CN112973173A

CN112973173A - Resource utilization method of super-enriched plant biomass

Info

Publication number: CN112973173A
Application number: CN201911315785.0A
Authority: CN
Inventors: 蔡文; 陈同斌
Original assignee: Institute of Geographic Sciences and Natural Resources of CAS
Current assignee: Institute of Geographic Sciences and Natural Resources of CAS
Priority date: 2019-12-18
Filing date: 2019-12-18
Publication date: 2021-06-18
Anticipated expiration: 2039-12-18
Also published as: CN112973173B

Abstract

The resource method of the biomass of the hyper-enriched plant provided by the invention comprises the steps of pretreating the hyper-enriched plant, extracting with alcohol and separating with a resin column, and separating to obtain six products; the alcohol extraction step comprises at least 2 times of alcohol extraction, wherein the volume fraction of the alcohol solution adopted in the first alcohol extraction is 35-75%, and the volume fraction of the alcohol solution adopted in the subsequent alcohol extraction is 35-95%; the six products are respectively: a mixture rich in cellulose and lignin; a mixture rich in inorganic elements; the mixture is rich in amino acids, proteins, monosaccharides, polysaccharides and inorganic elements; a mixture rich in polyphenols; a mixture rich in saponins; is rich in terpenoids and other liposoluble compounds. The resource method of the hyper-enriched plant biomass provided by the invention can separate, collect and utilize the soluble organic components and the inorganic elements in the hyper-enriched plant biomass rich in the harmful inorganic elements.

Description

Resource utilization method of super-enriched plant biomass

Technical Field

The invention relates to the technical field of environmental engineering, in particular to a resource method of hyper-enriched plant biomass.

Background

Currently, the area and extent of heavy metal contaminated soil is increasing year by year due to mining, metal smelting, and contamination by industrial sewage and sludge. With the increase of heavy metal pollution of soil, the agricultural cultivated land area is sharply reduced, and the soil quality of a considerable amount of farmlands is gradually reduced. Particularly serious is that the pollution generated by toxic heavy metals in a soil system has the characteristics of concealment, long-term property and irreversibility. Heavy metal elements entering the soil do not present harm to the environment and crops for a certain period of time, but when the accumulated amount exceeds the soil bearing capacity or soil capacity, harm is caused to crops and human bodies, thereby causing serious ecological problems.

The traditional environment-polluted soil remediation technology usually adopts physical and chemical methods, such as a soil dumping and burying method, a dilution method, a leaching method, a physical separation method, a stabilization and chemical method and the like, but the methods have the defects of high cost, difficult management, easy secondary pollution and large environmental disturbance, so the traditional treatment method cannot effectively solve the problem of heavy metal soil pollution. In recent years, Phytoremediation technology (Phytoremediation) has become ー which is a main approach for soil pollution treatment due to its low cost, suitability for large-scale application, benefit for soil ecosystem maintenance, aesthetic value for polluted land landscape and no damage to environment, and its mechanism is that plants have special absorption and enrichment capacity for pollution elements in soil.

Biomass of hyper-enriched plants (such as ciliate desert-grass, sedum alfredii hance, eriosema gigantea and the like) harvested from soil remediation and plant mining projects usually contains more than ten to ten thousand times of harmful inorganic elements (such as arsenic, lead, cadmium and mercury) than ordinary non-enriched plants. At present, the biomass rich in harmful inorganic elements is generally treated by the following three methods: 1. adopting harmless incinerated ash as a treatment strategy for hazardous waste landfill; 2. carrying out high-temperature high-pressure pyrolysis on the hyper-enriched plant biomass rich in the harmful inorganic elements to prepare pyrolysis oil or pyrolysis gas; 3. the method comprises the steps of firstly separating and removing harmful inorganic elements in the super-enriched plant biomass in a solvent extraction mode and the like, then changing the biomass into common biomass, and then switching into a conventional biomass resource treatment method.

