WO2020164340A1

WO2020164340A1 - Method for purifying 5-hydroxymethylfurfural

Info

Publication number: WO2020164340A1
Application number: PCT/CN2020/070387
Authority: WO
Inventors: 陈茁
Original assignee: 陈茁
Priority date: 2019-02-15
Filing date: 2020-01-06
Publication date: 2020-08-20
Also published as: CN109651308A

Abstract

Provided is a method for purifying 5-hydroxymethylfurfural. In the invention, 5-hydroxymethylfurfural is obtained by pumping a solution containing 5-hydroxymethylfurfural into a membrane separation device for filtration, collecting the filtrate filtered through the membrane core, and then removing the solvent. The result indicates that the reaction solution containing 5-hydroxymethylfurfural can be purified well by means of the method, wherein same has a fast purification speed and a large processing capacity, and the resulting HMF has a high purity and less loss.

Description

A kind of purification method of 5-hydroxymethyl furfural

This application claims the priority of a Chinese patent application filed with the Chinese Patent Office on February 15, 2019, the application number is 201910118960.0, and the invention title is "a method for purifying 5-hydroxymethyl furfural", the entire content of which is incorporated by reference In this application.

Technical field

The invention relates to the field of organic chemistry, in particular to a purification method of 5-hydroxymethyl furfural.

Background technique

5-Hydroxymethylfurfural (hereinafter referred to as HMF) is one of the important platform compounds released by the U.S. Energy Administration. The highly reactive furan ring, hydroxyl and aldehyde groups contained in the molecule make HMF can be hydrogenated and esterified. , Halogenation, polymerization and hydrolysis, and other processes for further transformation, as a polymer material synthesis monomer, macrocyclic compound synthesis raw material and important intermediate raw materials for medicine and pesticides, it has important potential application value in various fields, but at the same time these applications High requirements are also placed on the purity of HMF. HMF is mainly derived from the dehydration and conversion of six carbon sugars, and its purity is not high due to the occurrence of side reactions, which affects subsequent applications. Therefore, the establishment of high-purity 5-HMF separation and purification technology has important economic and social value.

HMF can be prepared by dehydration of six carbon sugars, and the reaction process is as follows:

In this reaction, in addition to HMF in the dehydrated reaction system, the main impurities are humin, a macromolecular substance produced by the polymerization reaction between sugar or HMF, and also contains levulinic acid, formic acid, and HMF derivatives. For complete sugars, these impurities are difficult to completely separate through differences in solubility, polarity, boiling point, etc.

At present, the separation and purification methods of HMF mainly include extraction, activated carbon adsorption, recrystallization and column chromatography. When the extraction method is used, the extraction process is complicated and requires repeated extractions, and the yield and purity of HMF are low; while using activated carbon adsorption to effectively remove impurities, it will also cause a large amount of HMF loss. The recrystallization process using purified HMF requires the entire process to be operated at low temperature, which has high energy consumption and low efficiency. In the column chromatography method, after selecting the appropriate filler and mobile phase, HMF with higher purity can usually be obtained, but the separation speed is extremely slow and it is difficult to industrialize. Therefore, it is of great significance to develop a simple, gentle and rapid method for directly separating and purifying high-purity HMF from the reaction solution after sugar dehydration reaction to prepare HMF.

Summary of the invention

In view of this, the technical problem to be solved by the present invention is to provide a purification method of 5-hydroxymethyl furfural. The method provided by the present invention has a fast separation speed, and the obtained product has high purity and low HMF loss.

The present invention provides a purification method of 5-hydroxymethyl furfural, which includes:

The solution containing 5-hydroxymethyl furfural is pumped into the membrane separation device for filtration, the filtrate filtered through the membrane core is collected, and the solvent is removed to obtain 5-hydroxymethyl furfural.

Preferably, the membrane core in the membrane separation device is a polyamide membrane core, a polyimide membrane core, a polyurethane membrane core, a cellulose acetate membrane core, a sulfonated polysulfone membrane core, and a polyethersulfone membrane core. , Sulfonated polyethersulfone membrane core, polyvinyl alcohol membrane core or polypiperazine membrane core.

Preferably, the membrane core in the membrane separation device is a nanofiltration membrane.

Preferably, the molecular weight cut-off of the membrane core is 100-400 Da.

Preferably, the membrane component form in the membrane separation device is one or more of hollow fiber membrane, roll membrane, plate and frame membrane and tubular membrane.

Preferably, the pressure in the membrane separation is 0.5-4 MPa.

Preferably, the content of 5-hydroxymethylfurfural in the 5-hydroxymethylfurfural-containing solution is greater than 0.1wt%.

