CN109836403A - The method for converting 5 hydroxymethyl furfural for biomass saccharide compound as catalyst using sulfomethylated lignin acidic group-aldehyde type resin - Google Patents
The method for converting 5 hydroxymethyl furfural for biomass saccharide compound as catalyst using sulfomethylated lignin acidic group-aldehyde type resin Download PDFInfo
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Abstract
The present invention relates to one kind using the biomass such as fructose, glucose carbohydrate as raw material, has fine chemicals -5 hydroxymethyl furfural method of high added value by its dehydration selectivity synthesis.This method uses sulfomethylated lignin acidic group-aldehyde type resin for catalyst, is capable of the acquisition 5 hydroxymethyl furfural of high yield under mild reaction conditions, and activity is apparently higher than currently used commercialization acidic resins.Secondly, primary raw material used in sulfomethylated lignin acidic group-aldehyde type resin catalyst preparation process is cheap and easy to get in this method, there can be reproducibility obtained by the byproduct in paper industry.In addition, the catalyst has good stability, and it is reusable, it is environmental-friendly, there is apparent advantage in futurity industry application.
Description
Technical field
The present invention relates to one kind to convert biomass saccharide compound to using sulfomethylated lignin acidic group-aldehyde type resin as catalyst
The method of 5 hydroxymethyl furfural.
Background technique
The energy needed for the world and the Organic Chemicals overwhelming majority derive from petroleum, coal and natural gas at present.These are changed
Stone class resource is that the development of society and economic prosperity have made huge contribution.But with non-renewable fossil energy
It peters out and the purpose in order to realize human kind sustainable development, the biomass resource based on plant will be future source of energy
Ideal chose.Wherein lignocellulosic is the main component of agriculture and forestry organic waste material, is biomass resource the most rich and easy to get.With
Lignocellulosic is raw material, is equalled a series of small molecule that its depolymerization generates high reaction activities by chemistry or biochemical method
Platform compound.Then from these platform chemicals, synthesize or be converted to other chemicals with can be convenient, and 5- methylol
Furfural is exactly such a platform chemicals.5 hydroxymethyl furfural (HMF) be across carbohydrate chemistry and petrochemistry it
Between a kind of important substance.Its potential commercial value can even match in excellence or beauty with terephthalic acid (TPA).
HMF can synthesize the high molecular material with the characteristics such as optical activity, biodegradable, for closing as monomer
At fiber, rubber and foundary industry.HMF can form 2,5- furans diacid through peroxidating.2,5- furans diacid is a kind of property
Stable furan derivatives can be used to prepare drug, insecticide, pesticide, fungicide and perfume etc..2,5- furans diacid may be used also
The reaction such as halogenated, esterification, amidation occurs, one of them most important conversion is exactly to generate polyamide.
The synthesis of HMF be by hexose and polysaccharide, obtained by acid-catalyzed dehydration, initially with liquid such as inorganic acids
Body acid is catalyst.In recent years, with the enhancing of people's environmental protection and awareness of saving energy, some strong inorganic proton acid catalysts are due to corruption
Lose equipment, it is difficult to separate, reclaiming complex process and pollution environment the disadvantages of and gradually taken by various solid acid catalysts
Generation.This is because solid acid catalyst have many advantages, such as to can be easily separated, can Hui Zaisheng and no pollution to the environment again, it is considered to be
A kind of " green " catalyst.It wherein, is to represent solid acid catalyst to show to carbohydrate with the commercialized resin such as Amberlyst
Compound dehydration synthesis HMF reacts reactivity and stability with higher, however these commercialized resins are with ethylene, benzene
The product that the petro chemical industries such as ethylene obtain is raw material, therefore is non-renewable.From the angle of long term growth and practical application
Degree, exploitation has more high activity and reproducible novel solid acid catalyst has great importance.
Lignosulfonates (such as sodium lignin sulfonate, calcium lignosulfonate) are that current slurrying and paper industry one kind are important
By-product be mainly used for high molecular material, cement water reducing agent, Surfactants Used for Oil field, dispersing agent, flocculant, inhibition resistance
Dirty agent, agricultural chemicals, industry adhesive etc. have vast potential for future development.We have found that sodium lignin sulfonate in this patent
Derivative acidic resins can be used as solid acid and be dehydrated the reaction for generating 5 hydroxymethyl furfural for biomass sugar, and in these reactions
In be demonstrated by well activity and stability.
