CN109836403B - Method for converting biomass carbohydrate into 5-hydroxymethylfurfural by using lignin sulfonic acid-aldehyde resin as catalyst - Google Patents

Abstract

The invention relates to a method for selectively synthesizing a fine chemical product, namely 5-hydroxymethylfurfural, with high added value by taking biomass saccharides such as fructose, glucose and the like as raw materials through dehydration reaction. The method adopts lignin sulfonic acid group-aldehyde type resin as a catalyst, can obtain the 5-hydroxymethylfurfural with high yield under mild reaction conditions, and has activity obviously higher than that of the current commonly used commercial acid resin. In addition, in the method, main raw materials used in the preparation process of the lignin sulfonic acid group-aldehyde type resin catalyst are cheap and easily available, can be obtained from byproducts in the paper industry, and have reproducibility. In addition, the catalyst has good stability, can be repeatedly used, is environment-friendly, and has obvious advantages in future industrial application.

Description

Conversion of biomass carbohydrates to lignosulfonic acid-aldehyde resin as catalyst The method for being transformed into 5-hydroxymethylfurfural

technical field

The invention relates to a method for converting biomass sugar compounds into 5-hydroxymethyl furfural by using lignosulfonic acid group-aldehyde resin as a catalyst.

Background technique

At present, most of the energy and organic chemical raw materials needed by the world come from petroleum, coal and natural gas. These fossil resources have made great contributions to social development and economic prosperity. However, with the gradual exhaustion of non-renewable fossil energy and in order to achieve the purpose of sustainable human development, plant-based biomass resources will be an ideal choice for future energy. Among them, lignocellulose is the main component of agricultural and forestry waste, and it is the most abundant and readily available biomass resource. Using lignocellulose as raw material, it can be depolymerized by chemical or biochemical methods to generate a series of highly reactive small molecule platform compounds. Then starting from these platform compounds, it can be easily synthesized or transformed into other chemicals, and 5-hydroxymethylfurfural is such a platform compound. 5-Hydroxymethylfurfural (HMF) is an important substance that bridges the gap between carbohydrate chemistry and petrochemistry. Its potential commercial value is even comparable to that of terephthalic acid.

As a monomer, HMF can synthesize polymer materials with optical activity, biodegradability and other properties, which are used in synthetic fibers, rubber and foundry industries. HMF can be oxidized to form 2,5-furandioic acid. 2,5-Furandioic acid is a stable furan derivative, which can be used to prepare medicines, insecticides, pesticides, fungicides and perfumes. 2,5-Furandioic acid can also undergo halogenation, esterification, amidation and other reactions, and one of the most important transformations is the formation of polyamides.

The synthesis of HMF starts from six-carbon sugars and polysaccharides, and is obtained through acid-catalyzed dehydration. Initially, liquid acids such as inorganic acids are used as catalysts. In recent years, with the enhancement of people's awareness of environmental protection and energy saving, some strong inorganic protonic acid catalysts have been gradually replaced by various solid acid catalysts due to the shortcomings of corrosion equipment, difficult separation, complex recycling and regeneration processes and environmental pollution. This is because the solid acid catalyst has the advantages of easy separation, recyclability, and no pollution to the environment, and is considered to be a "green" catalyst. Among them, solid acid catalysts represented by commercialized resins such as Amberlyst show high reactivity and stability for the dehydration of sugar compounds to synthesize HMF. However, these commercialized resins are obtained from petrochemical industries such as ethylene and styrene. The products are raw materials and are therefore non-renewable. From the perspective of long-term development and practical application, it is of great significance to develop new solid acid catalysts with higher activity and regeneration.

