A method for post-treatment of brewing residues

Abstract

The present invention relates to the technical field of brewing raw material treatment, and provides a post-treatment method for brewing residues, comprising the following steps: S1, extraction: extracting distillers' grains or brewing wastewater with an equal volume of an organic solvent to obtain an organic phase extraction solution and an aqueous phase extraction solution; S2, back-extraction and concentration: after subjecting the aqueous phase extraction solution to multi-stage vacuum concentration, two types of substances are obtained from the distillate, one type being monosaccharide substances and the other type being oligosaccharide and short peptide substances; after subjecting the organic phase extraction solution to vacuum concentration, adjusting the pH value to alkaline, and then adding water for back-extraction to obtain an aqueous phase back-extraction solution and an organic phase back-extraction solution; S3, adjusting pH; S4, vacuum concentration; S5, chromatography; S6, vacuum concentration. The present invention can effectively treat distillers' grains and brewing wastewater separately, recover a variety of reusable substances, greatly reduce resource waste, and effectively reduce the comprehensive treatment cost through reuse, which is extremely beneficial to green development.

Description

Technical Field

[0001] The present invention relates to a post-treatment method for brewing residues, belonging to the technical field of brewing raw material treatment. Background Art

[0002] During the brewing process, residues mainly including distiller's grains and brewing wastewater are generated. Currently, the treatment of such residues mainly focuses on distiller's grains, while most of the brewing wastewater is directly treated as wet garbage. However, the brewing wastewater also contains a large amount of recyclable substances. Directly treating it as wet garbage is a waste of resources, and due to the large quantity, the treatment cost is high, which is not conducive to green development. Summary of the Invention

[0003] To solve the above technical problems, the present invention provides a post-treatment method for brewing residues. This method can effectively treat distiller's grains and brewing wastewater separately, recover a variety of reusable substances, greatly reduce resource waste, and effectively reduce the comprehensive treatment cost through reuse, which is extremely conducive to green development.

[0004] The present invention is achieved through the following technical solutions.

[0005] A post-treatment method for brewing residues provided by the present invention includes the following steps:

[0006] S1. Extraction: Extract distiller's grains or brewing wastewater with an equal volume of organic solvent to obtain an organic phase extract and an aqueous phase extract.

[0007] S2. Back-extraction and concentration: After subjecting the aqueous phase extract to multi-stage vacuum concentration, two types of substances are obtained from the distillate, one is monosaccharide substances, and the other is oligosaccharide and short peptide substances; after vacuum concentrating the organic phase extract, adjust the pH value to alkaline, and then add water for back-extraction to obtain an aqueous phase back-extract and an organic phase back-extract.

[0008] S3. Adjust pH: Adjust the pH value of the aqueous phase back-extract to acidic with hydrochloric acid solution, and then extract with ethyl acetate to obtain a secondary organic phase extract; adjust the pH value of the organic phase back-extract to acidic with hydrochloric acid solution, and then add water for back-extraction to obtain a secondary organic phase back-extract.

[0009] S4. Vacuum concentration: Vacuum concentrate the secondary organic phase extract to constant weight to obtain organic acid substances; vacuum concentrate the secondary organic phase back-extract to a paste to obtain phenolic raw materials.

[0010] S5. Chromatography: Subject the phenolic raw materials to polyamide reverse-phase column chromatography to separate and obtain a water wash solution, a phenolic eluate, and a column flushing solution.

[0011] S6. Vacuum concentration: Discard the water wash solution and the column flushing solution, and vacuum concentrate the phenolic eluate to a constant amount to obtain phenolic substances.

[0012] In the step S1, the organic solvent is ethyl acetate; in the step S1, extraction is performed 3 times.

[0013] In the step S2, the aqueous phase extract is first concentrated under reduced pressure at 60 °C, and then concentrated under reduced pressure at 50 °C. After that, fractions are collected by ELSD detection to obtain two parts, and the two parts are concentrated under reduced pressure at 60 °C to constant weight to obtain two types of substances, one type is monosaccharide substances, and the other type is oligosaccharide and short peptide substances.

[0014] In the step S2, after the organic phase extract is concentrated under reduced pressure, the pH value is adjusted to alkaline, concentrated under reduced pressure at 45 °C, and then the pH value is adjusted to 10 with sodium carbonate.