Preferably, the content of 5-hydroxymethylfurfural in the 5-hydroxymethylfurfural-containing solution is 1wt%-80wt%

Preferably, the 5-hydroxymethyl furfural solution is prepared according to the following method:

The sugar containing the basic structural unit of the six-carbon sugar, the solvent and the catalyst are mixed and reacted to obtain a solution containing 5-hydroxymethyl furfural.

Preferably, the sugar containing the basic structural unit of six carbon sugars is one or more of glucose, fructose, maltose, sucrose, inulin, starch, galactose, cellobiose and cellulose.

Compared with the prior art, the present invention provides a method for purifying 5-hydroxymethyl furfural. The present invention filters the 5-hydroxymethyl furfural-containing solution by pumping it into a membrane separation device to collect and filter the membrane core. After removing the solvent from the filtrate to obtain 5-hydroxymethylfurfural, it was found through experiments that this method can very well purify the reaction liquid containing 5-hydroxymethylfurfural, the purification speed is fast, and the purity of the obtained HMF is high. And the loss of HMF is small.

detailed description

According to the present invention, the solution containing 5-hydroxymethyl furfural is pumped into the membrane separation device for filtration, the filtrate filtered through the membrane core is collected, and the solvent is removed to obtain 5-hydroxymethyl furfural; the filtration pressure is preferably 0.5 to 4 MPa, more preferably 1 to 3 MPa, most preferably 1.5 to 2 MPa; among them, when the purity of 5-hydroxymethyl furfural in the obtained filtrate is low, those skilled in the art can choose to pump again according to actual needs Filter again in the membrane separation device in order to obtain 5-hydroxymethyl furfural of suitable purity.

Wherein, the content of 5-hydroxymethyl furfural in the 5-hydroxymethyl furfural-containing solution is preferably greater than 0.1 wt%, more preferably 1 to 80 wt%, and more preferably 1.8 to 50 wt%; There is no special requirement for the source of hydroxymethyl furfural. Any solution containing 5-hydroxymethyl furfural prepared by a method known in the art that can prepare 5-hydroxymethyl furfural can be prepared according to the following method: The sugar of the basic structural unit of carbon sugar, the solvent and the catalyst are mixed and reacted to obtain a solution containing 5-hydroxymethyl furfural; wherein the sugar containing the basic structural unit of six carbon sugar may be glucose, fructose, maltose, sucrose, and inulin , Starch, galactose, cellobiose and cellulose; the solvent can be water, organic solvent or a mixed solution of organic solvent and salt solution; wherein, when the solvent is water, the solvent containing 5 -An aqueous reaction solution of hydroxymethylfurfural, wherein the pH of the aqueous reaction solution containing 5-hydroxymethylfurfural is preferably greater than 3, more preferably 5-8, most preferably 6.8-7.5; when the solvent is organic In the case of a solvent or a mixed solution of an organic solvent and a salt solution, an organic solution containing 5-hydroxymethyl furfural or a 5-hydroxymethyl furfural derivative solution formed by the reaction of 5-hydroxymethyl furfural with an organic solvent is obtained; The pH value of the organic solution containing 5-hydroxymethyl furfural has no special requirements and can be filtered directly; and the derivative solution of 5-hydroxymethyl furfural after filtration can be obtained through the solvent recovery step. The catalyst can be a catalyst known in the art that can be used to prepare 5-hydroxymethyl furfural from six-carbon sugars.

In the present invention, the membrane core in the membrane separation device is preferably a polyamide membrane core, a polyimide membrane core, a polyurethane membrane core, a cellulose acetate membrane core, a sulfonated polysulfone membrane core, and a polyethersulfone membrane core. Membrane core, sulfonated polyethersulfone membrane core, polyvinyl alcohol membrane core or polypiperazine membrane core, more preferably polyamide membrane core, polyimide membrane core, polyurethane membrane core, sulfonated polysulfone membrane core Core, polyethersulfone membrane core or sulfonated polyethersulfone membrane core; the molecular weight cut-off of the membrane core is preferably 100-400Da, more preferably 200-300Da; the present invention has no special effect on the membrane module form in the membrane separation device According to actual requirements, a suitable form can be selected according to actual needs. For example, it can be one or more of hollow fiber membranes, roll membranes, plate and frame membranes and tubular membranes; the present invention has no special requirements on the types of membrane separation devices. For example, it can be a cross-flow filter device.