Summary of the invention
The purpose of the present invention is to provide one kind using sulfomethylated lignin acidic group-aldehyde type resin as catalyst by biomass carbohydrate
The method that compound is converted into 5 hydroxymethyl furfural.
To achieve the above object, the technical solution adopted by the present invention are as follows:
Sulfomethylated lignin acidic group-aldehyde type resin catalyst the preparation method is as follows: first that sodium lignin sulfonate is soluble in water,
Controlling its mass concentration is 10~40%；Then aldehyde, aldehyde and sodium lignin sulfonate are added dropwise into lignin sulfonic acid sodium solution
Molar ratio be 0.1~10:1, after mixing by the two, be added dropwise into the mixture mass concentration be 37% hydrochloric acid it is molten
Liquid, controlling hydrogen ion concentration in final mixture is 0.1~5mol/L, and the reaction temperature of condensation reaction is 50~120 DEG C, reaction
Time is 1~12 hour.Gained condensation product after the solid abrasive that suction filtration obtains, in the hydrochloric acid of 0.1~5mol/L from
Son exchange 1~4 hour, after filtration washing 60~120 DEG C dry 4~12 hours to get arriving sulfomethylated lignin acidic group-aldehyde type resin
Catalyst；
5 hydroxymethyl furfural the preparation method is as follows: biomass sugar dehydration prepares 5 hydroxymethyl furfural in tank reactor
It carries out, it is anti-under the action of sulfomethylated lignin acidic group-aldehyde type resin catalyst after biomass saccharide compound is mixed with solvent
5 hydroxymethyl furfural should be generated.
In the preparation of sulfomethylated lignin acidic group-aldehyde type resin, the aldehyde of use are as follows: formaldehyde, acetaldehyde, butyraldehyde, furfural, glucose,
One or more of xylose.
In the preparation of sulfomethylated lignin acidic group-aldehyde type resin catalyst, the molar ratio of aldehyde and sodium lignin sulfonate is 0.1~
10:1.
Biomass saccharide compound are as follows: one or more of fructose, glucose, sucrose, synanthrin, cellulose mix
Close object.
Solvent are as follows: dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofurfuryl alcohol, water, tetrahydrofuran, in methylene chloride
It is one or more kinds of.
The mass ratio of biomass sugar and catalyst is 2~200:1, and reaction temperature is 50~160 DEG C, the reaction time 0.25
~9 hours.
The mass ratio of biomass sugar and catalyst is preferably 5~20:1, and reaction temperature is preferably 110~150 DEG C, reaction
Time is preferably 2~5 hours.
Sulfomethylated lignin acidic group-aldehyde type resin catalyst was once used for hydroxyalkylation, alkyl between 2- methylfuran and aldehydes
Change in (HAA) reaction (see document GreenChem., 2015,17,3644-3652), but this reaction mechanism is aldehyde and aromatic radical
The electrophilic substitution reaction of object is closed, and we are applied in itself sugared isomery dehydration, both reaction mechanisms have obviously
Difference.And above-mentioned HAA reaction is reacted under solvent-free conditions, and it is molten that we, which apply in sugared isomery dehydration,
It is reacted in agent, and different solvent effects is very different.(concrete outcome is shown in embodiment 122-138) we also by other
Acid is applied in sugared isomery dehydration as a comparison, it is found that some acid cannot be catalyzed such dehydration, only certain specific
Structure acid could be catalyzed, (concrete outcome is shown in embodiment 184-197) the present invention has the advantage that
Sulfomethylated lignin acidic group-aldehyde type resin catalyst is successfully applied to biomass sugar dehydration preparation 5- hydroxyl first by the present invention
Base furfural, sulfomethylated lignin acidic group-aldehyde type resin catalyst use aldehyde and sodium lignin sulfonate for raw material, after mixing by the two
Phenols functional group and aldehyde in acid catalysis sodium lignin sulfonate is added phenol formaldehyde condensation reaction occurs, to obtain a kind of water that is insoluble in
Then high molecular polymer exchanges to obtain solid acid catalyst through acid ion.The method of the present invention uses sulfomethylated lignin acidic group-aldehyde type
Resin is capable of the acquisition 5 hydroxymethyl furfural of high yield under mild reaction conditions, in catalysis biomass sugar as catalyst
Dehydration shows activity more higher than the acidic resins of traditional commerce change during preparing 5 hydroxymethyl furfural.With other solids
Acid is compared, due to preparing this sulfomethylated lignin acidic group-aldehyde type resin catalyst primary raw material in slurrying and paper industry
By-product, it is cheap and easy to get, independent of petroleum chemicals, therefore there is reproducibility.In addition, the catalyst has well surely
It is qualitative, it may be reused, it is environmental-friendly, there is good industrial applications prospect.
