CN109364898B

CN109364898B - Method for preparing chromatographic material from distiller's grains

Info

Publication number: CN109364898B
Application number: CN201811155144.9A
Authority: CN
Inventors: 刘启民; 程桂茹; 葛彦侠
Original assignee: Changchun University of Technology
Current assignee: Changchun University of Technology
Priority date: 2018-09-30
Filing date: 2018-09-30
Publication date: 2021-06-08
Anticipated expiration: 2038-09-30
Also published as: CN109364898A

Abstract

A method for preparing chromatographic material from distiller's grains belongs to the technical field of chemical engineering, and comprises centrifuging wet distiller's grains after fermenting to produce alcohol distilled liquor; the filtered distiller's dried grains are catalyzed and hydrolyzed in water by low-concentration acid, and cellulose, protein and lignin are reserved; fully washing the vinasse subjected to acid treatment by using alcohol; and (5) drying the vinasse subjected to alcohol washing treatment in vacuum to constant weight. The invention prepares the chromatographic material by simply processing the vinasse, so that most of components in the vinasse are utilized. The prepared chromatographic material has the advantage of lower cost and is beneficial to industrial application.

Description

Method for preparing chromatographic material from vinasse

Technical Field

The invention belongs to the technical field of fine chemical engineering, and relates to a method for preparing a chromatographic material.

Background

The chromatographic method or the preparative chromatography method is an effective method for separating, enriching or preparing pure substances from a mixture, and is widely applied to the industries of chemical engineering, medicine and the like. The chromatography materials are various, such as adsorbent resin, silica gel, polyamide, dextran, etc.

China has a plurality of alcohol and white spirit manufacturers and the yield of vinasse is very large. At present, vinasse is mainly used as animal feed. Research shows that a certain amount of vinasse is added into daily ration to promote animal growth and improve the output rate of animal products. However, the vinasse has large variation of various nutrient substances, and contains anti-nutritional factors such as lignin, phytic acid and the like and mycotoxin, so that the use of the vinasse in large quantities in animal daily rations is limited.

Regarding the utilization of the vinasse, more than 300 related patents exist in the country from 2015 to 2018, such as a method for producing high-purity cellulose, hemicellulose and lignin by using the vinasse in CN 201810108510.9; CN 201810072935.9A method for preparing biochar from distiller's grains and recycling intermediate waste; CN 201711203002.0A preparation method of a distillers' grains powder organic fertilizer; CN 201711323946.1A new process for brewing edible vinegar from distiller's grains; CN201711204678.1 a preparation method of vinasse small molecular peptide and application of the vinasse small molecular peptide in skin care products; and the like. The methods realize the reutilization of partial components in the vinasse, and provide a related solution for the vinasse utilization.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a method for preparing a chromatographic material from vinasse.

The main components of the distiller's grains include amino acids, proteins, hemicellulose, cellulose, lignin, etc., and small amount of organic acids, polyphenols, etc. The invention aims at the characteristics of main components in the vinasse, in particular to the characteristics of the components of the vinasse after the alcohol is produced by fermenting the corn, prepares a material mainly composed of protein, cellulose and lignin, and uses the material as a chromatographic material.

The technical scheme of the invention is as follows:

fermenting corn to produce alcohol, centrifugally filtering wet distiller's grains after distilling, drying the filtered clear liquid, and applying to other applications, such as feed; distiller's dried grain is ready for use in the present invention.

The method comprises the following specific steps:

the method comprises the steps of producing alcohol through corn fermentation, and centrifugally filtering wet distiller's grains after distilling wine;

and catalyzing and hydrolyzing the filtered dry vinasse in water by using low-concentration acid to remove hemicellulose and other components in the vinasse and retain cellulose, protein and lignin. The low-concentration acid is sulfuric acid or hydrochloric acid, wherein the concentration of hydrogen ions is 0.3-2mol/L, preferably 0.8-1.2 mol/L; the reaction temperature is between room temperature and 80 ℃, preferably between 40 and 60 ℃; the reaction time is 0.5 to 3 hours, preferably 1 to 2 hours; filtering the hydrolyzed distiller's dried grains, and washing with water to neutrality;