Lignin sulfonate (such as sodium lignosulfonate, calcium lignosulfonate) is an important by-product in pulp and paper industry. It is mainly used in polymer materials, concrete water reducers, oil field surfactants, Dispersants, flocculants, corrosion and scale inhibitors, agricultural chemicals, industrial adhesives, etc., have broad development prospects. In this patent, we found that the acid resin derived from sodium lignosulfonate can be used as a solid acid for the reaction of biomass sugar dehydration to 5-hydroxymethylfurfural, and has shown good activity and stability in these reactions.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a method for converting biomass sugar compounds into 5-hydroxymethylfurfural using lignosulfonic acid-aldehyde resin as a catalyst.

To achieve the above object, the technical scheme adopted in the present invention is:

The preparation method of the lignosulfonic acid group-aldehyde resin catalyst is as follows: first, dissolving sodium lignosulfonate in water, and controlling its mass concentration to be 10-40%; then adding aldehyde dropwise to the sodium lignosulfonate solution, The molar ratio of aldehyde and sodium lignosulfonate is 0.1～10:1. After mixing the two evenly, add 37% hydrochloric acid solution dropwise to the mixture, and control the hydrogen ion concentration in the final mixture to be 0.1～5mol /L, the reaction temperature of the condensation reaction is 50-120°C, and the reaction time is 1-12 hours. The obtained condensation product is ground after the solid obtained by suction filtration, ion-exchanged in 0.1-5 mol/L hydrochloric acid for 1-4 hours, filtered and washed, and dried at 60-120 DEG C for 4-12 hours to obtain the lignosulfonic acid group- Aldehyde resin catalyst;

The preparation method of 5-Hydroxymethylfurfural is as follows: the preparation of 5-Hydroxymethylfurfural by dehydration of biomass sugar is carried out in a kettle reactor, and the biomass sugar compound is mixed with a solvent and then mixed with a lignosulfonic acid group-aldehyde resin. The reaction generates 5-hydroxymethylfurfural under the action of the catalyst.

In the preparation of the lignosulfonic acid group-aldehyde resin, the aldehydes used are: one or more of formaldehyde, acetaldehyde, butyraldehyde, furfural, glucose, and xylose.

In the preparation of the lignosulfonic acid group-aldehyde resin catalyst, the molar ratio of the aldehyde to the sodium lignosulfonate is 0.1-10:1.

Biomass sugar compounds are: one or a mixture of two or more of fructose, glucose, sucrose, inulin, and cellulose.

The solvent is: one or more of dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofurfuryl alcohol, water, tetrahydrofuran, and dichloromethane.

The mass ratio of biomass sugar to catalyst is 2-200:1, the reaction temperature is 50-160 DEG C, and the reaction time is 0.25-9 hours.

The mass ratio of biomass sugar to catalyst is preferably 5-20:1, the reaction temperature is preferably 110-150°C, and the reaction time is preferably 2-5 hours.

Lignosulfonic acid group-aldehyde resin catalysts have been used in the hydroxyalkylation, alkylation (HAA) reaction between 2-methylfuran and aldehydes (see document GreenChem., 2015, 17, 3644-3652 ), but this reaction mechanism is the electrophilic substitution reaction of aldehyde and aromatic compound, and we apply it in the isomerization dehydration reaction of sugar itself, and the two reaction mechanisms are obviously different. And the above HAA reaction is carried out under solvent-free conditions, while our application in the sugar isomerization dehydration reaction is carried out in a solvent, and the effect of different solvents is very different. (See Examples 122-138 for the specific results) We also applied other acids in the sugar isomerization dehydration reaction as a comparison, and found that some acids could not catalyze this type of dehydration reaction, but only some acids with specific structures could catalyze, (see the specific results in Examples 184-197) The present invention has the following advantages:

