Sugar separation and purification material as well as preparation method and application thereof

Abstract

The invention relates to a saccharide separation and purification material as well as a preparation method and application thereof, acrylamide, azodiisobutyronitrile and ethylene glycol dimethacrylate are subjected to a polymerization reaction in a mixed solution of dimethyl sulfoxide and trichloromethane, and a formed solid substance is crushed, washed and dried to obtain the saccharide separation and purification material. The saccharide separation and purification material is good in separation effect, good in stability and convenient to store and use.

Description

Technical Field

[0001] The invention relates to a method for preparing a carbohydrate separation and purification material, a carbohydrate separation and purification material prepared by the method, and application of the material in carbohydrate separation and purification, belonging to the technical field of separation and purification. Background Art

[0002] For the separation and purification of sugars, currently, separation and purification materials based on ion exchange or molecular sieve principles are mainly used. For example, the invention patent application with publication number CN114014896A discloses a method for separation and purification of high-purity 3'-sialyllactose, which includes heating and inactivating enzymes in the conversion liquid, filtering after adjusting the pH of the filtrate to alkaline, adjusting the pH of the filtrate to neutral, concentrating, ion adsorption, drying and other steps to obtain separated and purified 3'-SL; this method uses heating and inactivating enzymes and adjusting the pH to alkaline to comprehensively improve the removal rate of macromolecular substances such as proteins in the conversion liquid, and at the same time controls the concentration of 3'-SL in the concentrated liquid, which plays an important role in further improving the purity of the product 3'-SL for anion and cation adsorption purification. The purity of the product 3'-SL obtained by the above method is ≥96%. For another example, the invention patent application with publication number CN102875607A discloses a method for separating and purifying raffinose, including: 1) using gel as filler and wet-loading a gel chromatography column; 2) preparing a raw material liquid with raffinose concentrate and loading it on the gel chromatography column; 3) eluting with deionized water or ethanol aqueous solution as eluent, collecting the eluent containing raffinose, and obtaining purified raffinose after rotary evaporation; the raffinose concentrate is obtained by extracting defatted cottonseed meal with water or alcohol aqueous solution to obtain a raffinose extract, which is then decolorized and concentrated with activated carbon. These existing technologies have their own characteristics and are respectively adapted to various adaptive uses and occasions. However, since the needs in reality are diverse, different materials need to be continuously developed to meet the ever-evolving user needs. Summary of the invention

[0003] The purpose of the present invention is to provide a new carbohydrate separation and purification material and the application of the carbohydrate separation and purification material.

[0004] The technical scheme for achieving the above-mentioned purpose of the present invention is: a method for preparing a sugar separation and purification material, wherein acrylamide, azobisisobutyronitrile and ethylene glycol dimethacrylate are subjected to polymerization reaction in a mixed solution of dimethyl sulfoxide and chloroform, and the formed solid matter is crushed, washed and dried to obtain the sugar separation and purification material.

[0005] Preferably, the mass parts of dimethyl sulfoxide and chloroform in the mixed solution are: 14-18 parts of dimethyl sulfoxide and 1-3 parts of chloroform.

[0006] Preferably, the mass proportions of acrylamide, azobisisobutyronitrile and ethylene glycol dimethacrylate added into the mixed solution are: 1.4-1.8 parts of acrylamide, 0.06-0.1 parts of azobisisobutyronitrile, and 6-8 parts of ethylene glycol dimethacrylate.

[0007] Preferably, acrylamide is first added to the mixed solution, and after the acrylamide is completely dissolved and the liquid is allowed to stand (for example, for 20 hours), azobisisobutyronitrile and ethylene glycol dimethacrylate are added.

[0008] The mixed solution with acrylamide added thereto may be shaken, for example, for 2 hours, to accelerate the dissolution rate of acrylamide and improve the dissolution effect.

[0009] The polymerization reaction temperature may be 60-65° C., and the time may be 20-24 hours. Preferably, the polymerization reaction temperature is 61° C., and the time is 24 hours.

[0010] The polymerization reaction can be carried out in a water bath.

[0011] Preferably, the polymerization reaction is carried out in a nitrogen environment. Nitrogen can be filled into a reaction container (such as a conical flask) for 10 minutes, the container mouth is quickly sealed, and then the reaction container is placed in a water bath for polymerization.