The above method 1 undoubtedly increases the risk of secondary pollution and additionally increases the application costs of the hyper-enriched plants; although the method 2 and the method 3 avoid the influence of harmful inorganic elements on the resource utilization of the hyper-enriched plant biomass to a certain extent, the two treatment methods only develop the resource utilization value of cellulose, lignin and other insoluble matters in the hyper-enriched plant biomass, neglect and waste other soluble components (such as secondary metabolites, amino acids, proteins and the like) with values far higher than those of the cellulose and the lignin in the plant, and cause the resource utilization economic value in the hyper-enriched plant biomass to be lower: in the biomass treatment mode of incineration or pyrolysis, soluble components with higher value are decomposed, denatured and inactivated along with extreme treatment conditions; the method for separating harmful inorganic elements from biomass by solvent extraction only separates inorganic elements from cellulose and the like, but cannot separate plant soluble organic components from harmful inorganic elements.

If the soluble organic components and the harmful inorganic elements in the super-enriched plant biomass rich in the harmful inorganic elements are separated, collected and recycled, the application cost of the super-enriched plant can be obviously reduced, the application potential of the super-enriched plant is greatly improved, and the practical problem that a large amount of harmful biomass is produced in the application process of the super-enriched plant is solved. Therefore, how to separate, collect and recycle the soluble organic components and the harmful inorganic elements in the hyper-enriched plant biomass rich in the harmful inorganic elements is a technical problem to be solved at present.

Disclosure of Invention

Therefore, the technical problem to be solved by the invention is to overcome the defect that the soluble organic components and the harmful inorganic elements in the hyper-enriched plant biomass rich in the harmful inorganic elements cannot be separated, collected and recycled in the prior art, thereby providing a method for recycling the hyper-enriched plant biomass.

Therefore, the invention provides the following technical scheme:

a resource utilization method of hyper-enriched plant biomass comprises the following steps: pretreating hyper-enriched plant, extracting with alcohol and separating with resin column to obtain six products; the alcohol extraction step comprises at least 2 times of alcohol extraction, wherein the volume fraction of the alcohol solution adopted in the first alcohol extraction is 35-75%, and the volume fraction of the alcohol solution adopted in the subsequent alcohol extraction is 35-95%;

the six products are respectively: the product is a mixture rich in cellulose and lignin, and the product is a mixture rich in inorganic elements; the third product is a mixture rich in amino acids, proteins, monosaccharides, polysaccharides and inorganic elements; the product IV is a mixture rich in polyphenol compounds; the fifth product is a mixture rich in saponin compounds; the product VI is a mixture rich in terpenoids and other fat-soluble compounds.

If fresh super-enriched plants are adopted, the water content in the fresh super-enriched plants is contained when the volume fraction of the alcohol solution adopted in the first alcohol extraction is calculated; if a dried super-enriched plant is used, the moisture in the dried super-enriched plant is not considered.

Based on the total weight of the product III, the content of amino acids and proteins in the product III is more than 15 wt%, the content of saccharides is more than 5 wt%, and the content of harmless inorganic elements is more than 1 wt%;

and/or, the content of the polyphenol compound in the product IV is more than 20 wt% based on the total weight of the product IV;

and/or, the content of the saponin compounds in the product five is more than 10 wt% based on the total weight of the product five;

and/or, the terpenoid content in the product VI is more than 11 wt% and the other fat-soluble compounds are more than 5 wt% based on the total weight of the product VI.

In the alcohol extraction step, in the first alcohol extraction, the mass-volume ratio of the super-enriched plant dry weight to the alcohol solution is 1:6-10(kg: L);

in the subsequent alcohol extraction, the mass-volume ratio of the super-enriched plant dry weight to the alcohol solution is 1:4-8(kg: L).

The alcohol extraction adopts heating extraction and/or ultrasonic extraction;

the temperature for heating and extracting is 40-80 deg.C, and the time is 20-180 min; the ultrasonic extraction temperature is 20-60 deg.C, the time is 20-180min, and the frequency is 20-60 KHz.

Extracting residues obtained after alcohol extraction are a first product;

concentrating the extracting solution obtained after alcohol extraction, adding water for dilution, loading the sample to an acidified resin column after acidification, and collecting the effluent of loading the sample;

wherein the volume-mass ratio of the volume of the resin column to the dry weight of the hyper-enrichment plant is 0.8-1.4:1(kg: L), and the sample loading flow rate is 1-3 BV/h.

Preferably, after each alcohol extraction, the temperature is kept for 1-2h, and then the extraction solution is separated from the extraction residue.

