A method for extracting complex organic acids from a waste liquid produced from a raspberry extract

Abstract

The present application provides a method for extracting complex organic acid from the waste liquid of the extract of Rubus corchorifolius L.f. The waste liquid of the column chromatography effluent of the Rubus corchorifolius L.f. extract is taken, the specific gravity of the secondary waste liquid is adjusted to obtain the column loading liquid, the column loading liquid is passed through a resin column A, water washing is performed, the column effluent and the water washing liquid are collected to obtain a combined liquid 1, the combined liquid 1 is passed through a resin column B, water washing is performed, reagent C is used for elution, and the eluate is collected. The combined liquid 2 is obtained by passing through a resin column D and collecting the effluent and the water washing liquid, vacuum concentration is performed, crystallization is performed, and filtration is performed to obtain quinic acid.

Description

Technical Field

[0001] This invention relates to the field of plant active ingredient extraction technology, and a method for extracting complex organic acids. Background Technology

[0002] Cranberries grow in the cold, wetlands of North America, with a global production area of ​​less than 40,000 acres, limited to five states in the northern United States (Massachusetts, Wisconsin, New Jersey, Oregon, and Washington), the Canadian provinces of Quebec and British Columbia, and Chile in South America. Cranberries were introduced to China in 2008, and after 10 years, fresh cranberries became available on the Chinese market, pioneering the cultivation of this high-efficiency crop in China and ending the country's reliance on imports. Functional factors (natural products) extracted from plants can be used as natural raw materials for pharmaceuticals, health products, cosmetics, food additives, and feed additives. Due to their definite functions, lack of toxic side effects, and natural origin, they meet people's requirements for "natural, nutritious, and multifunctional" products. The plant extraction industry has become one of the fastest-growing industries in China and also has a very broad market prospect in the international market.

[0003] Organic acids are a class of non-toxic, highly efficient organic substances, mainly including medium-chain fatty acids (formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, etc.), citric acid, benzoic acid, fumaric acid, lactic acid, etc. Organic acids are compounds whose molecular structure contains a carboxyl group (-COOH). They are widely distributed in the leaves, roots, and especially the fruits of traditional Chinese medicinal herbs, such as dried plum, schisandra chinensis, and raspberry. Common organic acids in plants include aliphatic mono-, di-, and polycarboxylic acids such as tartaric acid, oxalic acid, malic acid, citric acid, and ascorbic acid (i.e., vitamin C), as well as aromatic organic acids such as benzoic acid, salicylic acid, and caffeic acid. Except for a few existing in a free state, they generally combine with potassium, sodium, calcium, etc., to form salts, and some combine with alkaloids to form salts. Fatty acids often combine with glycerol to form esters or with higher alcohols to form waxes. Some organic acids are components of volatile oils and resins.

[0004] Cation and anion exchange resins are polymers of polybasic acids or bases with a network-like three-dimensional structure. There are many types of ion exchange resins, with polystyrene-based ion exchange resins being the most commonly used. These are polymerized from styrene and divinylbenzene to form a spherical network structure, with divinylbenzene acting as a crosslinking agent. Sulfonation with concentrated sulfuric acid yields polystyrene-based sulfonic acid ion exchange resins. Replacing the sulfonic acid groups with other groups yields a series of ion exchange resins, such as -COOH and -OH. The hydrogen ions on these groups can be exchanged with cations in the sample solution.

[0005] Macroporous adsorption resins are made by cross-linking and polymerizing styrene and propionate monomers with vinylbenzene as a cross-linking agent and toluene and xylene as porogens to form a porous framework structure. The resins are generally white, spherical particles and are a type of cross-linked polymer containing ion exchange groups. They are chemically stable, insoluble in acids, alkalis, and organic solvents, and unaffected by inorganic salts and strong ionic low-molecular-weight compounds. Summary of the Invention

[0006] A method for extracting complex organic acids from cranberry extract production waste liquid. This method utilizes plant waste.