[0015] In the step S3, the pH value of the aqueous phase back-extract is adjusted to acidic with a hydrochloric acid solution, and the pH value of the aqueous phase back-extract is adjusted to 4 with a 0.1% hydrochloric acid solution.

[0016] In the step S3, the pH value of the organic phase back-extract is adjusted to acidic with a hydrochloric acid solution, and the pH value of the organic phase back-extract is adjusted to 5 with a 0.1% hydrochloric acid solution.

[0017] In the step S4, the organic phase secondary extract is concentrated under reduced pressure to constant weight, and the organic phase secondary extract is concentrated under reduced pressure to constant weight at 45 °C.

[0018] In the step S4, the organic phase secondary back-extract is concentrated under reduced pressure to a paste, and the organic phase secondary back-extract is concentrated under reduced pressure to a paste at 45 °C.

[0019] In the step S5, chromatography is performed by detecting the eluent with TLC. Phenolic eluent is obtained using 90% methanol as the eluent, washing solution is obtained using pure water as the eluent, and column flushing solution is obtained using pure methanol as the eluent.

[0020] In the step S6, the phenolic eluent is concentrated under reduced pressure to a constant amount, and the phenolic eluent is concentrated under reduced pressure to a constant amount at 50 °C.

[0021] The beneficial effects of the present invention are as follows: It can effectively treat distiller's grains and brewing wastewater separately, recover various reusable substances, greatly reduce resource waste, and can effectively reduce the comprehensive treatment cost through reuse, which is extremely beneficial to green development. Description of the Drawings

[0022] Figure 1 It is a schematic flow chart of at least one embodiment of the present invention. Detailed Embodiments

[0023] The technical solutions of the present invention are further described below, but the scope of protection claimed is not limited thereto.

[0024] The first embodiment of the present invention relates to a post-treatment method for brewing residues as shown in Figure 1 and includes the following steps:

[0025] S1. Extraction: Extracting distillers' grains or brewing wastewater with an equal volume of an organic solvent to obtain an organic-phase extraction solution and an aqueous-phase extraction solution;

[0026] S2. Back-extraction and concentration: After subjecting the aqueous-phase extraction solution to multi-stage vacuum concentration, two types of substances are obtained from the fractions, one type is monosaccharide substances, and the other type is oligosaccharide and short peptide substances; after subjecting the organic-phase extraction solution to vacuum concentration, the pH value is adjusted to alkaline, and then water is added for back-extraction to obtain an aqueous-phase back-extraction solution and an organic-phase back-extraction solution;

[0027] S3. pH adjustment: Adjusting the pH value of the aqueous-phase back-extraction solution to acidic with a hydrochloric acid solution, and then extracting with ethyl acetate to obtain a secondary organic-phase extraction solution; adjusting the pH value of the organic-phase back-extraction solution to acidic with a hydrochloric acid solution, and then adding water for back-extraction to obtain a secondary organic-phase back-extraction solution;

[0028] S4. Vacuum concentration: Vacuum concentrating the secondary organic-phase extraction solution to a constant weight to obtain organic acid substances; vacuum concentrating the secondary organic-phase back-extraction solution to a paste to obtain phenolic raw materials;

[0029] S5. Chromatography: Subjecting the phenolic raw materials to polyamide reverse-phase column chromatography to separate and obtain a water washing solution, a phenolic elution solution, and a column flushing solution;

[0030] S6. Vacuum concentration: Discarding the water washing solution and the column flushing solution, and vacuum concentrating the phenolic elution solution to a constant amount to obtain phenolic substances.

[0031] The second embodiment of the present invention is substantially the same as the first embodiment, mainly in the further optimization of the step details. In step S1, the organic solvent is ethyl acetate; in step S1, extraction is performed 3 times.

[0032] Preferably, in step S2, the aqueous-phase extraction solution is first vacuum concentrated at 60 °C, and then vacuum concentrated at 50 °C. After that, the fractions are collected by ELSD detection and divided into two parts. These two parts are vacuum concentrated to a constant weight at 60 °C to obtain two types of substances, one type is monosaccharide substances, and the other type is oligosaccharide and short peptide substances.

[0033] Preferably, in step S2, after vacuum concentrating the organic-phase extraction solution, adjusting the pH value to alkaline means vacuum concentrating at 45 °C, and then adjusting the pH value to 10 with sodium carbonate.