Eluting the loaded resin column with an acidic aqueous solution to obtain an eluent, combining the eluent and the loaded effluent, performing chemical precipitation treatment, and filtering to obtain a solid precipitate and a filtrate, wherein the solid precipitate is a product II; drying the filtrate to obtain a third product;

preferably, the elution volume of the acidic aqueous solution is 2-5BV, and the flow rate is 1-3 BV/h;

more preferably, the filtrate is dried after being concentrated to a solid content of 25% to 35%.

The resin column is a neutral, nonpolar or weak polar macroporous resin column; preferably, the macroporous resin column is any one of D101, AB-8, H-60, XDA-1, D101b, LSA-20, LSA-30, HP-10, XDA-5 or XDA-6.

Acidifying the concentrated and diluted extracting solution and the resin column by using volatile acid;

preferably, the volatile acid is any one of acetic acid, formic acid and hydrochloric acid; the mass fraction of the acid in the acidified concentrated diluted extract, the mass fraction of the acid in the acidic aqueous solution used for acidifying the resin column and the mass fraction of the acid in the acidic aqueous solution used for eluting the acidified resin column are all 0.1%.

Preferably, the extract obtained after the alcohol extraction is concentrated until the volume concentration of the alcohol is lower than 2%.

Adding water into the concentrated extracting solution to dilute the volume (L) to 2-3 times of the dry weight (kg) of the hyper-enriched plants.

Sequentially eluting the resin column eluted by the acidic aqueous solution with 35-50% of alcoholic solution by volume fraction to obtain a fourth product, eluting the fourth product with 65-70% of alcoholic solution by volume fraction to obtain a fifth product, and eluting the fifth product with 90-95% of alcoholic solution by volume fraction to obtain a sixth product;

preferably, the eluates are concentrated to a solid content of 25-35% and then dried.

The elution volume of the 35-50% alcohol solution is 2-4BV, and the flow rate is 0.5-1.2 BV/h;

and/or the elution volume of the 65-70% volume fraction alcohol solution is 1-3BV, and the flow rate is 0.5-1.2 BV/h;

and/or the elution volume of the alcohol solution with the volume fraction of 90-95% is 3-4BV, and the flow rate is 1.5-2 BV/h.

The pretreatment is to crush and homogenize fresh super-enriched plants, or cut or crush dried super-enriched plants;

and/or the hyper-enriched plant is at least one of ciliate desert-grass, Alyssum murale, Sedum alfredii Hance and Trifolium pratense; preferably, the hyper-enriched plant is the aerial part of ciliate desert-grass planted in arsenic-contaminated soil;

and/or the fresh super-enriched plant means that the time interval from harvesting to pretreatment is within three days, and the dried super-enriched plant means that the fresh super-enriched plant is subjected to drying treatment within five days.

The drying treatment refers to drying the fresh hyper-enriched plants in any one of freeze-drying, sun-drying, drying and shade-drying modes, and the fresh hyper-enriched plants are prevented from being directly sun-dried, damp-shielded and exposed at high temperature during storage.

Preferably, the dried super enriched plant is cut or pulverized to 0.1mm-500 mm.

The super-enriched plant is derived from soil or other matrixes slightly polluted or polluted above, and the enrichment coefficient of the ground tissue of the plant exceeds 1.

The technical scheme of the invention has the following advantages:

1. the resource method of the super-enriched plant biomass provided by the invention combines alcohol extraction and resin column separation to separate and obtain six products: the alcohol extraction step comprises at least 2 times of alcohol extraction, wherein the volume fraction of the alcohol solution adopted in the first alcohol extraction is 35-75%, and the volume fraction of the alcohol solution adopted in the subsequent alcohol extraction is 35-95%; the six products are respectively: the product is a mixture rich in cellulose and lignin, and the product is a mixture rich in inorganic elements; the third product is a mixture rich in amino acid, protein, monosaccharide, polysaccharide and harmless inorganic elements; the product IV is a mixture rich in polyphenol compounds; the product fifthly is a mixture containing saponin compounds; sixthly, the product is a mixture rich in terpenoid and other fat-soluble compounds;