[0007] The technical solution of this invention can be summarized as follows: S1. Adjust the specific gravity of the cranberry effluent wastewater to obtain the column loading solution; S2. Pass the solution through resin column A, collect the washing and effluent, and obtain combined liquid 1; S3. Take the combined solution 1, load it onto resin column B and wash with water; S4. Elute with solvent C and collect; S5. The eluent containing complex organic acids is passed through the resin column D again; S6. Collect the effluent and washing liquid to obtain combined liquid 2; S7. Vacuum concentration, crystallization and filtration yield organic acids.

[0008] According to claim 1, the present invention provides a method for extracting complex organic acids from cranberry extract production wastewater. The method is characterized by adjusting the specific gravity of the secondary wastewater concentrate from 1.28 g / ml to <1 g / ml. The organic acid content of the secondary wastewater concentrate is 15%~20%, the sugar-acid ratio is >3, and the titratable acid (as citric acid) is 15%~20%.

[0009] According to claim 1, the present invention provides a method for extracting complex organic acids from cranberry extract production waste liquid. The method is characterized by having a column loading volume of 1-10 BV and a water washing volume of 1-3 BV; and obtaining an eluent containing complex organic acids by passing it through a resin column D with a column loading volume of 3-15 BV and a water washing volume of 1-3 BV.

[0010] According to claim 1, the present invention provides a method for extracting complex organic acids from cranberry extract production wastewater. The method is characterized by a column flow rate of 0.1 BV to 0.5 BV / h.

[0011] According to claim 1, the present invention provides a method for extracting complex organic acids from cranberry extract production waste liquid, wherein the vacuum concentration is performed at a vacuum degree of -0.07MPa to -0.088MPa, the concentration temperature is <65℃, and the concentration time of each segment does not exceed 2 hours.

[0012] According to claim 1, the present invention provides a method for extracting a complex organic acid from cranberry extract production waste liquid, wherein the organic acid solvent C has an elution volume fraction of 30-75%.

[0013] According to claim 1, the present invention provides a method for extracting a complex organic acid from cranberry extract production waste liquid, wherein the crystallization time is 3~48H and the crystallization temperature is 0~15°.

[0014] According to claim 1, the present invention provides a method for extracting complex organic acids from cranberry extract production waste liquid, wherein the sifting parameters are 1500 r / min and the filter bag is 500 mesh.

[0015] This invention provides a method for extracting complex organic acids from cranberry extract production wastewater. The method utilizes resin adsorption for selective adsorption of the target product, thereby efficiently obtaining the target product, the complex organic acid. Detailed Implementation

[0016] This invention utilizes resin column chromatography, combined with crystallization purification, to achieve a total organic acid content greater than 80%. The extracted complex organic acids are rapidly extracted, highly efficient, and energy-saving, allowing for solvent recovery and reuse. This process is environmentally friendly, non-toxic, and pollution-free, reducing waste emissions and meeting market demands for separated complex organic acids. The invention is simple to operate, requires minimal equipment investment, and is suitable for industrial production.

[0017] This invention pioneers the comprehensive utilization of cranberry resources, significantly improving their overall utilization and holding great significance for the in-depth development of cranberry resources. This invention has good economic benefits and practical significance. Example 1

[0018] S1. Adjust the specific gravity of the cranberry effluent wastewater to 0.8 g / ml and the volume to 200 ml; S2. Pass the 732 type cation exchange resin through a resin column. The resin volume is 200 ml, and the water washing volume is 600 ml. Collect the column effluent and water washing liquid to obtain 1200 ml of combined solution 1. S3. Take 1200ml of the combined resin and pass it through the HPD-130 anion exchange resin column. The amount of resin is 300ml, and the amount of water washing is 600ml. Then, pass it through the resin column B. S4. Elute using a 5% sulfuric acid aqueous solution, detect sulfate ions by barium chloride, and collect 400 ml of the eluent without sulfuric acid (and the solution containing complex organic acids). S5. Pass 400ml of eluent containing complex organic acids through macroporous resin, using 100ml of resin, and wash with 200ml of water. S6. Collect the effluent and washing solution to obtain 800 ml of combined solution; S7. Vacuum concentration: -0.07 MPa to -0.088 MPa; concentration temperature: <65℃; concentrate to 80 ml, then stir to crystallize. After stirring for 10 hours, filter by spin (1500 r / min, 500 mesh filter bag). Dry at 55℃ to obtain the target product. Example 2