In the present invention, the lignosulfonic acid group-aldehyde type resin catalyst is successfully applied to the dehydration of biomass sugar to prepare 5-hydroxymethyl furfural, the lignosulfonic acid group-aldehyde type resin catalyst adopts aldehyde and sodium lignosulfonate as raw materials, and the After the two are evenly mixed, an acid is added to catalyze the phenolic condensation reaction between the phenolic functional group and the aldehyde in the sodium lignosulfonate to obtain a water-insoluble polymer, and then a solid acid catalyst is obtained through acid ion exchange. The method of the invention adopts the lignosulfonic acid group-aldehyde resin as a catalyst, can obtain 5-hydroxymethyl furfural in high yield under mild reaction conditions, and catalyze the dehydration of biomass sugar to prepare 5-hydroxymethyl furfural. showed higher activity than conventional commercial acid resins. Compared with other solid acids, since the main raw material for the preparation of this lignosulfonic acid-aldehyde resin catalyst comes from by-products in the pulp and paper industry, it is cheap and easy to obtain, and does not depend on petrochemical products, so it is renewable. . In addition, the catalyst has good stability, can be reused, is environmentally friendly, and has good prospects for industrial application.

Description of drawings

FIG. 1 is a structural diagram of the lignosulfonic acid group-aldehyde type resin catalyst in Examples 1-52.

Fig. 2 is the FT-IR chart of the lignosulfonic acid group-aldehyde resin catalyst in Examples 1-52.

Detailed ways

The present invention will be described below with specific examples, but the protection scope of the present invention is not limited to these examples.

Example

1. Preparation of catalyst:

Preparation of solid acid catalysts prepared from aldehyde-sodium lignosulfonates under different reaction conditions.

First, the sodium lignosulfonate is dissolved in water, and its mass concentration is controlled to be 10-40%; then the aldehyde is added dropwise to the sodium lignosulfonate solution, and the molar ratio of the aldehyde to the sodium lignosulfonate is 0.1-10: 1. After the two are evenly mixed, dropwise adding a mass concentration of 37% hydrochloric acid solution to the mixture, controlling the hydrogen ion concentration in the final mixture to be 0.1～5mol/L, the reaction temperature of the condensation reaction is 50～120 ℃, the reaction The time is 1 to 12 hours, the obtained condensation product is ground after the solid obtained by suction filtration, ion-exchanged in 0.1 to 5 mol/L hydrochloric acid for 1 to 4 hours, filtered and washed, and dried at 60 to 120 ° C for 4 to 12 hours to obtain Lignosulfonic acid-aldehyde resin catalyst.

In the activity test of the synthesized catalysts under different reaction conditions, fructose dehydration was used as a model reaction. The dehydration reaction was carried out in a round bottom flask equipped with a condensing reflux device. 0.1 g of catalyst and 1 g of fructose were added to a 20 mL round-bottomed flask, and the mixture was stirred for 1.5 hours in an 80-degree water bath. The reaction products were quantitatively analyzed by high performance liquid chromatography (HPLC). See Examples 1-59 (see Tables 1-8)

1) The effect of catalysts prepared with different concentrations of sodium lignosulfonate on fructose dehydration reaction is shown in Table 1.

Table 1. Effects of catalysts prepared with different concentrations of sodium lignosulfonate on fructose dehydration

The conditions in the catalyst preparation process in Table 1 are: the dosage ratio of formaldehyde and sodium lignosulfonate is 15 mmol/g, the hydrogen ion concentration kept after mixing is 2 mol/L, the temperature of the reaction is 90 ℃, and the reaction time is 6h , During the final ion exchange, the hydrogen ion concentration is 2mol/L, the ion exchange time is 1 hour, the final washing and drying temperature is 80 ℃, and the drying time is 4 hours.

It can be seen from Table 1 that with the increase of the concentration of sodium lignosulfonate, the activity of the catalyst prepared by it also increases gradually, which may be because the increase of the concentration is conducive to the improvement of the degree of cross-linking, thereby generating more active groups.

2) The effect of catalysts prepared with different mass ratios of formaldehyde and sodium lignosulfonate on fructose dehydration reaction is shown in Table 2.