and thirdly, fully washing the vinasse subjected to acid treatment by using alcohol to remove organic small molecular impurities. The alcohol concentration is 70-100%, preferably 90-95%; the washing temperature is between room temperature and 78 ℃, preferably between 30 and 50 ℃; the washing treatment times are 2-10 times, and the washing solution is almost colorless after 3-5 times of washing. Filtering and recovering alcohol after each washing treatment, and repeatedly utilizing the alcohol after distillation.

Fourthly, drying the alcohol-washed vinasse in vacuum and drying the vinasse to constant weight. Drying under-0.04-0.1 MPa, preferably-0.08-0.1 MPa; the drying temperature is from room temperature to 100 deg.C, preferably from 70 to 90 deg.C.

Fifthly, screening the dried vinasse powder according to the requirement, and dividing the dried vinasse powder into components with different particle sizes, such as 80-120 meshes; 200-300 meshes; components with more than 400 meshes; to meet different experimental requirements.

The invention can simply process the vinasse to prepare the chromatographic material, so that most of the components in the vinasse are utilized. The prepared chromatographic material has the advantage of lower cost and is beneficial to industrial application.

Drawings

FIG. 1 is a chromatogram of a hop extract eluted with dichloromethane;

FIG. 2 is a chromatogram of an extract of hops eluted with ethyl acetate;

FIG. 3 is a chromatogram of an elution of hop extract with methanol;

FIG. 4 is a comparison of the above three sets of chromatograms.

Detailed Description

The present invention is further illustrated by, but not limited to, the following examples.

Example 1

Fermenting corn to produce alcohol, and centrifugally filtering wet distiller's grains after distilling the alcohol;

60 g of the filtered distiller's dried grain is taken, 400 ml of 10% hydrochloric acid (about 1.2 mol/L) is added, the mixture is heated to 60 ℃ to hydrolyze and remove hemicellulose, and the reaction lasts for 2 hours. Filtering, collecting insoluble substances, and washing with water to neutrality; and heating and washing the vinasse subjected to acid treatment by using 95% alcohol, wherein the washing treatment temperature is 50 ℃ so as to remove organic small molecular impurities. The washing treatment was performed 5 times, and the washing solution was almost colorless. Filtering and recovering alcohol after each washing treatment, and repeatedly utilizing the alcohol after distillation. The distillers 'grains after the alcohol washing treatment are dried in vacuum to constant weight under the conditions of-0.08 Mpa and 80 ℃, and 23 g of dried distillers' grains powder is obtained. Sieving with a standard sieve, sieving with a 400-mesh standard sieve to obtain components above 400 meshes, sieving with a 200-mesh standard sieve to obtain 200-mesh 400-mesh components, sieving with a 100-mesh standard sieve to obtain 100-mesh 200-mesh components, and sieving with a 50-mesh standard sieve to obtain 50-100-mesh components.

Example 2

60 g of the filtered distiller's dried grain is taken, 300 ml of 8% sulfuric acid (the acid concentration is about 1.7 mol/L) is added, the mixture is heated to 40 ℃ to hydrolyze and remove hemicellulose, and the reaction is carried out for 1 hour. Filtering, collecting insoluble substances, and washing with water to neutrality; and heating and washing the vinasse subjected to acid treatment by using 75% alcohol, wherein the washing treatment temperature is 40 ℃, so as to remove organic small molecular impurities. The washing treatment was 7 times, and the washing solution was almost colorless. Filtering and recovering alcohol after each washing treatment, and repeatedly utilizing the alcohol after distillation. The distillers 'grains after the alcohol washing treatment are dried in vacuum at 70 ℃ under the pressure of-0.09 Mpa to constant weight, and 24 g of dried distillers' grains powder is obtained. Sieving with standard sieve, sieving with 300 mesh standard sieve to obtain 300 mesh above component, sieving with 200 mesh standard sieve to obtain 200-.