[0019] S1. Adjust the specific gravity of the cranberry effluent wastewater to 0.6 g / ml and the volume to 900 ml; S2. Pass the 732 type cation exchange resin through a resin column. The resin volume is 400 ml, the water washing volume is 800 ml, and the effluent and water washing liquid are collected to obtain 2100 ml of combined solution 1. S3. Take 2100ml of the combined resin and pass it through a resin column of HPD-130 anion exchange resin. The amount of resin is 600ml and the amount of water used for washing is 900ml. Then, pass the resin through column B. S4. Elute using a 2% sulfuric acid aqueous solution, detect sulfate ions by barium chloride, and collect 1400 ml of the eluent without sulfuric acid (and the solution containing complex organic acids). S5. Pass 1400ml of eluent containing complex organic acids through macroporous resin, using 300ml of resin, and wash with 900ml of water. S6. Collect the effluent and washing solution to obtain 2600 ml of combined solution; S7. Vacuum concentration was performed at a vacuum level of -0.07 MPa to -0.088 MPa, with a concentration temperature of <65℃. The solution was concentrated to 260 ml, then stirred for crystallization. After stirring for 25 hours, the solution was filtered using a filtration parameter of 1500 r / min and a 500 mesh filter bag. The product was then dried at 55℃ to obtain the target product.

Claims

1. This invention provides a method for extracting complex organic acids from cranberry extract production wastewater. The method involves taking cranberry extract column chromatography effluent wastewater. Adjusting the specific gravity of the secondary wastewater to obtain the loading solution, passing it through resin column A, washing with water, and collecting the column effluent and washing solution to obtain combined solution 1. Combining solution 1 is then passed through resin column B, washed with water, and eluted with reagent C. The eluent containing the complex organic acids is collected. This eluent is then passed through resin column D, and the effluent and washing solution are collected to obtain combined solution 2. This solution is then concentrated under vacuum, crystallized, and filtered to obtain the organic acids. Reagent C is an acidic solution, resin A is an acidic anion exchange resin, resin C is a cation exchange resin, and resin D is a macroporous resin.

2. The present invention, according to claim 1, provides a method for extracting a complex organic acid from cranberry extract production wastewater. Its characteristics are... The specific gravity of the secondary wastewater concentrate was adjusted from 1.28 g / ml to <1 g / ml. The organic acid content of the secondary wastewater concentrate was 15%~20%, the sugar-acid ratio was >3, and the titratable acid (as citric acid) was 15%~20%.

3. The present invention provides a method for extracting complex organic acids from cranberry extract production waste liquid according to claim 1. The method is characterized by having a column loading volume of 1-10 BV and a water washing volume of 1-3 BV; and obtaining an eluent containing complex organic acids by passing it through a resin column D with a column loading volume of 3-15 BV and a water washing volume of 1-3 BV.

4. The present invention, according to claim 1, provides a method for extracting a complex organic acid from cranberry extract production wastewater. Its characteristics are... The flow rate on the upper column is 0.1 BV~0.5 BV / h.

5. According to claim 1, the present invention provides a method for extracting complex organic acids from cranberry extract production waste liquid, wherein the vacuum concentration is performed at a vacuum degree of -0.07MPa to -0.088MPa, the concentration temperature is <65℃, and the concentration time for each stage of the stage does not exceed 2 hours.

6. According to claim 1, the present invention provides a method for extracting a complex organic acid from cranberry extract production waste liquid, wherein the organic acid solvent C is an aqueous solution of at least one inorganic acid or an aqueous solution of at least one organic acid.

7. According to claim 1, the present invention provides a method for extracting a complex organic acid from cranberry extract production waste liquid, wherein the crystallization time is 3~48H and the crystallization temperature is 0~15°C. According to claim 1, the present invention provides a method for extracting complex organic acids from cranberry extract production waste liquid, wherein the sifting parameters are 1500 r / min and the filter bag is 500 mesh.