The method for purifying 5-hydroxymethyl furfural provided by the present invention is to filter a solution containing 5-hydroxymethyl furfural into a membrane separation device, collect the filtrate filtered through the membrane core, and remove the solvent to obtain 5-hydroxymethyl It was found that this method can purify the reaction solution containing 5-hydroxymethyl furfural, so that the purity of the obtained HMF is high, and the loss of HMF is small; and the solution after sugar dehydration can be directly For separation, the whole process is continuous and fast, with large processing capacity, and can be directly applied to industrial applications; and the whole separation process is simple and efficient, with little contact with air, light, etc., and can be carried out at room temperature, thereby further improving the 5-hydroxymethyl The purity of furfural.

The following will clearly and completely describe the technical solutions of the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.

Example 1

The reaction solution containing 5-hydroxymethyl furfural can be prepared by the following method:

When the solvent is water: add a solid acid catalyst to 1L of 10% glucose-containing aqueous solution. After passing in N ₂ for 15 minutes, stir the reaction for 1 hour at 160°C and 1.5 MPa N ₂ atmosphere, cool to stop the reaction, and filter to remove the catalyst. An aqueous reaction liquid containing 5-hydroxymethyl furfural is obtained.

When the solvent is an organic solvent: add glucose to 1L saturated NaCl aqueous solution to prepare a solution with a glucose content of 10%, add 3L tetrahydrofuran and 10% catalyst, and after 15min of N _{2 is} passed in, at 160℃, 1.2MPa N ₂ atmosphere The reaction was stirred for 1.5 hours and cooled to stop the reaction. The upper organic phase solution was the organic phase extract containing 5-hydroxymethyl furfural.

Or add glucose and catalyst directly into methanol, add 15min of N ₂ and stir the reaction for 2.0h at 180°C and 1.2MPa N ₂ atmosphere, then cool to stop the reaction to obtain 5-hydroxymethyl furfural and 5-hydroxymethyl furfural. Organic solution of methyl furfural derivatives.

Take 2000ml of the organic phase extract containing 5-hydroxymethyl furfural (HMF content 1.8wt%, organic phase is tetrahydrofuran), add it to the raw material tank of the cross-flow filtration experiment device, and pump into the solvent-resistant polyimide membrane core Filtration is performed in the filter, the molecular weight cut-off of the membrane is 200Da, the pressure is 1MPa, the filtrate is collected, the solution that has not filtered through the membrane core is recycled to the raw material tank, and the solvent in the filtrate is recovered to obtain 32.5g of HMF.

The purity of HMF analyzed by high performance liquid chromatography (HPLC) was 98.6%, and the yield was 99%.

Example 2:

Take 4000ml of the organic phase extract containing 5-hydroxymethylfurfural prepared in Example 1 (HMF content 1.8wt%, organic phase is tetrahydrofuran), add it to the raw material tank of the cross-flow filtration experiment device, and pump into the solvent-resistant poly Filtration is performed in the urethane membrane core, the molecular weight cut-off of the membrane is 200Da, the pressure is 2MPa, the filtrate is collected, and the solution that has not filtered through the membrane core is recycled back to the raw material tank. Add the collected filtrate to a clean raw material tank for secondary filtration, collect the filtrate, and recover the solvent in the filtrate to obtain 62.5 g of HMF.

The purity of HMF by HPLC analysis was 99.5%, and the yield was 96%.

Example 3:

Take 2000ml of the organic solution containing 5-hydroxymethyl furfural and its derivatives prepared in Example 1 (where HMF is 2.8wt%, HMF derivative is 2.0wt%, and the organic phase is methanol), and added to the raw material tank of the cross-flow filtration experiment device In the process, it is pumped into a solvent-resistant polyurethane membrane core for filtration. The membrane has a molecular weight cut-off of 200Da and a pressure of 1MPa. The filtrate is collected. The solution that has not filtered through the membrane core is recycled back to the raw material tank to recover the solvent in the filtrate. Obtained HMF 85.7g.

The purity of HMF by HPLC analysis was 99.8%, and the yield was 99%.

Example 4:

Take 2000 ml of the aqueous reaction solution containing 5-hydroxymethyl furfural prepared in Example 1, with an HMF content of 5.9% by weight and a pH of 6.8, add it to the raw material tank of the cross-flow filtration experiment device, and pump it into the polyamide membrane core. After filtering, the molecular weight cut-off of the membrane is 300Da, the pressure is 1.5MPa, the filtrate is collected, the solution that has not filtered through the membrane core is recycled back to the raw material tank, and the solvent in the filtrate is recovered to obtain HMF121.4g.

The purity of HMF analyzed by high performance liquid chromatography (HPLC) was 96.2%, and the yield was 99%.

