CN106279076B - A method of catalysis hexose prepares 5 hydroxymethyl furfural - Google Patents
A method of catalysis hexose prepares 5 hydroxymethyl furfural Download PDFInfo
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- CN106279076B CN106279076B CN201510260221.7A CN201510260221A CN106279076B CN 106279076 B CN106279076 B CN 106279076B CN 201510260221 A CN201510260221 A CN 201510260221A CN 106279076 B CN106279076 B CN 106279076B
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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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Abstract
The present invention provides a kind of methods that catalysis hexose prepares 5 hydroxymethyl furfural.This method is to include the sugared for substrate of hexose in hexose or structure, and the metal phthalocyanine complex for using acidic functionality to modify is catalyst, catalysis sugar dehydration generation 5 hydroxymethyl furfural.It is experimentally confirmed that this method is simple and easy, catalyst is environmentally protective, and the yield that catalysis generates 5 hydroxymethyl furfural is high, and the easy recycling and reusing of the catalyst, has a good application prospect.
Description
Technical field
The invention belongs to biomass energy technology fields, and in particular to a kind of catalysis hexose prepares 5 hydroxymethyl furfural
The method of (5-HMF).
Background technique
5-HMF is a kind of multi-functional compounds of great potential, is the important biomolecule of the synthetic fuel energy, chemicals etc.
Based platform compound is described as " giant being sunk into sleep " by U.S. Department of Energy.For example, compound 2,5-furandicarboxylic acid, 2 downstream,
5- furyl dimethyl carbinol, 2,5- dihydroxymethyl tetrahydrofuran etc. are the important monomers of synthesizing new high molecular material；Its derivative two
Having a extensive future in terms of methylfuran liquid fuel within, it is extensive that the derivative that furan nucleus restores can be used as organic solvent
It uses.
5-HMF after hexose triple dewatering by obtaining, research shows that acidic catalyst is added in the reaction system effectively to be mentioned
High-carbohydrate dehydration generates the efficiency of 5-HMF.Currently, main acidic catalyst type includes inorganic acid, highly acidic cation friendship
Change resin, zeolite, solid acid, ionic liquid etc..Wherein, the sour cheap and catalysis activity of minerals is high, but catalyst is not
It can recycle, product is not readily separated and the high requirements on the equipment；Solid acid is easily separated and recoverable, but catalysis activity is general
All over not high；The thermal stability of acid cation exchange resin is generally poor.How suitable catalyst optimization reaction system is selected
It is most important in the preparation of 5-HMF.
Carbohydrate dehydration can be improved the present invention is based on acidic catalyst and generates this basic theory of 5-HMF, with acidic functionality
The metal phthalocyanine complex of modification is catalyst, and high-temperature catalytic carbohydrate is dehydrated the method for preparing 5-HMF.Present invention uses novel
Catalyst, the yield of 5-HMF can be effectively improved；Magnetic metal phthalocyanine complex is selected also to act on using magnetic-adsorption effective
Separating catalyst, recycling, reduces cost；And reaction environment is weakly acidic, it is low for equipment requirements.
Summary of the invention
Phthalocyanine is a kind of macrocyclic compound, there is a cavity in ring, and two hydrogen atoms in center cavity can be by almost institute
Some metallic elements replace, and can introduce a variety of different acidic functionalities on phthalocyanine ring, are a kind of extremely strong big rings of plasticity point
Minor structure.
The inventors discovered that using sugar for substrate, the process that sugar dehydration prepares 5-HMF is catalyzed under the conditions of acidic catalyst
In, when acidic catalyst selects the metal phthalocyanine complex of acidic functionality modification, the yield of 5-HMF is high, and catalyst
Easily recycling.
That is, the technical solution of the present invention is as follows: a kind of catalysis hexose method for preparing 5-HMF, this method using sugar as substrate,
It is catalyzed sugar juice dehydration under the conditions of acidic catalyst and generates 5-HMF, the sugar is the structure of hexose or the sugar
In include hexose, it is characterized in that: the acidic catalyst be acidic functionality modification metal phthalocyanine complex.
The metal phthalocyanine complex of the acidic functionality modification refers to is matched using acidic functionality modified metal phthalocyanine
Close the mother nucleus structure of object.The mother nucleus structure of metal phthalocyanine complex is as follows:
Wherein, metallic element M be can be with the metallic element of hydrogen atom in substituted phthalocyanine center cavity.The metallic element is unlimited,
Including iron, copper, cobalt, aluminium, nickel, calcium, sodium, zinc etc., preferably, the metal have magnetic absorption, such as iron, cobalt, nickel or
Zinc etc..α, β refer to that acidic functionality modifies position in phthalocyanine ring.