[0012] Preferably, after the solid material is crushed, it is sieved with a sieve to obtain fine powder, and the fine powder is washed.

[0013] The solid material can be crushed by a suitable crusher in the prior art, and the sieve is preferably a 60-mesh sieve.

[0014] Preferably, the fine powder is washed (repeatedly) with a mixture of methanol and acetic acid, wherein the weight proportions of methanol and acetic acid in the mixture are: 160-200 parts of methanol and 16-24 parts of acetic acid.

[0015] The fine powder may be first wrapped with filter paper, and then the filter paper wrapped with the fine powder is placed in a Soxhlet extractor, and the mixed solution is added, heated to reflux, and washed for 1 hour.

[0016] Preferably, the washed fine powder is dispersed in water, the upper suspended particles are removed, and the middle and lower particles are dried to obtain the sugar separation and purification material.

[0017] The drying temperature may be 40-50°C, preferably 45°C.

[0018] The carbohydrate separation and purification material is prepared by using any of the preparation methods for the carbohydrate separation and purification material disclosed in the present invention.

[0019] Application of any carbohydrate separation and purification material disclosed in the present invention in carbohydrate separation and purification.

[0020] The beneficial effects of the present invention are as follows: this is a brand-new carbohydrate separation and purification material different from existing ion exchange resins and molecular sieve gels, and can effectively separate and purify carbohydrates such as galacturonic acid, galactose and polygalacturonic acid, and obtain good separation and purification effects. Its form can be powdery, with a large specific surface area, strong separation ability, good stability, and convenient storage and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 The elution curve diagram is when galacturonic acid, galactose and polygalacturonic acid are separated and purified by using the carbohydrate separation and purification material of the present invention. DETAILED DESCRIPTION

[0022] The preparation method of the sugar separation and purification material comprises the following steps: subjecting acrylamide, azobisisobutyronitrile and ethylene glycol dimethacrylate to a polymerization reaction in a mixed solution of dimethyl sulfoxide and chloroform, and crushing, washing and drying the formed solid matter to obtain the sugar separation and purification material.

[0023] The weight parts of dimethyl sulfoxide and chloroform in the mixed solution are preferably: 14-18 parts of dimethyl sulfoxide, 1-3 parts of chloroform. The weight parts of acrylamide, azobisisobutyronitrile and ethylene glycol dimethacrylate added to the mixed solution are preferably: 1.4-1.8 parts of acrylamide, 0.06-0.1 parts of azobisisobutyronitrile, and 6-8 parts of ethylene glycol dimethacrylate.

[0024] In the process of preparing the sugar separation and purification material, acrylamide is first added to the mixed solution, and after the acrylamide is completely dissolved and the liquid is allowed to stand (for example, for 20 hours), azobisisobutyronitrile and ethylene glycol dimethacrylate are added. Generally, the mixed solution with acrylamide added can be shaken, for example, for 2 hours, to accelerate the dissolution rate of acrylamide and improve the dissolution effect.

[0025] The polymerization reaction may be carried out at a temperature of 60-65°C, such as 60°C, 61°C, 62°C or 65°C, and for a time of 20-24 hours, such as 20 hours, 21 hours, 23 hours or 24 hours.

[0026] The polymerization reaction can be carried out in a water bath, in which a constant temperature is maintained.

[0027] The polymerization reaction is preferably carried out under a nitrogen environment. Nitrogen can be filled into a reaction container (such as a conical flask) for 10 minutes, the container mouth is quickly sealed, and the reaction container is placed in a water bath to carry out the polymerization reaction.

[0028] In the preparation process of the sugar separation and purification material, the solid material formed by the polymerization reaction is crushed, preferably sieved with a screen to obtain fine powder, and the fine powder is washed. The solid material can be crushed by a suitable crusher under the existing technology, and the screen is preferably a 60-mesh screen.

[0029] During the washing process, the fine powder is washed (repeatedly washed) with a mixture of methanol and acetic acid, and the weight proportions of methanol and acetic acid in the mixture are preferably: 160-200 parts of methanol and 16-24 parts of acetic acid. The fine powder can be first wrapped with filter paper, and then the filter paper bag containing the fine powder is placed in a Soxhlet extractor, the mixture is added, heated to reflux, and washed for 1 hour. The washed fine powder is dispersed in water, the upper suspended particles are removed, and the middle and lower particles are dried to obtain the sugar separation and purification material. Any drying equipment suitable for drying powdered materials under the prior art can be used for drying, and the drying temperature can be 40-50°C, preferably 45°C.