[0034] Preferably, in step S3, adjusting the pH value of the aqueous-phase back-extraction solution to acidic means adjusting the pH value of the aqueous-phase back-extraction solution to 4 with a 0.1% hydrochloric acid solution.

[0035] Preferably, in step S3, the pH value of the organic reverse extraction solution is adjusted to acidic with a hydrochloric acid solution, and the pH value of the organic reverse extraction solution is adjusted to 5 with a 0.1% hydrochloric acid solution.

[0036] The third embodiment of the present invention is substantially the same as the first embodiment, mainly in the further optimization of the step details. In step S4, the organic phase secondary extraction solution is concentrated under reduced pressure to a constant weight, and the organic phase secondary extraction solution is concentrated under reduced pressure to a constant weight at 45°C.

[0037] Preferably, in step S4, the organic phase secondary reverse extraction solution is concentrated under reduced pressure to a paste, and the organic phase secondary reverse extraction solution is concentrated under reduced pressure to a paste at 45°C.

[0038] Preferably, in step S5, TLC is used to detect the eluent by chromatography. 90% methanol is used as the eluent to obtain the phenolic eluent, pure water is used as the eluent to obtain the water-washed solution, and pure methanol is used as the eluent to obtain the column-washing solution.

[0039] Preferably, in step S6, the phenolic eluent is concentrated under reduced pressure to a constant amount, and the phenolic eluent is concentrated under reduced pressure to a constant amount at 50°C.

[0040] The step division of the above various methods is only for clear description. When implemented, they can be combined into one step or some steps can be split into multiple steps. As long as the same logical relationship is included, it is within the protection scope of this patent; adding insignificant modifications to the process or introducing insignificant designs, but not changing the core design of the process, are all within the protection scope of this patent.

[0041] Example 1

[0042] Based on the above embodiments, the following instruments, reagents and materials are used:

[0043] 1. Instruments:

[0044] 5L rotary evaporation unit (BC-R501CA); low-temperature cooling circulation pump (DLF-30 / 30); evaporative light scattering detector (Alltech ELSD6000); preparative HPLC system (DAC-150): ultrasonic cleaner (BK-1000B); electrothermal constant temperature forced air drying oven (DHG-9140A); refrigerator; electrothermal constant temperature vacuum drying oven (DZF-6050AB); electronic balance (LT2002E); medium-pressure column system (Φ5cm); 5000ml suction flask (GG-17); 200mm Buchner funnel; 500ml beaker.

[0045] 2. Reagents and materials:

[0046] (1) Reagents: methanol (chromatographic grade); ethyl acetate (analytical grade); sodium carbonate (analytical grade); hydrochloric acid; pure water.

[0047] (2) Materials: medium-speed qualitative filter paper; glass spotting capillary; polyamide (60 - 80 mesh); polyamide thin-layer plate; B - wide-range test paper; C18 packing.

[0048] (3) Fermentation broth raw materials.

[0049] Example 2

[0050] Based on the above implementation method, and using the instruments, reagents and materials of Example 1, as Figure 1 shown, the following steps are adopted:

[0051] (1 - 1) Extraction: A total of 3.5 L of distiller's grains or brewing wastewater is extracted 3 times with an equal volume of ethyl acetate to obtain an organic phase extract and an aqueous phase extract;

[0052] (2 - 1) Back-extraction: A total of 11 L of the extracted organic phase (ethyl acetate phase) extract is concentrated under reduced pressure to 2 L at 45 °C, then sodium carbonate is added to adjust the pH value to about 10, and it is back-extracted 3 times with an equal volume of water to obtain a neutral organic phase back-extract and an alkaline aqueous phase back-extract.

[0053] (3 - 1) Adjusting the pH of the aqueous phase: The aqueous phase back-extract is adjusted to a pH value of about 4 with 0.1% hydrochloric acid, and then extracted 3 times with an equal volume of ethyl acetate. After extraction, the organic phases are combined, concentrated under reduced pressure to constant weight at 45 °C, and then dried to constant weight by blowing air at 45 °C to obtain an organic acid fraction.

[0054] (4 - 1) Adjusting the pH of the organic phase: The organic phase back-extract is adjusted to a pH value of about 5 with 0.1% hydrochloric acid solution, and the resulting organic phase secondary back-extract after back-extracting 3 times with an equal volume of water is concentrated under reduced pressure to constant weight at 45 °C to obtain 800 mg of a paste.

