliographical information to adopt simple SX can reach this purpose; Like (Amarasekara such as Amarasekara; Mechanism of the dehydration of D-fructose to 5-hydroxymethylfurfural in dimethyl sulfoxide at 150degrees C:an NMR study.Carbohydr Res; 2008; 343 (18): after 3021-3024) dehydration of catalysis glucose and fructose generates the reaction completion of 5 hydroxymethyl furfural in ionic liquid, in reaction medium, add a certain amount of water and ether, at room temperature extract three times to isolate 5 hydroxymethyl furfural; 100 ℃ of other lower-boiling impurities of removing generation again, thus realize that ionic liquid and catalyzer reuse.(Moreau et al such as Moreau; Dehydration of fructose and sucrose into 5-hydroxymethylfurfural in the presence of 1-H-3-methyl imidazolium chloride acting both as solvent and catalyst.Mol Catal A:Chem; 2006; 253 (1-2): 165-169) adopt [HMIM] Cl as catalyzer and solvent catalysis fructose and sucrose dehydration generation 5 hydroxymethyl furfural, 5 hydroxymethyl furfural is come out by extracted with diethyl ether in batches or continuously completely.With ether continuous extraction 8h.After ionic liquid was reused 5 times, the 5 hydroxymethyl furfural yield still had 82%.Although bibliographical information can adopt the low boiling point organic solvent method of extraction from the ionic liquid reaction medium, to isolate 5 hydroxymethyl furfural; Yet there is obvious defects in these methods: (1) at first; This method needs a large amount of circulating solvents; And, when extraction, must add water in order to alleviate the big shortcoming of viscosity of il and to be beneficial to layering, make extraction process very complicated; (2) secondly, experiment shows that the balance of 5 hydroxymethyl furfural between ionic liquid phase and organic phase needs the very long time, makes that its industrial applications prospect is not good; (3) percentage extraction is low, and often needing repeatedly, extraction just can reach satisfied yield; (4) also there are 5 hydroxymethyl furfural and the problem that extracts the organic solvent secondary separation after extraction is accomplished.
Summary of the invention
The invention provides the method that a kind of ionic liquid degradable carbon hydrate prepares 5 hydroxymethyl furfural (5-HMF); Reaction-vacuum distilling coupling process that employing is strengthened based on entrainment agent; Promote carbohydrate degradation; Obtain high yield, highly purified 5 hydroxymethyl furfural crystal product simultaneously, solved that product is difficult to isolating problem in the prior art.
A kind of ionic liquid degradable carbon hydrate prepares the method for 5 hydroxymethyl furfural, comprising:
In reactor drum, add glucide, ionic liquid and promotor, and feed entrainment agent, simultaneously reaction system is continued to vacuumize, make vacuum tightness maintain 100-500Pa, carry out catalyzed reaction at 120-180 ℃, reaction times 10-60 minute; In the time of reaction, the separator that will be connected with the reactor product outlet places ice bath to collect product, and described separator is communicated with through the insulation pipe connecting with described reactor product outlet, and described separator keeps identical vacuum tightness with said reactor drum;
Wherein, described glucide is monose, disaccharides or polysaccharide, and described ionic liquid is an imidazolitm chloride type ionic liquid, and described promotor is metal-salt or MOX, and described entrainment agent is nitrogen, rare gas element, carbonic acid gas, C
1～C
8Alkane, acetone, MIBK in a kind of; By percentage to the quality, the consumption of described glucide is the 1%-10% of described ionic liquid consumption.
The product warp of collecting
1H-MR with
13The C-MR spectral characterization is confirmed as 5 hydroxymethyl furfural.
In the optimized technical scheme, described monose is fructose or glucose, and described disaccharides is sucrose or SANMALT-S, and described polysaccharide is Mierocrystalline cellulose or starch.
In the optimized technical scheme; The amount of substance of described promotor is the 3%-10% of glucose in the glucide (or fructose) unit amount of substance; That is: when said glucide was fructose or glucose, the amount of substance of described promotor was the 3%-10% of the amount of substance of said glucide; When said glucide was sucrose, the amount of substance of described promotor was the 3%-10% of total amount of substance of glucose unit and fructose units in the said glucide; When said glucide was SANMALT-S, Mierocrystalline cellulose or starch, the amount of substance of described promotor was the 3%-10% of the amount of substance of glucose unit in the said glucide.