the inventor finds that the main reason that soluble organic components and harmful inorganic elements in super-enriched plant biomass rich in harmful inorganic elements cannot be separated, collected and recycled in the prior art is that the concentration of an alcohol solution is not properly selected in the primary extraction process of the super-enriched plant in the alcohol solution, only the inorganic elements are separated from cellulose and the like, but various available products such as amino acids, proteins, saccharides, phenols, saponins, terpenes and lipid soluble compounds contained in the alcohol extract cannot be obtained through fine separation or the yield of the separation is extremely low, the resource utilization cannot be carried out, and particularly, in the alcohol extraction process, if the proportion of alcohol in the extract is too high, the extraction of active substances is influenced, the extraction yield of the active substances is reduced, and chlorophyll and the like are excessively dissolved out, so that the influence is caused on process equipment and the product quality; and the dissolving-out efficiency of water-soluble harmful inorganic elements is reduced, a large amount of water-soluble harmful inorganic elements remain in the extracted biomass, and the harmless quality of the biomass is reduced; when the alcohol ratio is too low, the solubility of partial active substances is reduced, and the yield and the quality of the product IV-VI are greatly reduced; therefore, the extracting solution obtained by the first alcohol extraction and the extracting solution obtained by the subsequent alcohol extraction need to be ethanol solutions with specific volume fractions, so that the extraction efficiency of soluble components and the release efficiency of harmful inorganic elements can be both considered, and the soluble organic components and the harmful inorganic elements in the super-enriched plant biomass rich in the harmful inorganic elements can be separated, collected and recycled;

further, the product for separation has the following functions and can be recycled: the first product is rich in cellulose and lignin, and can be subjected to conventional biomass treatment after being dried until the water content is lower than 15%, such as: composting, pyrolysis, fuels, building materials, and the like; the product II is rich in inorganic elements and can be used for smelting heavy metals; the product III is rich in amino acids, proteins, monosaccharides, polysaccharides and inorganic elements, and has potential value as dietary supplement and nutriment; the product IV is rich in polyphenol compounds, and has the effects of resisting oxidation, inhibiting bacteria, resisting tumors and diminishing inflammation; the product V is rich in saponin compounds and has potential antibacterial and antitumor effects; the product VI is rich in terpenoids and other fat-soluble compounds; has anthelmintic and antioxidant effects; not only the soluble organic components and the harmful inorganic elements in the hyper-enriched plant biomass are separated, but also the soluble organic components are classified, separated and recycled; realizes the recycling of the biomass of the hyper-enriched plants, and brings more economic values for the planting and the application of the hyper-enriched plants. Moreover, the technology has strong controllability and green and environment-friendly process, and secondary pollution can not occur after harmful elements are collected.

2. According to the resource method of the super-enriched plant biomass provided by the invention, the inventor finds that the elution parameters in the resin separation process have great influence on the quality of products III to VI, if the parameter selection is not proper, the products III to VI cannot be separated, and various products are mixed up, especially when the resin column is eluted by alcohol solution for the first time, if the alcohol proportion in the eluent exceeds 50% or the elution volume exceeds 4BV, the polyphenol proportion in the product IV is reduced and the saponin proportion is increased, so that the molecular structure difference in the final product IV is large, and the final effect is unstable or changed; the invention can ensure the product quality of products three to six by limiting the elution order, the alcohol content in the eluent, the elution volume and the elution flow rate in the separation process of the resin column.

Detailed Description

The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.

The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.

Example 1

The embodiment provides a resource utilization method of hyper-enriched plant biomass, which specifically comprises the following steps:

collecting 2.5 tons of overground part of fresh ciliate desert-grass with water content of 60% from a moderate arsenic-polluted farmland, directly crushing and homogenizing, ultrasonically extracting for 180min at 60 ℃ and 25KHz by 6000L of ethanol aqueous solution with volume fraction of 47%, preserving heat for 2 hours after extraction is finished, and collecting a first extracting solution and first extracting residues;

further heating and extracting the first extraction residue with 8000L of 95% ethanol water solution at 80 deg.C for 180min, maintaining the temperature for 2 hr, and collecting the second extractive solution and the second extraction residue;

dissolving the second extraction residue in 65% ethanol water 5000L, ultrasonic extracting at 40 deg.C and 25KHz for 20min, maintaining the temperature for 1 hr, and collecting the third extractive solution and the third extraction residue;

the third extraction residue is a mixture which does not contain harmful inorganic elements and mainly contains cellulose and lignin, namely a product I; after the product is dried in the sun until the water content is lower than 15%, conventional biomass treatment is carried out, such as: composting, pyrolysis, fuels, building materials, and the like.