Table 2. Effect of catalysts prepared with different mass ratios of formaldehyde and sodium lignosulfonate on fructose dehydration reaction

ring

The conditions in the process of preparing the catalyst in Table 2 are: the concentration of sodium lignosulfonate is 35%, the hydrogen ion concentration maintained after mixing is 2mol/L, the temperature of the reaction is 90°C, the reaction time is 6h, and during the last ion exchange The hydrogen ion concentration was 2 mol/L, the ion exchange time was 2 hours, the final washing and drying temperature was 80°C, and the drying time was 6 hours.

As can be seen from Table 2, as the amount of formaldehyde increases, the degree of crosslinking increases, which increases the number of sulfonates on the catalyst per unit mass, thereby improving its catalytic activity.

3) The effect of the concentration of acid used in different catalytic condensation reactions on the activity of the synthesized catalysts is shown in Table 3.

Table 3. Effect of the concentration of acid used to catalyze the condensation reaction on the activity of the synthesized catalysts

The conditions in the preparation catalyst process in table 3 are: the concentration of sodium lignosulfonate is 35%, the consumption ratio of formaldehyde and sodium lignosulfonate is 15mmol/g, the temperature of reaction is 90 ℃, the reaction time is 6h, and finally During ion exchange, the hydrogen ion concentration was 2 mol/L, the ion exchange time was 3 hours, and the final washing and drying temperature was 80°C, and the drying time was 8 hours.

It can be seen from Table 3 that with the increase of the acid concentration used, the degree of crosslinking increases, so that the number of sulfonate groups per unit mass of the catalyst increases, thereby improving its catalytic activity.

4) The effect of different condensation reaction temperatures on the activity of the synthesized catalysts is shown in Table 4.

Table 4. Effect of condensation reaction temperature on the activity of synthesized catalysts

The condition in the preparation catalyst process in table 3 is: the concentration of sodium lignosulfonate is 35%, and the consumption ratio of formaldehyde and sodium lignosulfonate is 15mmol/g, and the hydrogen ion concentration kept after mixing is 2 mol/L, The reaction time was 6h, the hydrogen ion concentration was 2mol/L during the final ion exchange, the ion exchange time was 4 hours, the final washing and drying temperature was 80°C, and the drying time was 12 hours.

As can be seen from Table 4, as the temperature of the condensation reaction increases, the degree of cross-linking increases, which increases the number of sulfonates on the catalyst per unit mass, thereby improving its catalytic activity, but after further increasing the temperature, the degree of cross-linking reaches a certain level will not increase, so the activity remains unchanged.

5) The effect of different condensation reaction times on the activity of the synthesized catalysts is shown in Table 5.

Table 5. Effect of condensation reaction time on the activity of synthesized catalysts

The condition in the preparation catalyst process in table 5 is: the concentration of sodium lignosulfonate is 35%, and the consumption ratio of formaldehyde and sodium lignosulfonate is 15mmol/g, and the hydrogen ion concentration kept after mixing is 2 mol/L, The reaction temperature was 90℃, the hydrogen ion concentration was 2mol/L during the final ion exchange, and the final washing and drying temperature was 80℃.

As can be seen from Table 5, as the condensation reaction time increases, the degree of cross-linking increases, but it hardly changes after 6 hours, indicating that the condensation reaction has been completed, and the degree of cross-linking does not increase after reaching a certain level, so the activity remains constant.

6) The effect of different ion-exchange solution concentrations on the activity of the synthesized catalysts is shown in Table 6.

Table 6. Effect of solution concentration for ion exchange on the activity of the synthesized catalysts

The condition in the preparation catalyst process in table 6 is: the concentration of sodium lignosulfonate is 35%, and the consumption ratio of formaldehyde and sodium lignosulfonate is 15mmol/g, and the hydrogen ion concentration kept after mixing is 2 mol/L, The reaction temperature was 90 °C, the reaction time was 6 h, and the final washing and drying temperature was 80 °C.