[0055] (5 - 1) Chromatography: Polyamide reversed-phase column chromatography is used, and it is eluted with pure water, 80% methanol, and pure methanol respectively, and fractions with absorption when examined at 254 nm and 365 nm are collected by TLC detection;

[0056] TLC conditions: methanol - water (50 - 50), polyamide plate, examined under ultraviolet at 254 nm and 365 nm;

[0057] (6 - 1) Concentration of the aqueous phase: After multi-stage concentration under reduced pressure of the aqueous phase extract obtained in step (1 - 1), the fractions are collected by ELSD detection in the following manner:

[0058] Preparation conditions: Φ = 8 cm, AQ-C18 column, wavelength = 210 nm, flow rate = 140 ml / min, mobile phase: methanol-water (10:90), detected and tracked by HPLC;

[0059] HPLC conditions: methanol - 0.1% formic acid water (10:90), AQ-C18 column (4.6 * 250 mm, 5 μm), flow rate = 1.0 ml / min, ELSD (3.5 L / min, 110 °C);

[0060] It was concentrated under reduced pressure to constant weight at 60 °C to obtain two types of substances. One type was monosaccharide substances, and the other type was oligosaccharide and short peptide substances. The monosaccharide substances may contain glycerol.

[0061] Those of ordinary skill in the art can understand that the above embodiments are specific implementation concepts for realizing the present invention. In practical applications, various changes can be made to them in form and details without departing from the spirit and scope of the present invention.

Claims

1. A post-treatment method for brewing residues, characterized in that It includes the following steps: S1. Extraction: Extract distillers' grains or brewing wastewater with an equal volume of an organic solvent to obtain an organic phase extract and an aqueous phase extract; the organic solvent is ethyl acetate; S2. Back-extraction and concentration: First, concentrate the aqueous phase extract under reduced pressure at 60 °C, then concentrate it under reduced pressure at 50 °C, and then collect fractions by ELSD detection to obtain two parts. Concentrate these two parts under reduced pressure at 60 °C to constant weight to obtain two types of substances, one is monosaccharide substances, and the other is oligosaccharide and short peptide substances; Concentrate the organic phase extract under reduced pressure and then under reduced pressure at 45 °C, then adjust the pH value to 10 with sodium carbonate, and then perform back-extraction with water to obtain an aqueous phase back-extract and an organic phase back-extract; S3. pH adjustment: Adjust the pH value of the aqueous phase back-extract to acidic with a hydrochloric acid solution, and then extract with ethyl acetate to obtain a secondary organic phase extract; Adjust the pH value of the organic phase back-extract to acidic with a hydrochloric acid solution, and then perform back-extraction with water to obtain a secondary organic phase back-extract; S4. Vacuum concentration: Concentrate the secondary organic phase extract under reduced pressure at 45 °C to constant weight to obtain organic acid substances; Concentrate the secondary organic phase back-extract under reduced pressure at 45 °C to a paste to obtain phenolic raw materials; S5. Chromatography: Perform polyamide reverse-phase column chromatography on the phenolic raw materials, specifically chromatograph by detecting the eluent with TLC, use 90% methanol as the eluent to obtain a phenolic eluent, use pure water as the eluent to obtain a water wash solution, and use pure methanol as the eluent to obtain a column flushing solution; S6. Vacuum concentration: Discard the water wash solution and the column flushing solution, and concentrate the phenolic eluent under reduced pressure to a constant amount to obtain phenolic substances.

2. The post-treatment method for brewing residues according to claim 1, wherein In the step S1, extraction is performed 3 times.

3. The post-treatment method for brewing residues according to claim 1, wherein, In the step S3, when adjusting the pH value of the aqueous phase back-extract to acidic, the pH value of the aqueous phase back-extract is adjusted to 4 with a 0.1% hydrochloric acid solution.

4. The post-treatment method for brewing residues according to claim 1, characterized in that, In the step S3, when adjusting the pH value of the organic phase back-extract to acidic, the pH value of the organic phase back-extract is adjusted to 5 with a 0.1% hydrochloric acid solution.

5. The post-treatment method for brewing residues according to claim 1, wherein, In the step S6, when concentrating the phenolic eluent to a constant amount, the phenolic eluent is concentrated to a constant weight under reduced pressure at 50 °C.

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