Detailed description of the invention
Fig. 1 is sulfomethylated lignin acidic group-aldehyde type resin catalyst structure chart in embodiment 1-52.
Fig. 2 is sulfomethylated lignin acidic group-aldehyde type resin catalyst FT-IR figure in embodiment 1-52.
Specific embodiment
The present invention will be illustrated with specific embodiment below, but protection scope of the present invention is not limited to these
Example.
Embodiment
1. the preparation of catalyst:
The preparation of aldehyde-sodium lignin sulfonate preparation solid acid catalyst under the conditions of differential responses.
First that sodium lignin sulfonate is soluble in water, controlling its mass concentration is 10~40%；Then to lignin sulfonic acid
It is added dropwise aldehyde in sodium solution, the molar ratio of aldehyde and sodium lignin sulfonate is 0.1~10:1, after mixing by the two, to this
It is 37% hydrochloric acid solution that mass concentration is added dropwise in mixture, and controlling hydrogen ion concentration in final mixture is 0.1~5mol/
L, the reaction temperature of condensation reaction are 50~120 DEG C, and the reaction time is 1~12 hour, and gained condensation product is obtained by suction filtration
Solid abrasive after, exchanged 1~4 hour in the hydrochloric acid intermediate ion of 0.1~5mol/L, at 60~120 DEG C dry 4 after filtration washing
Obtain lignin sulfonic acid base-aldehyde type resin catalyst within~12 hours.
Under the conditions of differential responses in the active testing of synthesized catalyst, using fructose dehydration as model reaction.Dehydration is anti-
It should be carried out in the round-bottomed flask equipped with condensation reflux unit.0.1g catalyst, 1g fructose are added into the round-bottomed flask of 20mL,
It is stirred 1.5 hours under 80 degree of water-baths.Quantitative analysis is carried out to reaction product by high performance liquid chromatography (HPLC).See embodiment
1-59 (is shown in Table 1-8)
1) influence of the catalyst of different lignin sulfonic acid na concn preparations to fructose dehydration, is shown in Table 1.
Influence of the catalyst of the different lignin sulfonic acid na concn preparations of table 1. to fructose dehydration
The condition in catalyst process is prepared in table 1 are as follows: the amount ratio of formaldehyde and sodium lignin sulfonate is 15 mmol/g,
The hydrogen ion concentration kept after mixing is 2mol/L, and the temperature of reaction is 90 DEG C, reaction time 6h, hydrogen when final ion exchanges
Ion concentration is 2mol/L, and ion-exchange time is that 1 hour last washing drying temperature is 80 DEG C, and drying time is 4 hours.
As can be seen from Table 1 with the raising of lignin sulfonic acid na concn, the activity of the catalyst of preparation is also gradually mentioned
Height, this may be to be conducive to the raising of the degree of cross linking due to improving concentration, and then generate more active groups.
2) influence of the catalyst of the mass ratio preparation of different formaldehyde and sodium lignin sulfonate to fructose dehydration, is shown in Table
2。
Shadow of the catalyst of the mass ratio preparation of the different formaldehyde of table 2. and sodium lignin sulfonate to fructose dehydration
It rings
The condition in catalyst process is prepared in table 2 are as follows: the concentration of sodium lignin sulfonate is 35%, the hydrogen kept after mixing
Ion concentration is 2mol/L, and the temperature of reaction is 90 DEG C, reaction time 6h, and hydrogen ion concentration is when final ion exchanges
2mol/L, ion-exchange time are that 2 hours last washing drying temperatures are 80 DEG C, and drying time is 6 hours.
From table 2 it can be seen that the degree of cross linking increases, so that the sulphur on unit mass catalyst with the increase of formaldehyde dosage
Acid group quantity increases, to improve its catalytic activity.
3) influence of the concentration of different catalyzing and condensing reaction acid used to synthesized catalyst activity, is shown in Table 3.