It can be seen from Table 6 that with the increase of the hydrogen ion concentration of the ion exchange solution, the number of protons obtained by the catalyst exchange increases, and the catalyst activity increases significantly. When the hydrogen ion concentration exceeds 2 mol/L, the catalyst activity does not increase any more, indicating that in this The sodium ions on the catalyst have all been exchanged for hydrogen ions under the conditions.

7) The effects of different washing and drying temperatures on the activity of the synthesized catalysts are shown in Table 7.

Table 7 The effect of the final washing and drying temperature on the activity of the synthesized catalysts

The condition in the preparation catalyst process in table 7 is: the concentration of sodium lignosulfonate is 35%, and the consumption ratio of formaldehyde and sodium lignosulfonate is 15mmol/g, and the hydrogen ion concentration kept after mixing is 2 mol/L, The reaction temperature was 90℃, the reaction time was 6h, and the concentration of hydrogen ions in the ion exchange was kept at 2mol/L.

It can be seen from Table 7 that the drying temperature has little effect on the activity of the synthesized catalyst.

8) The effect of different aldehydes on the synthesized catalytic activity is shown in Table 8.

Table 8. Effects of different aldehydes on the synthesized catalytic activity

The condition in the preparation catalyst process in table 8 is: the concentration of sodium lignosulfonate is 35%, and the consumption ratio of aldehyde and sodium lignosulfonate is 15mmol/g, and the hydrogen ion concentration kept after mixing is 2mol/L, and the reaction The temperature was 90 °C, the reaction time was 6 h, the concentration of hydrogen ions in the ion exchange was maintained at 2 mol/L, and the drying temperature was 80 °C.

It can be seen from Table 8 that the polymer resins prepared by different aldehydes and sodium lignosulfonate have an impact on the reaction of catalyzing fructose dehydration, and the resin prepared from formaldehyde has the highest activity.

2. The prepared catalyst was applied to biomass sugar dehydration reaction to prepare 5-hydroxymethylfurfural.

5-Hydroxymethylfurfural was prepared under different reaction conditions.

The dehydration reaction was carried out in a round-bottomed flask equipped with a condensing reflux device. Biomass sugar compounds and a solvent were added to a 20-mL round-bottomed flask. After mixing, under the action of a catalyst, the reaction temperature was 50-160 °C, and the reaction time was For 0.25 to 9 hours, the mass ratio of biomass sugar to catalyst is 2 to 200:1. The mass ratio of biomass sugar and catalyst is preferably 5-20:1, the reaction temperature is preferably 110-150°C, and the reaction time is preferably 2-5 hours. See Examples 60-183 (see Tables 9-16).

1) The influence of different reaction temperatures on fructose dehydration to prepare 5-Hydroxymethylfurfural, the results are shown in Table 9.

Table 9. Effect of reaction temperature on the preparation of 5-Hydroxymethylfurfural by fructose dehydration

The reaction conditions of fructose dehydration in Table 9 are: 1 g of fructose, 0.1 g of the catalyst prepared in Example 6, 7 g of dimethyl sulfoxide (DMSO), 1.5 h.

It can be seen from Table 9 that with the increase of the reaction temperature, the activity of fructose dehydration gradually increased, and the corresponding yield of 5-hydroxymethylfurfural also gradually increased. When the temperature increased to 120 degrees, the increase in yield was no longer obvious. .

2) The effect of different reaction times on the preparation of 5-Hydroxymethylfurfural by fructose dehydration, the results are shown in Table 10.

Table 10. Effect of reaction time on the preparation of 5-Hydroxymethylfurfural by fructose dehydration

The reaction conditions of fructose dehydration in Table 10 are: 1 g of fructose, 0.1 g of the catalyst prepared in Example 13, 7 g of dimethyl sulfoxide (DMSO), 80°C.

It can be seen from Table 10 that with the increase of the reaction time, the fructose conversion rate and the yield of 5-hydroxymethylfurfural all increase, but after the reaction time reaches 4 hours, the conversion rate of fructose reaches the highest, but the yield of fructose is It no longer increased after 1.8 hours, and gradually decreased after 7 hours, indicating that 5-hydroxymethylfurfural was unstable at this temperature and was prone to side reactions.