In the optimized technical scheme, described imidazolitm chloride type ionic liquid is chlorination hexyl methyl imidazoles [HexMIM] Cl or chlorination octyl group Methylimidazole [OMIM] Cl, most preferably is to have more high boiling chlorination octyl group Methylimidazole [OMIM] Cl.
In the optimized technical scheme, described metal-salt is metal chloride or metal nitrate.For the degraded that contains the fructose units glucide, described metal-salt further is preferably AlCl
3, FeCl
3, IrCl
3, AuCl
3Or (NH
4)
2Ce (NO
3)
6, also can adopt other disclosed similar substance on document and patent; For the degraded that contains the glucose unit glucide, described metal-salt is the excellent CrCl that is preferably further
2, CrCl
3, SnCl
4, TiCl
4Or Zr (NO
3)
4, also can adopt other material of having reported on the document.
In the optimized technical scheme, described MOX is ZrO
2, also can adopt other material of having reported on the document.
Among the present invention, necessary Heat stability is good of described entrainment agent and the reaction of not participation system, therefore, described entrainment agent can also be selected the polarity or the non-polar gas solvent of aforementioned other Heat stability is good do not enumerated and the reaction of not participation system for use.Described entrainment agent is preferably nitrogen, cheaply is easy to get.
In the optimized technical scheme, also can carry out aftertreatment to the product of collecting, as: the product of collecting is obtained the 5 hydroxymethyl furfural crystal-5 ℃～4 ℃ crystallizations, perhaps with the spray-dried acquisition 5 hydroxymethyl furfural of the product of collecting powder.
Among the present invention, be raw material with the glucide, adopting imidazolitm chloride type ionic liquid is reaction solvent and catalyzer, and adds metal-salt or MOX is formed catalystsystem as catalyst aid, in reactor drum, carries out catalyzed reaction, generates product 5-HMF.Reactor drum is communicated with and is connected the high vacuum oil pump with separator, makes system be in high vacuum state through starting the high vacuum oil pump, and catalyzed reaction is carried out under high vacuum condition.Under high vacuum condition, water and 5-HMF that reaction generates can be evaporated, and get into the separator condensation that places ice bath.In addition, it is inner that entrainment agent gas feeds imidazolitm chloride type ionic liquid, promotes the evaporation of 5-HMF and moisture, strengthens reaction and the isolating purpose of product thereby reach.That is, the present invention adopts molecular distillation in reaction process, and the feeding of entrainment agent makes the moisture of generation and 5-HMF leave reaction system, strengthens 5-HMF and generates and the isolating purpose of product thereby reach.
Among the present invention, when being raw material with fructose, the recovery of 5-HMF reaches 95%; When being raw material with glucose, the recovery of 5-HMF reaches 88%.These data be up to now document that we know and patent report be the optimal experimental result of 5-HMF about carbohydrate degradation.And the present invention has the reaction times weak point, installs simple advantage.What is more important, document in the past and patent do not propose effective means the 5-HMF product are separated from reaction medium when report is obtained higher 5-HMF yield; And the present invention separates catalyzed reaction and is coupled with product, adopts the method for simple molecular distillation and gas entrainment to solve separating of 5-HMF effectively.
Description of drawings
Fig. 1 prepares the synoptic diagram of a kind of reaction unit that method adopted of 5 hydroxymethyl furfural for ionic liquid degradable carbon hydrate of the present invention.
The product that Fig. 2 makes for embodiment 1
1The H-NMR spectrogram.
The product that Fig. 3 makes for embodiment 1
13The C-NMR spectrogram.
Embodiment
Specify the present invention below in conjunction with embodiment and accompanying drawing, but the present invention is not limited to this.
Reaction unit as shown in Figure 1 comprises: there-necked flask reactor drum 3 and two mouthfuls of flask separators 8, there-necked flask reactor drum 3 are built-in with magnetic agitation 2, and are provided with entrainment agent inlet 4, and there-necked flask reactor drum 3 places oil bath 1; Two mouthfuls of flask separators 8 are provided with interface 7, connect the high vacuum oil pump, and two mouthfuls of flask separators 8 place ice bath groove 9; There-necked flask reactor drum 3 is provided with that 5, two mouthfuls of flask separators 8 of first communication port are provided with second communication port, 10, the first communication ports 5 and second communication port 10 is communicated with through pipe connecting, and is provided with insulation jacket 6 in the pipe connecting periphery.