Influence of the concentration of 3. catalyzing and condensing of table reaction acid used to synthesized catalyst activity
The condition in catalyst process is prepared in table 3 are as follows: the concentration of sodium lignin sulfonate is 35%, formaldehyde and sulfomethylated lignin
The amount ratio of sour sodium is 15mmol/g, and the temperature of reaction is 90 DEG C, reaction time 6h, and hydrogen ion is dense when final ion exchanges
Degree is 2mol/L, and ion-exchange time is that 3 hours last washing drying temperatures are 80 DEG C, and drying time is 8 hours.
From table 3 it can be seen that the degree of cross linking increases, so that on unit mass catalyst with the increase of acid concentration used
Sulfonate radical quantity increases, to improve its catalytic activity.
4) influence of the different setting-up points to synthesized catalyst activity, is shown in Table 4.
Influence of 4. setting-up point of table to synthesized catalyst activity
The condition in catalyst process is prepared in table 3 are as follows: the concentration of sodium lignin sulfonate is 35%, formaldehyde and sulfomethylated lignin
The amount ratio of sour sodium is 15mmol/g, and the hydrogen ion concentration kept after mixing is 2 mol/L, reaction time 6h, final ion
Hydrogen ion concentration is 2mol/L when exchange, and ion-exchange time is that 4 hours last washing drying temperatures are 80 DEG C, and drying time is
12 hours.
From table 4, it can be seen that the temperature with condensation reaction increases, the degree of cross linking increases, so that on unit mass catalyst
Sulfonate radical quantity increase, to improve its catalytic activity, but after further increasing temperature, the degree of cross linking reache a certain level after just
It is not further added by, so that activity remains unchanged.
5) influence of the different condensation reaction times to synthesized catalyst activity, is shown in Table 5.
Influence of 5. condensation reaction time of table to synthesized catalyst activity
The condition in catalyst process is prepared in table 5 are as follows: the concentration of sodium lignin sulfonate is 35%, formaldehyde and sulfomethylated lignin
The amount ratio of sour sodium be 15mmol/g, the hydrogen ion concentration kept after mixing be 2 mol/L, reaction temperature be 90 DEG C, finally from
Hydrogen ion concentration is 2mol/L when son exchange, and finally washing drying temperature is 80 DEG C.
As can be seen from Table 5, as condensation reaction time increases, the degree of cross linking increases, but hardly changes after 6 hours,
Show that condensation reaction is complete, the degree of cross linking is not just further added by after reaching a certain level, so that activity remains unchanged.
6) influence of the solution concentration of different ions exchange to synthesized catalyst activity, is shown in Table 6.
Table 6. is used for influence of the solution concentration of ion exchange to synthesized catalyst activity
The condition in catalyst process is prepared in table 6 are as follows: the concentration of sodium lignin sulfonate is 35%, formaldehyde and sulfomethylated lignin
The amount ratio of sour sodium is 15mmol/g, and the hydrogen ion concentration kept after mixing is 2 mol/L, and reaction temperature is 90 DEG C, when reaction
Between be 6h, finally wash drying temperature be 80 DEG C.
As can be seen from Table 6, with the increase of ion exchanged soln hydrogen ion concentration, proton number that catalyst exchanges
Amount increases, and catalyst activity increases obviously, and after hydrogen ion concentration is more than 2mol/L, catalyst activity is not further added by, and is shown
Sodium ion under the conditions of this on catalyst is all exchanged for hydrogen ion.
7) influence of the different washing drying temperatures to synthesized catalyst activity, is shown in Table 7.
Finally influence of the washing drying temperature to synthesized catalyst activity of table 7
The condition in catalyst process is prepared in table 7 are as follows: the concentration of sodium lignin sulfonate is 35%, formaldehyde and sulfomethylated lignin
The amount ratio of sour sodium is 15mmol/g, and the hydrogen ion concentration kept after mixing is 2 mol/L, and reaction temperature is 90 DEG C, when reaction
Between be 6h, hydrionic concentration keeps 2mol/L in ion exchange.
Drying temperature does not influence synthesized catalyst activity substantially as can be seen from Table 7.
8) influence of the different aldehyde to synthesized catalytic activity, is shown in Table 8.
Influence of the different aldehyde of table 8. to synthesized catalytic activity
The condition in catalyst process is prepared in table 8 are as follows: the concentration of sodium lignin sulfonate is 35%, aldehyde and lignin sulfonic acid
The amount ratio of sodium is 15mmol/g, and the hydrogen ion concentration kept after mixing is 2mol/L, and reaction temperature is 90 DEG C, the reaction time
For 6h, hydrionic concentration keeps 2mol/L in ion exchange, and drying temperature is 80 DEG C.