3) The effect of different catalyst dosages on the preparation of 5-hydroxymethylfurfural from fructose dehydration, the results are shown in Table 11.

Table 11. The effect of catalyst dosage on the preparation of 5-Hydroxymethylfurfural by fructose dehydration

The reaction conditions of fructose dehydration in Table 11 are: 1 g of fructose, 7 g of dimethyl sulfoxide (DMSO), 80° C., 1.5 h, and the catalyst is the catalyst prepared in Example 16.

As can be seen from Table 11, the amount of catalyst has an impact on its catalytic activity. With the increase of the amount of catalyst, the conversion rate of fructose and the yield of 5-hydroxymethylfurfural gradually increase.

4) The effect of different solvents on the preparation of 5-hydroxymethylfurfural from fructose dehydration, the results are shown in Table 12.

Table 12. Effects of different solvents on the preparation of 5-hydroxymethylfurfural from fructose dehydration

The reaction conditions of table 12 fructose dehydration are: 1g fructose, 7g solvent, 80°C, 1.5h, 0.1g catalyst prepared in Example 24

As can be seen from Table 12, these solvents all have an effect on the dehydration of fructose to prepare 5-Hydroxymethylfurfural, but the selectivity of dimethyl sulfoxide is the highest, so in this reaction, using dimethyl sulfoxide as solvent is more conducive to reaction.

5) The results of preparing 5-hydroxymethylfurfural from different biomass sugars are shown in Table 13.

Table 13. Preparation of 5-Hydroxymethylfurfural with Different Biomass Sugars

Table 13 The reaction conditions for biomass sugar dehydration are: 1 g biomass sugar, 7 g dimethyl sulfoxide, 120° C., 1.5 h, and 0.1 g of the catalyst prepared in Example 33.

It can be seen from Table 13 that sugars with fructosyl structure can efficiently generate 5-hydroxymethylfurfural, while sugars with glucose-based structure have lower activity to generate 5-hydroxymethylfurfural due to isomerization.

6) Using fructose as a raw material, the stability of the catalyst was investigated, and the results are shown in Table 14.

Table 14. Catalyst Stability Investigation

Table 14 The reaction conditions of biomass sugar dehydration are: 1 g of fructose, 7 g of dimethyl sulfoxide, 120° C., 1.5 h, and 0.1 g of the catalyst prepared in Example 42.

As can be seen from Table 14, under this condition, this catalyst can stably catalyze fructose to generate 5-hydroxymethylfurfural, and still maintain good activity after 13 times of use.

7) Using inulin as a raw material, the effects of different reaction temperatures on the dehydration of inulin to prepare 5-hydroxymethylfurfural, the results are shown in Table 15.

Table 15. Effect of reaction temperature on the preparation of 5-hydroxymethylfurfural by dehydration of inulin

Table 15 The reaction conditions of biomass sugar dehydration are: 1 g of inulin, 7 g of dimethyl sulfoxide, 1.5 h, and 0.1 g of the catalyst prepared in Example 48.

As can be seen from Table 15, compared with fructose, under the same time, inulin requires a higher temperature to achieve complete conversion, this is because inulin is the structure of polyfructose, which needs to be hydrolyzed into fructose first, Then continue dehydration to generate 5-hydroxymethylfurfural.

8) Using inulin as a raw material, the effects of different reaction times on the dehydration of inulin to prepare 5-hydroxymethylfurfural, the results are shown in Table 16.

Table 16. Effect of reaction time on the preparation of 5-Hydroxymethylfurfural by dehydration of inulin

Table 16 The reaction conditions of biomass sugar dehydration are: 1 g of inulin, 7 g of dimethyl sulfoxide, 120° C., 0.1 g of the catalyst prepared in Example 6.