In the above-mentioned reaction unit, there-necked flask reactor drum 3 is communicated with and is connected the high vacuum oil pump with two mouthfuls of flask separators 8, makes system be in high vacuum state through starting the high vacuum oil pump, and catalyzed reaction is carried out under high vacuum condition.Under high vacuum condition, water and 5-HMF that reaction generates can be evaporated, and get into two mouthfuls of flask separator 8 condensations that place ice bath.In addition, entrainment agent gas feeds ionic liquid inside through entrainment agent inlet 4, promotes the evaporation of 5-HMF and moisture, strengthens reaction and the isolating purpose of product thereby reach.Reaction can be collected yellow oily liquid after finishing in two mouthfuls of flask separators 8, can obtain faint yellow 5-HMF crystal through (4 ℃) crystallization in the further refrigerator; Also can adopt spraying drying to obtain the powder of 5-HMF.
Embodiment 1:
Adopt reaction unit as shown in Figure 1, the method that a kind of ionic liquid degradable carbon hydrate prepares 5 hydroxymethyl furfural (5-HMF) is following:
Take by weighing 20g [OMIM] Cl and place there-necked flask reactor drum 3, oil bath is warming up to 180 ℃.Take by weighing 2g fructose and 0.065g IrCl
3(1-2) H
2O (7mol% that is equivalent to the amount of fructose approximately) adds there-necked flask reactor drum 3 fast.Feed nitrogen as entrainment agent, and start the high vacuum oil pump reaction system is continued to vacuumize, keep vacuum tightness, finish reaction behind the 10min at 300Pa-500Pa.Collect in pipe connecting and the two mouthfuls of flask separators 8 residual product in sedimentary product and the there-necked flask reactor drum 3, carry out the absolute mass that HPLC calculates product respectively.
Product passes through
1H-NMR with
13C-NMR characterizes, and respectively as shown in Figures 2 and 3, through the documents analysis, confirms that product is 5 hydroxymethyl furfural (5-HMF).Specify as follows:
1H NMR (400MHz, CDCl
3, 29 ℃): δ=9.56 (s, 1H
a), 7.21 (d, J=3.5Hz, 1H
b), 6.51 (d, J=3.5Hz, 1H
c), 4.71 (s, 2H
d), 2.73 (s, 1H
e). confirm as 5-HMF through contrast.
13C NMR (101MHz, CDCl
3, 29 ℃): δ
C=177.40 (1C
a), 160.42 (1C
b), 152.12 (1C
c), 122.68 (1C
d), 109.90 (1C
e), 57.62 (1
CF). confirm as 5-HMF through contrast.
Take to prepare 5 hydroxymethyl furfural with embodiment 1 identical method and process, difference only is reaction substrate and reaction conditions.
Among the embodiment 2～16, ionic liquid is [OMIM] Cl, and entrainment agent is nitrogen, normal hexane or MIBK organic vapor, and the vacuum tightness of reaction system is maintained 300-500Pa.
When glucide was fructose, proportioning raw materials was: 2g glucide and 0.065g IrCl
3(1-2) H
2O is dissolved in 20g [OMIM] Cl.
When glucide was glucose, sucrose, alphalise starch or Mierocrystalline cellulose, proportioning raw materials was: 2g glucide and 0.049g CrCl
36H
2O is dissolved in 20g [OMIM] Cl.
The reaction substrate that each embodiment taked, entrainment agent, temperature of reaction and reaction times see for details in the table 2 listed.
Reference examples D1～D6
Among reference examples D1～D6, ionic liquid is [OMIM] Cl, does not all feed entrainment agent, is reflected under the normal pressure and carries out.
Proportioning raw materials is satisfied equally:
When glucide was fructose, proportioning raw materials was: 2g glucide and 0.065g IrCl
3(1-2) H
2O is dissolved in 20g [OMIM] Cl.
When glucide was glucose, sucrose, alphalise starch or Mierocrystalline cellulose, proportioning raw materials was: 2g glucide and 0.049g CrCl
36H
2O is dissolved in 20g [OMIM] Cl.
Reaction yield and the recovery result of embodiment 1～16 and reference examples D1～D6 products therefrom 5-HMF all are listed in the table 2.