Example 5:

Take 1000 ml of the organic phase extract containing 5-hydroxymethyl furfural prepared in Example 1 (HMF content 1.8%, organic phase is tetrahydrofuran), remove organic solvents as much as possible, add 20% ethanol-containing aqueous solution and mix well, add cross-flow The raw material tank of the filtration experiment device is pumped into the polyamide membrane core for filtration. The membrane has a molecular weight cut-off of 300Da and a pressure of 1.2MPa. The filtrate is collected. The solution that has not filtered through the membrane core is recycled back to the raw material tank to recover the filtrate. Solvent, obtain 16.0g HMF.

The purity of HMF analyzed by high performance liquid chromatography (HPLC) was 98.8%, and the yield was 98%.

Comparative example 1

Take 4000 ml of the organic phase extract containing 5-hydroxymethyl furfural prepared in Example 1 (HMF content 1.8%, organic phase is tetrahydrofuran), add it to the raw material tank of the cross-flow filtration experimental device, and pump it into the polyamide membrane core. Filtration, the molecular weight cut-off of the membrane is 500Da, the pressure is 1MPa, the filtrate is collected, and the solution that has not filtered through the membrane core is recycled back to the raw material tank. Add the collected filtrate to a clean raw material tank for secondary filtration, collect the filtrate, and recover the solvent in the filtrate to obtain 77.9 g of HMF.

The purity of HMF by HPLC analysis was 82.5%, and the yield was 99.2%.

Comparative example 2

Take 4000ml of 5-hydroxymethylfurfural-containing aqueous reaction solution prepared in Example 1 (HMF content 1.8%), add it to the raw material tank of the cross-flow filtration experiment device, and pump it into the polyethersulfone membrane core for filtration. The molecular weight cut-off is 200Da, the pressure is 2MPa, the filtrate is collected, and the solution that has not filtered through the membrane core is recycled back to the raw material tank. Add the collected filtrate to a clean raw material tank for secondary filtration, collect the filtrate, and recover the solvent in the filtrate to obtain 80.6 g of HMF.

The purity of HMF by HPLC analysis was 88.9%, and the yield was 99.6%.

Comparative example 3

Take the 5-hydroxymethylfurfural-containing aqueous reaction solution prepared in Example 1, and its HMF content is 5.9wt%, add a certain amount of acid to it, adjust the pH to 2.8, and add 2000ml of the solution to the cross-flow filtration experimental device In the raw material tank, pump into the polyamide membrane core for filtration. The membrane has a molecular weight cut-off of 300Da and a pressure of 1.5MPa. The filtrate is collected. The solution that has not filtered through the membrane core is recycled back to the raw material tank to recover the solvent in the filtrate to obtain HMF. 122.4g.

The purity of HMF analyzed by high performance liquid chromatography (HPLC) was 95.4%, and the yield was 99%.

The description of the above embodiments is only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

A purification method of 5-hydroxymethyl furfural, including:

The solution containing 5-hydroxymethyl furfural is pumped into the membrane separation device for filtration, the filtrate filtered through the membrane core is collected, and the solvent is removed to obtain 5-hydroxymethyl furfural.
The purification method according to claim 1, wherein the membrane core in the membrane separation device is a polyamide membrane core, a polyimide membrane core, a polyurethane membrane core, a cellulose acetate membrane core, Polysulfone membrane core, sulfonated polyethersulfone membrane core, polyvinyl alcohol membrane core or polypiperazine membrane core.
The purification method according to claim 1, wherein the membrane core in the membrane separation device is a nanofiltration membrane.
The purification method according to claim 1, wherein the molecular weight cut-off of the membrane core is 100-400 Da.
The purification method according to claim 1, wherein the membrane module in the membrane separation device is one or more of hollow fiber membranes, roll membranes, plate and frame membranes and tubular membranes.
The purification method according to claim 1, wherein the pressure in the membrane separation is 0.5-4 MPa.
The purification method according to claim 1, wherein the content of 5-hydroxymethylfurfural in the solution containing 5-hydroxymethylfurfural is greater than 0.1wt%.
The purification method according to claim 1, wherein the content of 5-hydroxymethylfurfural in the 5-hydroxymethylfurfural-containing solution is 1wt%-80wt%.
The purification method according to claim 1, wherein the solution of 5-hydroxymethyl furfural is prepared according to the following method:

The sugar containing the basic structural unit of the six-carbon sugar, the solvent and the catalyst are mixed and reacted to obtain a solution containing 5-hydroxymethyl furfural.
The purification method according to claim 9, characterized in that the sugar containing the basic structural unit of six carbon sugars is glucose, fructose, maltose, sucrose, inulin, starch, galactose, cellobiose and cellulose. One or more.