Different aldehyde and the macromolecule resin of sodium lignin sulfonate preparation are for catalysis fructose dehydration as can be seen from Table 8
Reaction is influential, wherein the active highest of the resin by formaldehyde preparation.
2. prepared catalyst, which is applied to biomass sugar dehydration, prepares 5 hydroxymethyl furfural.
5 hydroxymethyl furfural is prepared under the conditions of differential responses.
Dehydration carries out in the round-bottomed flask equipped with condensation reflux unit, and biology is added into the round-bottomed flask of 20mL
Matter saccharide compound and solvent, after mixing under the effect of the catalyst, reaction temperature are 50~160 DEG C, the reaction time 0.25
~9 hours, the mass ratio of biomass sugar and catalyst was 2~200:1.；The mass ratio of biomass sugar and catalyst is preferably 5
~20:1, reaction temperature are preferably 110~150 DEG C, and the reaction time is preferably 2~5 hours.See that embodiment 60-183 (is shown in Table 9-
16)。
1) differential responses temperature prepares the influence of 5 hydroxymethyl furfural to fructose dehydration, the results are shown in Table 9.
9. reaction temperature of table prepares the influence of 5 hydroxymethyl furfural to fructose dehydration
The reaction condition that fructose is dehydrated in table 9 are as follows: 1g fructose, catalyst prepared by 0.1g embodiment 6,7g dimethyl are sub-
Mock (DMSO), 1.5h.
As can be seen from Table 9 with the raising of reaction temperature, the activity of fructose dehydration is gradually increased, corresponding 5- methylol
The yield of furfural is also gradually increased, and after temperature increases to 120 degree, yield is increased no longer obvious.
2) the differential responses time prepares the influence of 5 hydroxymethyl furfural to fructose dehydration, the results are shown in Table 10.
10. reaction time of table prepares the influence of 5 hydroxymethyl furfural to fructose dehydration
The reaction condition that fructose is dehydrated in table 10 are as follows: 1g fructose, catalyst prepared by 0.1g embodiment 13,7g dimethyl are sub-
It mocks (DMSO), 80 DEG C.
As can be seen from Table 10 with the increase in reaction time, fructose converting rate, 5 hydroxymethyl furfural yield all increase,
But after the reaction time to 4 hours, the conversion ratio of fructose reaches highest, but the yield of fructose just no longer increases after 1.8 hours,
And it is being gradually reduced after 7 hours, is showing that 5 hydroxymethyl furfural is unstable at this temperature, is easy to happen side reaction.
3) different catalysts dosage prepares the influence of 5 hydroxymethyl furfural to fructose dehydration, the results are shown in Table 11.
11. catalyst amount of table prepares the influence of 5 hydroxymethyl furfural to fructose dehydration
The reaction condition that fructose is dehydrated in table 11 are as follows: 1g fructose, 7g dimethyl Asia are mocked (DMSO), and 80 DEG C, 1.5h, catalysis
Agent is catalyst prepared by embodiment 16.
As can be seen from Table 11, catalyst amount has an impact for its catalytic activity, with the increase of catalyst amount, fruit
The conversion ratio of sugar, the yield of 5 hydroxymethyl furfural are gradually increased.
4) different solvents prepare the influence of 5 hydroxymethyl furfural to fructose dehydration, the results are shown in Table 12.
12. different solvents of table prepare the influence of 5 hydroxymethyl furfural to fructose dehydration
The reaction condition of 12 fructose of table dehydration are as follows: 1g fructose, 7g solvent, 80 DEG C, 1.5h, prepared by 0.1g embodiment 24
Catalyst
As can be seen from Table 12, these solvents, which prepare 5 hydroxymethyl furfural to fructose dehydration, effect, but dimethyl is sub-
The selective highest mocked, therefore use dimethyl Asia to mock as solvent in this reaction and be more advantageous to reaction.
5) 13 be the results are shown in Table by what different biomass sugars prepared 5 hydroxymethyl furfural.
The different biomass sugars of table 13. prepare 5 hydroxymethyl furfural
The reaction condition of 13 biomass sugar of table dehydration are as follows: 1g biomass sugar, 7g dimethyl sulfoxide, 120 DEG C, 1.5h, 0.1g
Catalyst prepared by embodiment 33.