Experimental example:

9 g of prepared dried distillers' grains chromatography material (50-100 meshes) is filled into a column, the diameter of the column is 16 mm, the volume of the column is 28 ml.

Dissolving 3 g of hop extract in dichloromethane, loading 7 ml of the solution on a column, then eluting with dichloromethane, collecting 30 ml of eluent, concentrating and evaporating to dryness to obtain brown solid; 0.5mg/ml solution was prepared for HPLC analysis, and its chromatogram was shown in FIG. 1.

Collecting about 20 ml of ethyl acetate eluent, concentrating and evaporating to dryness to obtain an orange substance; 0.5mg/ml solution was prepared for HPLC analysis, and its chromatogram was shown in FIG. 2.

And collecting 20 ml of methanol eluent, precipitating light yellow solid, not filtering, directly evaporating to dryness to obtain yellow solid. 0.5mg/ml solution was prepared for HPLC analysis, and its chromatogram was shown in FIG. 3.

The HPLC analysis chromatograms were compared, and the results are shown in FIG. 4.

According to our previous study results, the component with retention time of 14.8 minutes is xanthohumol, the component with retention time of 13.7 minutes is xanthohumol D, and the component with retention time of 13.3 is an unidentified flavone compound.

As can be seen from the comparison results, the content of xanthohumol in the dichloromethane eluate is higher, the content of the flavone compounds of xanthohumol D and retention time 13.3 in the ethyl acetate eluate is higher, the content of the flavone compounds of xanthohumol, xanthohumol D and retention time 13.3 in the methanol eluate is less, the main component is a yellowish substance which is not absorbed at the detection wavelength and therefore is not visible in the chromatogram.

The experimental results show that the chromatographic material prepared from the vinasse has certain separation function.

Claims

1. a kind of application of distiller's grains as chromatographic material, it is characterized in that being realized by following steps:

(1) Centrifugal filtration of wet distiller's grains after fermentation to produce alcoholic distilled liquor;

(2) The filtered dried distiller's grains are hydrolyzed by low concentration acid in water to retain cellulose, protein and lignin;

(3) Fully wash the acid-treated distiller's grains with alcohol;

(4) Vacuum-drying the distiller's grains after alcohol washing treatment to constant weight;

The dry distiller's grains chromatography material in step (4) is packed into a column of 9g, the column is ф16*140mm, and the volume is 28ml; 3g of the hop extract is dissolved in dichloromethane, and the solution is loaded on the column with 7ml, and then eluted with dichloromethane, Collect 30 ml of the eluate, concentrate and evaporate to dryness to obtain a brown solid; then collect about 20 ml of the ethyl acetate eluent, concentrate and evaporate to dryness to obtain an orange substance; then collect 20 ml of the methanol eluent, and precipitate a light yellow solid, which is not Filter and evaporate to dryness directly to obtain a yellow solid.

2. application according to claim 1 is characterized in that: the described low-concentration acid of step (2) is sulfuric acid or hydrochloric acid, and wherein hydrogen ion concentration is 0.3-2mol/L; Temperature of reaction is room temperature-80 ℃; Reaction Time 0.5-3 hours.

3. The application according to claim 2, wherein the hydrogen ion concentration in the low-concentration acid is 0.8-1.2 mol/L; the reaction temperature is 40-60°C; the reaction time is 1-2 hours.

4 . The application according to claim 1 , wherein: the alcohol concentration in step (3) is 70%-100%; the washing treatment temperature is room temperature-78° C.; the washing treatment times are 2-10 times. 5 .

5. The application according to claim 4, characterized in that: the alcohol concentration is 90-95%; the washing treatment temperature is 30-50°C; and the washing treatment times are 3-5 times.

6 . The application according to claim 1 , wherein the drying pressure in step (4) is -0.04-0.1Mpa; the drying temperature is room temperature -100°C.

7. The application according to claim 6, characterized in that: the drying pressure is -0.08-0.1Mpa; the drying temperature is 70-90°C.