The acidic functionality is can to mention protogenic functional group, including carboxyl (- COOH), phenolic hydroxyl group (- OH), sulphur
Acidic group (- SO3H), hydroxyl (- OH), nitro (- NO3) etc..Preferably, the acidic functionality is carboxyl, sulfonic group and nitre
Acidic group.
Such as structure above, the modification substitution mode of the acidic functionality includes α, phthalocyanine ring modifications and/or phthaleins
The modification that cyanines ring is β.Since the structural formula is symmetrical structure, eight α, eight β are shared.Preferably, the acidity
Four modifications and/or β, phthalocyanine ring four modifications that the modification mode of functional group is α, phthalocyanine ring.
The sugar is the monosaccharide for having hexose in hexose or structure, disaccharides, oligosaccharides, polysaccharide etc., including fruit
Sugar, glucose, galactolipin, Tagatose, lactose, sucrose, starch, fibrous polysaccharaide, algal polysaccharides etc..Preferably, the sugar
For the mixing of one or more of fructose, glucose, Tagatose, sucrose, algal polysaccharides.Further preferably, described
Sugar is fructose and/or Tagatose.
Solvent in the sugar juice is unlimited, including water, organic solvent, ionic liquid, two-phase solvent etc..As excellent
Choosing, the solvent are water and/or dimethyl sulfoxide.
Preferably, the sugar juice concentration be 10 grams per liters~500 grams per liters, more preferably 50 grams per liter~200 gram/
It rises.
Preferably, acidic catalyst concentration is 0.1 grams per liter~10 grams per liters in the sugar juice.
Preferably, the catalytic reaction temperature is 60~200 degrees Celsius, more preferably 80~140 degrees Celsius.
Preferably, the catalysis reaction time is 0.5~24 hour, more preferably 1~6 hour.
After reaction, the acidic catalyst can be recycled by magnetic-adsorption.That is, in solution after the reaction plus
Enter magnet grains, stirring or standing, to adsorb the acidic catalyst, then filters, separates, recycle the acidic catalyst.Make
To be preferred, the additive amount of the magnet grains is 1~10 times, stirring and adsorbing 1~10 hour of acidic catalyst.
In conclusion the metal phthalocyanine complex that the present invention is modified using acidic functionality as catalyst, is catalyzed sugar dehydration life
At 5-HMF, have the following beneficial effects:
(1) yield is high
This method selects the metal phthalocyanine complex of acidic functionality modification as catalyst, and not only having expanded can be used for sugar
The selection of the catalyst of degradation, and can select to introduce the acidic functionality of variety classes and number according to different substrate sugar
And metallic element, to improve the yield of 5-HMF, experiment confirms that this method can make the yield of 5-HMF reach 30~99%.
(2) catalyst easily recycles
This method selects the metal phthalocyanine complex of acidic functionality modification as catalyst, which has magnetism,
Therefore the method that magnet absorption can be used after reaction recycles the catalyst, simple and easy to do, and the rate of recovery is high, greatly reduces
Production cost.
(3) environmental-friendly
Catalyst used in this method is weakly acidic, low for equipment requirements, environmentally protective.
Detailed description of the invention
Fig. 1 is tetrasulfonic acid iron-phthalocyanine catalysis gluconate dehydratase preparation 5-HMF reaction under the conditions of each temperature of l of the embodiment of the present invention
In fructose converting rate and 5-HMF yield change over time curve；
Fig. 2 is that different acidic functionality modification ZnPcs are dehydrated as catalyst Tagatose in the embodiment of the present invention 2
Prepare fructose converting rate and 5-HMF yield in the reaction of 5-HMF；
Fig. 3 be in the embodiment of the present invention 3 eight sulfonic acid cobalt phthalocyanines as catalyst reuse 5 catalysis fructose dehydrations
Fructose conversion ratio and 5-HMF yield after preparation 5-HMF.
Specific embodiment
Present invention is further described in detail for embodiment with reference to the accompanying drawing, it should be pointed out that implementation as described below
Example is intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1:
In the present embodiment, urged under the conditions of iron-phthalocyanine (the referred to as tetrasulfonic acid iron-phthalocyanine) of acidic catalyst tetrasulfonic acid modification
Change glucose solution dehydration and generate 5-HMF, the structural formula of the tetrasulfonic acid iron-phthalocyanine is as follows:
The preparation process is as follows:
Configuration concentration is 100 milliliters of glucose solution of 100 grams per liters, and 1 gram of tetrasulfonic acid iron-phthalocyanine is added in the solution,
3 parts of samples are dispensed after completely dissolution, it is 30 milliliters every part, closed, it is respectively placed under 100 degrees Celsius, 120 degrees Celsius, 140 degrees Celsius
Quiescence in high temperature reaction sampled 500 microlitres every 1 hour, remaining concentration of glucose and production in high performance liquid chromatography detection reaction solution
The content of raw 5 hydroxymethyl furfural.3 grams of magnet grains are added in each reaction solution after reaction, after being sufficiently stirred 1 hour
Filtering, catalyst is separated from reaction solution, and final high temperature selects the sieve separation magnet grains in suitable aperture after so that magnet is demagnetized
And catalyst.