Mixing the first extract, the second extract and the third extract, heating and concentrating until the volume fraction of ethanol is 1%, then adding water to dilute until the volume of the solution is 2000L, then adding concentrated hydrochloric acid with the mass fraction of 36% until the final mass fraction of hydrochloric acid in the diluent is 0.1%, and uniformly stirring for later use; balancing the macroporous resin column D101 with 0.1% hydrochloric acid aqueous solution by mass fraction, wherein the volume of the macroporous resin bed is 1000L, then loading the acidified extract to the balanced macroporous resin column D101 at a flow rate of 3BV/h, and collecting the effluent.

After the sample loading is finished, eluting the macroporous resin column D101 by using 0.1 percent hydrochloric acid aqueous solution by mass fraction, wherein the elution volume is 4BV, the flow rate is 2BV/h, collecting eluent, combining the eluent with the effluent, concentrating under reduced pressure, adding calcium hydroxide to adjust the pH value to 8, then adding ferric trichloride to the concentrated solution until the final concentration of the ferric trichloride is 0.8g/L, precipitating inorganic elements, and carrying out centrifugal filtration to obtain a precipitate rich in the inorganic elements and a filtrate rich in amino acid, protein, monosaccharide, polysaccharide and the inorganic elements; and crushing the precipitate rich in the inorganic elements by using freeze-dried powder to obtain a product II, concentrating the filtrate until the solid content is 25%, and drying and crushing to obtain a product III.

Continuously eluting the macroporous resin column D101 by using an ethanol aqueous solution with the volume fraction of 50 percent, wherein the elution volume is 3BV, and the flow rate is 0.8 BV/h; collecting eluent, concentrating the eluent until the solid content is 30%, and then carrying out spray drying to obtain a product IV rich in polyphenol compounds.

Continuously eluting the macroporous resin column D101 by using 65 percent ethanol water solution with the volume fraction of 1BV and the flow rate of 0.5 BV/h; collecting eluent, concentrating the eluent until the solid content is 35%, and then drying and crushing the eluent to obtain a product V rich in saponin compounds.

Continuously eluting the macroporous resin column D101 by using an ethanol aqueous solution with the volume fraction of 92 percent, wherein the elution volume is 4BV, and the flow rate is 1.8 BV/h; collecting the eluent, concentrating the eluent until the solid content is 28%, drying in the shade, and crushing to obtain a product six rich in terpenoid.

Example 2

collecting 3.1 tons of overground part of fresh ciliate desert-grass from a heavily arsenic-polluted farmland, wherein the moisture content of the overground part is 80%, the moisture content of the overground part is 60%, the temperature of the overground part is 10 ℃, the overground part is stored for 2 days under the condition that sunlight is prevented from being directly exposed to the sun, after freeze drying treatment is carried out for 3 days, the moisture content of the overground part is measured to be 10%, after the overground part is cut to be 0.1mm, 4340L of ethanol water solution with the volume fraction of 75% is used for carrying out ultrasonic extraction at 40 ℃ and 60KHz for 20min, after the extraction is finished, the temperature is;

extracting the first extraction residue with 35% ethanol aqueous solution 3500L at 40 deg.C for 140min, maintaining the temperature for 1 hr, and collecting the second extractive solution and the second extraction residue;

dissolving the second extraction residue in 35% ethanol water 3500L, heating at 80 deg.C for 180min, extracting, holding the temperature for 2 hr, and collecting the third extractive solution and the third extraction residue;

Mixing the first extractive solution, the second extractive solution and the third extractive solution, heating and concentrating until the volume fraction of ethanol is 1.2%, adding water to 1860L, adding acetic acid to the final mass fraction of acetic acid in the diluent is 0.1%, and stirring well for use; equilibrating macroporous resin column LSA-20 with 0.1% citric acid aqueous solution, wherein the volume of macroporous resin bed is 868L, then loading acidified extract to the equilibrated macroporous resin column LSA-20 at flow rate of 1BV/h, and collecting effluent.