As can be seen from Table 13, the sugar with fructose based structures can efficiently generate 5 hydroxymethyl furfural, and glucose
The sugar of base because isomerization generating the active lower of 5 hydroxymethyl furfural.
6) using fructose as raw material, the stability of catalyst is investigated, the results are shown in Table 14.
14. catalyst stability of table is investigated
The reaction condition of 14 biomass sugar of table dehydration are as follows: 1g fructose, 7g dimethyl sulfoxide, 120 DEG C, 1.5h, 0.1g are implemented
Catalyst prepared by example 42.
As can be seen from Table 14, with this condition, the catalysis fructose that this catalyst can be stable generates 5- methylol chaff
Aldehyde, using still maintaining good activity after 13 times.
7) using synanthrin as raw material, differential responses temperature prepares the influence of 5 hydroxymethyl furfural to synanthrin dehydration, as a result sees
Table 15.
15. reaction temperature of table prepares the influence of 5 hydroxymethyl furfural to synanthrin dehydration
The reaction condition of 15 biomass sugar of table dehydration are as follows: 1g synanthrin, 7g dimethyl sulfoxide, 1.5h, 0.1 g embodiment 48 system
Standby catalyst.
As can be seen from Table 15, for compared to fructose, under the identical time, synanthrin needs higher temperature to be just able to achieve
Conversion completely, this is because synanthrin is the structure of polyfructosan, needs first to be hydrolyzed to fructose, then proceedes to dehydration and generates 5- hydroxyl
Methyl furfural.
8) using synanthrin as raw material, the differential responses time prepares the influence of 5 hydroxymethyl furfural to synanthrin dehydration, as a result sees
Table 16.
Influence of 16. reaction time of table to 5 hydroxymethyl furfural is prepared to synanthrin dehydration
The reaction condition of 16 biomass sugar of table dehydration are as follows: 1g synanthrin, 7g dimethyl sulfoxide, 120 DEG C, 0.1g embodiment 6 is made
Standby catalyst.
When as can be seen from Table 16 using synanthrin as raw material, at 120 DEG C, when reacted between more than 4h after, synanthrin turns completely
Change.And 5 hydroxymethyl furfural reaches highest after 6h.
9) model catalyst of different structure prepares the influence of 5 hydroxymethyl furfural to fructose dehydration, the results are shown in Table 17.
The model catalyst of 17. different structure of table prepares the influence of 5 hydroxymethyl furfural to fructose dehydration
The reaction condition of 17 biomass sugar of table dehydration are as follows: 1g fructose, 7g dimethyl sulfoxide, 80 DEG C, 0.28mmol model is urged
Agent.
As can be seen from Table 17, the type calculated in different model catalysts is dehydrated preparation 5- methylol chaff to fructose
The activity of aldehyde be it is different, from the point of view of Acidity, strong acid is conducive to this reaction, and in addition to acid strength, hydroxyl, carboxyl is deposited
Whether and there are positions all to have a great impact to its activity.
Claims (5)
1. one kind converts 5- methylol chaff for biomass saccharide compound using sulfomethylated lignin acidic group-aldehyde type resin as catalyst
The method of aldehyde, it is characterised in that:
Sulfomethylated lignin acidic group-aldehyde type resin catalyst is the preparation method is as follows: use aldehyde and sodium lignin sulfonate for raw material, by two
Person phenols functional group and aldehyde in acid catalysis sodium lignin sulfonate is added after mixing, phenol formaldehyde condensation reaction occurs, and obtains a kind of difficulty
It is dissolved in the high molecular polymer of water, then exchanges to obtain solid acid catalyst through acid ion；
5 hydroxymethyl furfural the preparation method is as follows: biomass sugar dehydration prepare 5 hydroxymethyl furfural in tank reactor into
Row reacts under the action of sulfomethylated lignin acidic group-aldehyde type resin catalyst after mixing biomass saccharide compound with solvent
Generate 5 hydroxymethyl furfural.
2. it is described in accordance with the claim 1 using sulfomethylated lignin acidic group-aldehyde type resin as catalyst by biomass saccharide compound
The method for being converted into 5 hydroxymethyl furfural, it is characterised in that:
In the sulfomethylated lignin acidic group-aldehyde type resin catalyst preparation method, the aldehyde used is formaldehyde, acetaldehyde, butyraldehyde, chaff
One or more of aldehyde, glucose or xylose；
The molar ratio of the aldehyde and sodium lignin sulfonate is 0.1~10:1.