[0030] This material can effectively separate and purify sugars and achieve good separation and purification effects.

[0031] Embodiment 1: (1) Take a conical flask (appropriate volume), add 140 g of dimethyl sulfoxide, 20 g of chloroform, weigh 18 g of acrylamide, shake for 2 hours to completely dissolve the acrylamide, and let it stand for 20 hours; (2) Add 0.6 g of azobisisobutyl cyanide and 70 g of ethylene glycol dimethacrylate into a conical flask; (3) Fill the conical flask with nitrogen for 10 minutes, quickly seal it, and place it in a water bath to maintain a constant temperature of 61°C for 24 hours to obtain a white solid; (4) crushing the white solid with a grinder, sieving with a 60-mesh sieve to obtain fine powder, and wrapping the fine powder with filter paper; (5) Place the filter paper bag containing fine powder in a Soxhlet extractor, add 240 g of acetic acid and 1600 g of methanol, heat to reflux, and wash for 1 hour; (6) The washed material is dispersed in water, the upper suspended particles are removed, the middle and lower particles are taken, and dried at 45°C to obtain the sugar separation and purification material.

[0032] Embodiment 2: (1) Take a conical flask (appropriate volume), add 160 g of dimethyl sulfoxide, 30 g of chloroform, weigh 14 g of acrylamide, shake for 2 hours to completely dissolve the acrylamide, and let it stand for 20 hours; (2) Add 0.8 g of azobisisobutyl cyanide and 80 g of ethylene glycol dimethacrylate into a conical flask; (3) Fill the conical flask with nitrogen for 10 minutes, quickly seal it, and place it in a water bath to maintain a constant temperature of 60°C for 23 hours to obtain a white solid; (4) crushing the white solid with a grinder, sieving with a 60-mesh sieve to obtain fine powder, and wrapping the fine powder with filter paper; (5) Place the filter paper bag containing fine powder in a Soxhlet extractor, add 160 g of acetic acid and 2000 g of methanol, heat under reflux, and wash for 1 hour; (6) The washed material is dispersed in water, the upper suspended particles are removed, the middle and lower particles are taken, and dried at 40°C to obtain the sugar separation and purification material.

[0033] Embodiment 3: (1) Take a conical flask (appropriate volume), add 180 g of dimethyl sulfoxide, 10 g of chloroform, weigh 16 g of acrylamide, shake for 2 hours to completely dissolve the acrylamide, and let it stand for 20 hours; (2) Add 1 g of azobisisobutyl cyanide and 60 g of ethylene glycol dimethacrylate into a conical flask; (3) Fill the conical flask with nitrogen for 10 minutes, quickly seal it, and place it in a water bath to maintain a constant temperature of 65°C for 20 hours to obtain a white solid; (4) crushing the white solid with a grinder, sieving with a 60-mesh sieve to obtain fine powder, and wrapping the fine powder with filter paper; (5) Place the filter paper bag containing fine powder in a Soxhlet extractor, add 200 g of acetic acid and 1800 g of methanol, heat under reflux, and wash for 1 hour; (6) The washed material is dispersed in water, the upper suspended particles are removed, the middle and lower particles are taken, and dried at 50°C to obtain the sugar separation and purification material.

[0034] Embodiment 4: (1) Take a conical flask (appropriate volume), add 9 ml of dimethyl sulfoxide, 1 ml of chloroform, weigh 0.8080 g of acrylamide, shake for 2 hours to completely dissolve the acrylamide, and let it stand for 20 hours; (2) Add 0.0403 g of azobisisobutyl cyanide and 3.770 ml of ethylene glycol dimethacrylate into a conical flask; (3) Fill the conical flask with nitrogen for 10 minutes, quickly seal it, and place it in a water bath to maintain a constant temperature of 61°C for 24 hours to obtain a white solid; (4) crushing the white solid with a grinder, sieving with a 60-mesh sieve to obtain fine powder, and wrapping the fine powder with filter paper; (5) Place the filter paper bag containing fine powder in a Soxhlet extractor, add 10 ml of acetic acid and 90 ml of methanol, heat to reflux, and wash for 1 hour; (6) The washed material is dispersed in water, the upper suspended particles are removed, the middle and lower particles are taken, and dried at 45°C to obtain the sugar separation and purification material.