It is as shown in Figure 1 to change over time curve for inversion rate of glucose and 5-HMF yield after above-mentioned each part example reaction.From
As can be seen that 5-HMF is made in tetrasulfonic acid iron-phthalocyanine catalysis gluconate dehydratase under the conditions of above-mentioned each temperature in Fig. 1；Also, four sulphurs
The catalytic effect of sour iron-phthalocyanine is optimal at 140 degrees Celsius, 140 degrees Celsius react 4 hours after, 5-HMF content be 32 grams/
It rises, yield 45.7%, at this point, inversion rate of glucose is 77%, there is 59% glucose to be converted into purpose product；With temperature
It reduces, the catalytic effect of tetrasulfonic acid iron-phthalocyanine weakens, and 120 degrees Celsius of catalytic effect and 140 degrees Celsius of differences are little, after of continuing rising
Reaction effect will not be remarkably reinforced in high-temperature.
Embodiment 2:
In the present embodiment, the dehydration of catalytic tower lattice sugar juice generates 5-HMF, the acidic catalyst under the conditions of acidic catalyst
For the ZnPc that acidic functionality R tetra- is modified, structural formula is as follows, and wherein R can be carboxyl, sulfonic group or phenolic hydroxyl group.
That is, the ZnPc that the acidic catalyst can be the ZnPc (abbreviation tetrabasic carboxylic acid ZnPc) of the modification of carboxylic acid four, sulfonic acid four is modified
The ZnPc (referred to as four phenolic hydroxyl group ZnPcs) of (abbreviation tetrasulfonic acid ZnPc) or phenolic hydroxyl group four modification.
The preparation process is as follows:
With 100 milliliters of Tagatose solution that DMSO configuration concentration is 200 grams per liters, 3 parts of samples, every part of 30ml, at this are dispensed
0.1 gram of tetrabasic carboxylic acid ZnPc, 0.1 gram of tetrasulfonic acid ZnPc, 0.1 gram of four phenolic hydroxyl group ZnPc are separately added into 3 parts of samples, then
It is at the uniform velocity stirred to react at 80 degrees Celsius 3 hours, the concentration and Tagatose of the 5 hydroxymethyl furfural that high performance liquid chromatography measurement generates
Residual concentration, as a result as shown in Figure 2.
As shown in Figure 2, in DMSO solution, tetrabasic carboxylic acid ZnPc, tetrasulfonic acid ZnPc and four phenolic hydroxyl group ZnPcs are equal
Tagatose can be catalyzed and be dehydrated obtained 5-HMF；Also, tetrabasic carboxylic acid ZnPc is best to the catalytic effect of Tagatose, after reaction 3 hours
Tagatose is totally converted, and 5-HMF yield has reached 95%.
Embodiment 3:
In the present embodiment, it is catalyzed fructose soln dehydration under the conditions of acidic catalyst and generates 5-HMF, which is
The cobalt phthalocyanine (referred to as eight sulfonic acid cobalt phthalocyanines) that sulfonic acid eight is modified, structural formula is as follows,
The preparation process is as follows:
(1) with 100 milliliters of fructose soln that DMSO configuration concentration is 50 grams per liters, 0.5 gram of catalyst, the catalyst is added
For eight sulfonic acid cobalt phthalocyanines, 120 degrees Celsius are at the uniform velocity stirred to react 1 hour, the 5 hydroxymethyl furfural that high performance liquid chromatography measurement generates
The residual concentration of concentration and fructose then proceedes to step (2)；
(2) after reaction in reaction solution be added 5 grams of magnet grains, filtered after being sufficiently stirred 2 hours, by catalyst from
It is separated in reaction solution.Final high temperature selects the sieve separation magnet grains and catalyst in suitable aperture after so that magnet is demagnetized, then after
Continuous step (3)；
(3) it using the catalyst recycled in step (2) as catalyst used in step (1), repeats step (1).
Fig. 3 is the catalytic effect diagram that above-mentioned catalyst is recycled 5 times.From the figure 3, it may be seen that the catalyst urges fructose
It is good to change effect, and can be recycled, during preceding recycling three times, catalyst performance does not lose substantially,
Fructose converting rate maintains 100%, 5-HMF yield after 90% or more, recycling 4 times, and catalytic effect slightly weakens, and repeats
After 5 times, fructose converting rate is 90%, and 5-HMF yield is 80% or so.
Above-described embodiment is used to illustrate the present invention, rather than limits the invention, in spirit of the invention and
In scope of protection of the claims, to any modifications and changes that the present invention makes, protection scope of the present invention is both fallen within.