In the table 2; The reaction yield of 5-HMF is meant that carbohydrate degradation is the actual recovery of this step chemical reaction of 5-HMF; The percentage ratio that the mole number sum of residual 5-HMF accounts for the mole number of the 5-HMF that the glucide that adds before the reaction can generate in theory in the mole number of the 5-HMF that distills out through calculating and the reaction solution obtains, that is:
In the table 2, the recovery of 5-HMF is meant that the quality of the 5-HMF that from reaction system, distills out accounts for the percentage ratio of total 5-HMF quality of reaction generation, and its method of calculation are:
Visible from table 2, take method of the present invention (embodiment 1～16) preparation 5 hydroxymethyl furfural, when being raw material with fructose, the reaction yield of 5-HMF reaches as high as 95.1%, and simultaneously, the recovery of 5-HMF is up to 95%; When being raw material with glucose, the reaction yield of 5-HMF reaches as high as 71.8%, and simultaneously, the recovery of 5-HMF is up to more than 88%.And in reference examples (among the reference examples D1～D6); Although when being substrate with fructose, the reaction yield of 5-HMF also can reach 90%, owing to do not carry distillatory technology secretly; The 5-HMF that is generated can only rest in the reaction system, and can't be separated (recovery of 5-HMF is zero).
Experiment is reclaimed in the reaction of table 2 glucide in the ionic liquid reaction system
It is thus clear that; The present invention separates catalyzed reaction and is coupled with product; In reaction process, adopt molecular distillation; And the feeding of entrainment agent makes the moisture content of generation and 5-HMF leave reaction system, strengthens 5-HMF and generates and the isolating purpose of product thereby reach, and solved the difficult problem of separation of 5-HMF effectively.
Claims (7)
1. an ionic liquid degradable carbon hydrate prepares the method for 5 hydroxymethyl furfural, it is characterized in that, comprising:
In reactor drum, add glucide, ionic liquid and promotor, and feed entrainment agent, simultaneously reaction system is continued to vacuumize, make vacuum tightness maintain 100-500Pa, carry out catalyzed reaction at 120-180 ℃, reaction times 10-60 minute; In the time of reaction, the separator that will be connected with the reactor product outlet places ice bath to collect product, and described separator is communicated with through the insulation pipe connecting with described reactor product outlet, and described separator keeps identical vacuum tightness with said reactor drum;
Wherein, described glucide is monose, disaccharides or polysaccharide, and described ionic liquid is an imidazolitm chloride type ionic liquid, and described promotor is metal-salt or MOX, and described entrainment agent is nitrogen, rare gas element, carbonic acid gas, C
1～C
8Alkane, acetone, MIBK in a kind of; By percentage to the quality, the consumption of described glucide is the 1%-10% of described ionic liquid consumption.
2. ionic liquid degradable carbon hydrate as claimed in claim 1 prepares the method for 5 hydroxymethyl furfural, it is characterized in that, described monose is fructose or glucose, and described disaccharides is sucrose or SANMALT-S, and described polysaccharide is Mierocrystalline cellulose or starch.
3. ionic liquid degradable carbon hydrate as claimed in claim 1 prepares the method for 5 hydroxymethyl furfural, it is characterized in that, described imidazolitm chloride type ionic liquid is chlorination hexyl methyl imidazoles or chlorination octyl group Methylimidazole.
4. ionic liquid degradable carbon hydrate as claimed in claim 3 prepares the method for 5 hydroxymethyl furfural, it is characterized in that, described imidazolitm chloride type ionic liquid is a chlorination octyl group Methylimidazole.
5. ionic liquid degradable carbon hydrate as claimed in claim 1 prepares the method for 5 hydroxymethyl furfural, it is characterized in that, described metal-salt is metal chloride or metal nitrate.
6. ionic liquid degradable carbon hydrate as claimed in claim 1 prepares the method for 5 hydroxymethyl furfural, it is characterized in that, described MOX is ZrO
2
7. ionic liquid degradable carbon hydrate as claimed in claim 1 prepares the method for 5 hydroxymethyl furfural, it is characterized in that, described entrainment agent is a nitrogen.
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| US9169227B2 (en) | 2011-12-13 | 2015-10-27 | Basf Se | Production of 5 hydroxymethyulfurfural (HMF) from hexose solutions in the presence of steam |
| US9162998B2 (en) | 2011-12-13 | 2015-10-20 | Basf Se | Preparation of 5-hydroxymethylfurfural (HMF) from saccharide solutions in the presence of a solvent having a boiling point greater than 60° C. and less than 200° C. (at standard pressure, called low boiler for short) |
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| CN116143731B (en) * | 2022-11-11 | 2024-04-19 | 合肥利夫生物科技有限公司 | Preparation method of 5-hydroxymethylfurfural |
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