3. it is according to claim 1 or 2 using sulfomethylated lignin acidic group-aldehyde type resin as catalyst by biomass carbohydrate chemical combination
The method that object is converted into 5 hydroxymethyl furfural, it is characterised in that:
The sulfomethylated lignin acidic group-aldehyde type resin catalyst the preparation method is as follows: first that sodium lignin sulfonate is soluble in water,
Controlling its mass concentration is 10~40%；Then aldehyde is added dropwise into lignin sulfonic acid sodium solution, after mixing by the two,
Be added dropwise into mixture mass concentration be 37% hydrochloric acid solution, control final mixture in hydrogen ion concentration be 0.1~
5mol/L, reaction temperature are 50~120 DEG C, and the reaction time is 1~12 hour, obtain condensation product, and gained condensation product passes through
After filtering obtained solid abrasive, exchanged 1~4 hour in the hydrochloric acid intermediate ion of 0.1~5mol/L, after filtration washing 60~
120 DEG C obtain lignin sulfonic acid base-aldehyde type resin catalyst in drying 4~12 hours.
4. it is described in accordance with the claim 1 using sulfomethylated lignin acidic group-aldehyde type resin as catalyst by biomass saccharide compound
The method for being converted into 5 hydroxymethyl furfural, it is characterised in that:
In the preparation method of the 5 hydroxymethyl furfural, biomass saccharide compound is fructose, glucose, sucrose, synanthrin or fibre
Tie up one or more of element；
Solvent is one of dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofurfuryl alcohol, water, tetrahydrofuran or methylene chloride
Or it is two or more.
5. according to method described in claim 1 or 4, it is characterised in that:
The mass ratio of biomass sugar and catalyst is 2~200:1, preferably 5~20:1；
Reaction temperature is 50~160 DEG C, preferably 110~150 DEG C；
Reaction time is 0.25~9 hour, preferably 2~5 hours.
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| CN113559930A (en) * | 2021-07-26 | 2021-10-29 | 南京林业大学 | Preparation method and application of solid catalyst taking sodium lignosulfonate as carrier |
| CN115350726A (en) * | 2022-09-20 | 2022-11-18 | 石河子大学 | Catalyst for synthesizing fatty acid triglyceride, preparation method of catalyst, fatty acid triglyceride, preparation method of fatty acid triglyceride and application of fatty acid triglyceride |
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| CN101531479A (en) * | 2009-04-03 | 2009-09-16 | 南京瑞迪高新技术公司 | Method for preparing low cost aliphatic high efficiency water reducing agent |
| US20140121389A1 (en) * | 2011-05-16 | 2014-05-01 | Université Claude Bernard Lyon 1 | Method for Producing 5-Hydroxymethylfurfural |
| CN103842349A (en) * | 2011-09-29 | 2014-06-04 | 韩国生产技术研究院 | Method for producing 5- hydroxymethyl-2- furfural or alkyl ether derivatives thereof using an ion exchange resin in the presence of an organic solvent |
| CN102399201A (en) * | 2011-11-24 | 2012-04-04 | 中国科学院西双版纳热带植物园 | Method for preparing 5-hydroxymethylfurfural by solid acid catalysis |
| WO2014058859A2 (en) * | 2012-10-11 | 2014-04-17 | Wisconsin Alumni Research Foundation | Method to convert monosaccharides to 5-(hydroxymethyl) furfural (hmf) using biomass-derived solvents |
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| CN113559930A (en) * | 2021-07-26 | 2021-10-29 | 南京林业大学 | Preparation method and application of solid catalyst taking sodium lignosulfonate as carrier |
| CN113559930B (en) * | 2021-07-26 | 2023-05-23 | 南京林业大学 | Preparation method and application of solid catalyst taking sodium lignin sulfonate as carrier |
| CN115350726A (en) * | 2022-09-20 | 2022-11-18 | 石河子大学 | Catalyst for synthesizing fatty acid triglyceride, preparation method of catalyst, fatty acid triglyceride, preparation method of fatty acid triglyceride and application of fatty acid triglyceride |
| CN115350726B (en) * | 2022-09-20 | 2024-05-28 | 石河子大学 | Catalyst for synthesizing triglyceride, preparation method thereof, triglyceride and preparation method and application thereof |
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