It can be seen from Table 16 that when inulin is used as the raw material, at 120° C., when the reaction time exceeds 4 h, the inulin is completely converted. And 5-hydroxymethylfurfural reached the highest after 6h.

9) The effect of model catalysts with different structures on the preparation of 5-hydroxymethylfurfural by fructose dehydration, the results are shown in Table 17.

Table 17. Effects of model catalysts with different structures on the dehydration of fructose to 5-hydroxymethylfurfural

Table 17 The reaction conditions for biomass sugar dehydration are: 1 g fructose, 7 g dimethyl sulfoxide, 80° C., 0.28 mmol model catalyst.

It can be seen from Table 17 that the activities of different model catalysts for the preparation of 5-hydroxymethylfurfural by fructose dehydration are different. From the perspective of acidity, strong acid is beneficial to this reaction. , the presence or absence and location of carboxyl groups have a great influence on its activity.

Claims (4)

1. a method that biomass saccharide is converted into 5-Hydroxymethylfurfural with lignosulfonic acid group-aldehyde type resin as catalyzer, it is characterized in that: The preparation method of the lignosulfonic acid group-aldehyde resin catalyst is as follows: using aldehyde and sodium lignosulfonate as raw materials, mixing the two evenly, and adding acid to catalyze the phenolic functional group in the sodium lignosulfonate and the aldehyde to undergo a phenolic condensation reaction , obtain a kind of high molecular polymer that is insoluble in water, and then obtain a solid acid catalyst through acid ion exchange; wherein, the molar ratio of the aldehyde to sodium lignosulfonate is 0.1~10:1; The specific preparation process of the catalyst is as follows: First, the sodium lignosulfonate is dissolved in water, and its mass concentration is controlled to be 10-40%; then the aldehyde is added dropwise to the sodium lignosulfonate solution, and after the two are mixed evenly, the mass concentration is added dropwise to the mixture. Be 37% hydrochloric acid solution, control the hydrogen ion concentration in the final mixture to be 0.1～5 mol/L, the reaction temperature is 50～120 ℃, and the reaction time is 1～12 hours, obtain the condensation product, the solid that the gained condensation product obtains through suction filtration After grinding, ion-exchange in 0.1-5 mol/L hydrochloric acid for 1-4 hours, filter and wash, and dry at 60-120°C for 4-12 hours to obtain a lignosulfonic acid-aldehyde resin catalyst; The preparation method of 5-Hydroxymethylfurfural is as follows: the preparation of 5-Hydroxymethylfurfural by dehydration of biomass sugar is carried out in a kettle reactor, and the biomass sugar compound is mixed with a solvent and then mixed with a lignosulfonic acid group-aldehyde resin. The reaction generates 5-hydroxymethylfurfural under the action of the catalyst; wherein, the mass ratio of the biomass carbohydrate compound to the catalyst is 2~200:1, the reaction temperature is 50~160°C, and the reaction time is 0.25~9 hours. 2. according to claim 1 with lignosulfonic acid group-aldehyde type resin as catalyzer, biomass carbohydrate is converted into the method for 5-hydroxymethyl furfural, it is characterized in that: In the preparation method of the lignosulfonic acid group-aldehyde resin catalyst, the aldehyde used is one or more of formaldehyde, acetaldehyde, butyraldehyde, furfural, glucose or xylose. 3. according to claim 1 with lignosulfonic acid group-aldehyde type resin as catalyzer, biomass carbohydrate is converted into the method for 5-hydroxymethyl furfural, it is characterized in that: In the preparation method of 5-hydroxymethylfurfural, the biomass carbohydrate compound is one or more of fructose, glucose, sucrose, inulin or cellulose; The solvent is one or more of dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofurfuryl alcohol, water, tetrahydrofuran or dichloromethane. 4. according to the described method of claim 1 or 3, it is characterized in that: The mass ratio of biomass carbohydrates to catalyst is 5~20:1; The reaction temperature is 110～150 ℃; The reaction time is 2 to 5 hours.

Images