Claims (14)
1. it is de- to be catalyzed sugar juice using sugar as substrate under the conditions of acidic catalyst for a kind of method that catalysis hexose prepares 5-HMF
Water generates 5-HMF, and the sugar is in the structure of hexose or the sugar including hexose, it is characterized in that: the acid
Property catalyst is the mother nucleus structure of acidic functionality modified magnetic metal phthalocyanine complex and is formed, the magnetic metal phthalein
The mother nucleus structure of cyanines complex is as follows:
Wherein, M be can be with the magnetic metal element of hydrogen atom in substituted phthalocyanine center cavity；α, β refer to acidic functionality in phthalocyanine
The modification position of ring；
The acidic functionality is carboxyl, phenolic hydroxyl group or sulfonic group.
2. the method that catalysis hexose prepares 5-HMF as described in claim 1, it is characterized in that: the magnetic metal element M
It is iron, cobalt or nickel.
3. the method that catalysis hexose prepares 5-HMF as described in claim 1, it is characterized in that: the acidic functionality
Modification mode includes α, phthalocyanine ring modifications and/or β, phthalocyanine ring modifications.
4. the method that catalysis hexose prepares 5-HMF as described in claim 1, it is characterized in that: the acidic functionality
Four modifications and/or β, phthalocyanine ring four modifications that modification mode is α, phthalocyanine ring.
5. the method that catalysis hexose prepares 5-HMF as described in claim 1, it is characterized in that: the sugar is monosaccharide, two
Sugar, oligosaccharides, polysaccharide.
6. the method that catalysis hexose prepares 5-HMF as described in claim 1, it is characterized in that: the sugar is fructose, grape
The mixing of one or more of sugar, galactolipin, Tagatose, lactose, sucrose, starch, fibrous polysaccharaide, algal polysaccharides.
7. the method that catalysis hexose prepares 5-HMF as described in claim 1, it is characterized in that: the sugar juice concentration is
10 grams per liters~500 grams per liters.
8. the method that catalysis hexose prepares 5-HMF as claimed in claim 7, it is characterized in that: the sugar juice concentration is
50 grams per liters~200 grams per liters.
9. the method that catalysis hexose prepares 5-HMF as described in claim 1, it is characterized in that: in the sugar juice, it is acid
Catalyst concn is 0.1 grams per liter~10 grams per liters.
10. the method that catalysis hexose prepares 5-HMF as described in claim 1, it is characterized in that: the catalytic reaction temperature
It is 60~200 degrees Celsius.
11. the method that catalysis hexose prepares 5-HMF as claimed in claim 10, it is characterized in that: temperature is reacted in the catalysis
Degree is 80~140 degrees Celsius.
12. the method that catalysis hexose prepares 5-HMF as described in claim 1, it is characterized in that: the catalysis reaction time
It is 0.5~24 hour.
13. the method that catalysis hexose prepares 5-HMF as claimed in claim 12, it is characterized in that: when the catalysis is reacted
Between be 1~6 hour.
14. the method that catalysis hexose prepares 5-HMF as described in claim 1, it is characterized in that: after reaction, passing through magnetic
Acidic catalyst described in power adsorption recovery.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249307A (en) * | 1999-08-19 | 2000-04-05 | 北京工业大学 | Metallic phthalocyanine carboxylic acid derivatives and its preparing process and application |
| CN1944395A (en) * | 2006-10-27 | 2007-04-11 | 北京工业大学 | Process for preparing P-nitro benzoic acid by bionically catalystically oxidizing P-nitro toluene with oxygen |
| CN102212046A (en) * | 2011-04-19 | 2011-10-12 | 天津理工大学 | Catalytic system for synthesizing 5-hydroxymethylfurfural by dehydration of sugar or polysaccharide |
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2015
- 2015-05-20 CN CN201510260221.7A patent/CN106279076B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249307A (en) * | 1999-08-19 | 2000-04-05 | 北京工业大学 | Metallic phthalocyanine carboxylic acid derivatives and its preparing process and application |
| CN1944395A (en) * | 2006-10-27 | 2007-04-11 | 北京工业大学 | Process for preparing P-nitro benzoic acid by bionically catalystically oxidizing P-nitro toluene with oxygen |
| CN102212046A (en) * | 2011-04-19 | 2011-10-12 | 天津理工大学 | Catalytic system for synthesizing 5-hydroxymethylfurfural by dehydration of sugar or polysaccharide |
Non-Patent Citations (1)
| Title |
|---|
| Elucidating the role of cobalt phthalocyanine in the dehydration of carbohydrates in ionic liquids;Kumar Karitkey Yadav et al.;《Journal of Molecular Catalysis A: Chemical》;20140718;第394卷;第170-176页 * |
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