After the sample loading is finished, eluting the LSA-20 of the macroporous resin column by using 0.1 percent citric acid aqueous solution by mass fraction, wherein the elution volume is 5BV, the flow rate is 3BV/h, collecting eluent, merging the eluent with the effluent, concentrating under reduced pressure, adding calcium hydroxide to adjust the pH value to 10, then adding ferric trichloride to the concentration liquid until the final concentration of the ferric trichloride is 0.9g/L, precipitating inorganic elements, and centrifugally filtering to obtain inorganic element-rich precipitate and filtrate rich in amino acid, protein, monosaccharide, polysaccharide and inorganic elements; drying and crushing the precipitate rich in the inorganic elements to obtain a second product, concentrating the filtrate until the solid content is 30%, and then performing spray drying to obtain a third product.

Continuously eluting the LSA-20 macroporous resin column with 35% ethanol water solution by volume fraction, wherein the elution volume is 2BV, and the flow rate is 0.5 BV/h; collecting eluent, concentrating the eluent until the solid content is 32%, and crushing the freeze-dried powder to obtain a product IV rich in the polyphenol compounds.

Continuously eluting the macroporous resin column LSA-20 by using an ethanol water solution with the volume fraction of 75 percent, wherein the elution volume is 3BV, and the flow rate is 0.9 BV/h; collecting eluent, concentrating the eluent until the solid content is 32%, and then drying in the shade and crushing to obtain a product V rich in saponin compounds.

Continuously eluting the LSA-20 macroporous resin column with 90% ethanol water solution by volume fraction, wherein the elution volume is 3BV, and the flow rate is 2 BV/h; collecting the eluent, concentrating the eluent until the solid content is 27%, and drying and crushing the eluent to obtain a product six rich in terpenoid.

Example 3

collecting 1 ton of fresh rhodiola Dongnan from farmland with moderate cadmium pollution, wherein the water content is 60%; 1.6 tons of fresh aerial parts of ciliate desert-grass, its moisture content is 75%; collecting mixture of Sedum alfredii Hance and herba Pteridis Multifidae, pulverizing, homogenizing, extracting with 64% methanol water solution 8000L at 80 deg.C for 120min, maintaining the temperature for 2 hr, and collecting first extractive solution and first extraction residue;

further extracting the first extraction residue with 55% methanol water solution 5600L at 60 deg.C under 40KHz ultrasonic for 20min, maintaining the temperature for 2 hr after extraction is completed, and collecting the second extractive solution and the second extraction residue;

further dissolving the second extraction residue in 95% methanol water 3200L at 60 deg.C under 20KHz ultrasonic extraction for 100min, maintaining the temperature for 2 hr after extraction, and collecting the third extractive solution and the third extraction residue;

Mixing the first extract, the second extract and the third extract, heating and concentrating until the volume fraction of methanol is 1.5%, then adding water until the volume of the solution is 1600L, then adding 85% formic acid until the final mass fraction of acetic acid in the diluent is 0.1%, and uniformly stirring to obtain an acidified extract for later use; balancing macroporous resin column H-60 with acetic acid water solution with mass fraction of 0.1% and macroporous resin bed volume of 1120L, loading acidified extractive solution onto the balanced macroporous resin column H-60 at flow rate of 2BV/H, and collecting effluent.

After the sample loading is finished, eluting a macroporous resin column H-60 by using an acetic acid aqueous solution with the mass fraction of 0.1%, wherein the elution volume is 2BV, the flow rate is 1BV/H, collecting eluent, combining the eluent with the effluent, concentrating under reduced pressure, adding calcium hydroxide to adjust the pH value to 9, then adding ferric trichloride to the concentrated solution until the final concentration of the ferric trichloride is 1.0g/L, precipitating inorganic elements, and carrying out centrifugal filtration to obtain a precipitate rich in the inorganic elements and a filtrate rich in amino acid, protein, monosaccharide, polysaccharide and the inorganic elements; and crushing the precipitate rich in the inorganic elements into a second product by using freeze-dried powder, concentrating the filtrate until the solid content is 35%, and then drying in the shade and crushing to obtain a third product.