[0035] Test Example 1: The carbohydrate separation and purification material prepared in Example 1 was loaded into a chromatographic column and balanced with water. 0.0050 g of galacturonic acid was weighed, 0.5 ml of water was added, loaded onto the chromatographic column, eluted with water, and the eluate was collected. Each tube had 1 ml, and a total of 20 tubes were collected. 0.2 ml of the eluate from each tube was taken, 0.1 ml of 6% phenol and 0.5 ml of sulfuric acid were added, and the absorbance (or optical density value) was measured at 490 nm. The elution curve was as shown in FIG. Figure 1 shown.

[0036] Test Example 2: The carbohydrate separation and purification material prepared in Example 2 was loaded into a chromatographic column, 0.0050 g of polygalacturonic acid was weighed, 0.5 ml of water was added, loaded onto the chromatographic column, eluted with water, and the eluate was collected, 1 ml per tube, and a total of 20 tubes were collected. 0.2 ml of the eluate from each tube was taken, 0.1 ml of 6% phenol and 0.5 ml of sulfuric acid were added, and the absorbance was measured at 490 nm. The elution curve was as shown in FIG. Figure 1 shown.

[0037] Test Example 3: The sugar separation and purification material prepared in Example 3 was loaded into a chromatographic column, 0.0053 g of galactose was weighed, 0.5 ml of water was added, loaded onto the chromatographic column, eluted with water, and the eluate was collected, 1 ml per tube, and a total of 20 tubes were collected. 0.2 ml of the eluate from each tube was taken, 0.1 ml of 6% phenol and 0.5 ml of sulfuric acid were added, and the absorbance was measured at 490 nm. The elution curve is as shown in FIG. Figure 1 shown.

[0038] Unless otherwise specified or one preferred or optional technical means is a further limitation of another technical means, all preferred and optional technical means disclosed in the present invention can be arbitrarily combined to form several different technical solutions.

Claims

1. A method for preparing a carbohydrate separation and purification material, characterized in that The polymerization reaction of acrylamide, azobisisobutyronitrile and ethylene glycol dimethacrylate is carried out in a mixed solution of dimethyl sulfoxide and chloroform, and the formed solid matter is crushed, washed and dried to obtain a sugar separation and purification material.

2. The method for preparing a carbohydrate separation and purification material according to claim 1, characterized in that The mass parts of dimethyl sulfoxide and chloroform in the mixed solution are: 14-18 parts of dimethyl sulfoxide and 1-3 parts of chloroform.

3. The method for preparing a carbohydrate separation and purification material according to claim 2, characterized in that The mass proportions of acrylamide, azobisisobutyronitrile and ethylene glycol dimethacrylate added into the mixed solution are: 1.4-1.8 parts of acrylamide, 0.06-0.1 parts of azobisisobutyronitrile, and 6-8 parts of ethylene glycol dimethacrylate.

4. The method for preparing a carbohydrate separation and purification material according to claim 1, characterized in that First, acrylamide is added to the mixed solution, and after the acrylamide is completely dissolved and the liquid is allowed to stand, azobisisobutyronitrile and ethylene glycol dimethacrylate are added.

5. The method for preparing a carbohydrate separation and purification material according to claim 1, characterized in that The polymerization temperature is 60-65°C and the time is 20-24 hours.

6. The method for preparing a carbohydrate separation and purification material according to claim 1, characterized in that The polymerization reaction was carried out under nitrogen environment.

7. The method for preparing a carbohydrate separation and purification material according to claim 1, characterized in that After the solid material is crushed, it is sieved with a sieve to obtain fine powder, and the fine powder is washed.

8. The method for preparing a carbohydrate separation and purification material according to claim 7, characterized in that The fine powder is washed with a mixed solution of methanol and acetic acid, wherein the weight proportions of methanol and acetic acid in the mixed solution are: 160-200 parts of methanol and 16-24 parts of acetic acid.

9. A carbohydrate separation and purification material, characterized in that The material is prepared by the method for preparing a carbohydrate separation and purification material according to any one of claims 1 to 8.

10. Use of the carbohydrate separation and purification material according to claim 9 in carbohydrate separation and purification.

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