Continuously eluting the macroporous resin column H-60 by using 40 percent methanol aqueous solution with the volume fraction, wherein the elution volume is 4BV, and the flow rate is 1.2 BV/H; collecting eluent, concentrating the eluent until the solid content is 33%, and then drying and crushing to obtain a product IV rich in polyphenol compounds.

Continuously eluting the macroporous resin column H-60 by using a methanol aqueous solution with the volume fraction of 70 percent, wherein the elution volume is 2BV, and the flow rate is 1.2 BV/H; collecting eluent, concentrating the eluent until the solid content is 30%, and spray drying to obtain product V rich in saponin compounds.

Continuously eluting the macroporous resin column H-60 by using 95 percent methanol aqueous solution with the volume fraction of 3BV and the flow rate of 1.5 BV/H; collecting the eluent, concentrating the eluent until the solid content is 29%, and then drying in the shade and crushing to obtain a product six rich in terpenoid.

Comparative example 1

The comparative example provides a resource method of hyper-enriched plant biomass, which specifically comprises the following steps:

collecting 2.5 tons of overground part of fresh ciliate desert-grass with water content of 60% from a moderate arsenic-polluted farmland, directly crushing and homogenizing, ultrasonically extracting for 180min at 60 ℃ and 25KHz by using 6000L of ethanol aqueous solution with volume fraction of 95%, preserving heat for 2 hours after extraction is finished, and collecting a first extracting solution and first extracting residues;

dissolving the second extraction residue in 95% ethanol at a volume fraction of 5000L, ultrasonically extracting at 40 deg.C and 25KHz for 20min, maintaining the temperature for 1 hr, and collecting the third extractive solution and the third extraction residue;

and the third extraction residue is the product I.

Mixing the first extract, the second extract and the third extract, heating and concentrating until the volume fraction of ethanol is 1%, then adding water until the volume of the solution is 2000L, adding concentrated hydrochloric acid with the mass fraction of 36% until the final mass fraction of hydrochloric acid in the diluent is 0.1%, and uniformly stirring to obtain an acidified extract for later use; balancing the macroporous resin column D101 with 0.1% hydrochloric acid aqueous solution by mass fraction, wherein the volume of the macroporous resin bed is 1000L, then loading the acidified extract to the balanced macroporous resin column D101 at a flow rate of 3BV/h, and collecting the effluent.

After the sample loading is finished, eluting the macroporous resin column D101 by using 0.1 percent hydrochloric acid aqueous solution by mass fraction, wherein the elution volume is 4BV, the flow rate is 2BV/h, collecting eluent, combining the eluent with the effluent, concentrating under reduced pressure, adding calcium hydroxide to adjust the pH value to 8, then adding ferric trichloride to the concentrated solution until the final concentration of the ferric trichloride is 0.8g/L, precipitating inorganic elements, and carrying out centrifugal filtration to obtain precipitate and filtrate; and crushing the precipitate by using freeze-dried powder to obtain a product II, concentrating the filtrate until the solid content is 25%, and drying and crushing to obtain a product III.

Continuously eluting the macroporous resin column D101 by using an ethanol aqueous solution with the volume fraction of 50 percent, wherein the elution volume is 3BV, and the flow rate is 0.8 BV/h; and collecting eluent, concentrating the eluent until the solid content is 30%, and then carrying out spray drying to obtain a product IV.

Continuously eluting the macroporous resin column D101 by using 65 percent ethanol water solution with the volume fraction of 1BV and the flow rate of 0.5 BV/h; collecting eluent, concentrating the eluent until the solid content is 35%, and then drying and crushing the eluent to obtain a product V.

Continuously eluting the macroporous resin column D101 by using an ethanol aqueous solution with the volume fraction of 92 percent, wherein the elution volume is 4BV, and the flow rate is 1.8 BV/h; collecting eluent, concentrating the eluent until the solid content is 28%, drying in the shade and crushing to obtain a product six.

Comparative example 2

collecting 2.5 tons of fresh ciliate desert-grass with water content of 60% from farmland with moderate arsenic pollution, crushing, homogenizing, ultrasonically extracting with 6000L of 35% ethanol water solution at 60 deg.C and 25KHz for 180min, keeping the temperature for 2 hours after extraction, and collecting the first extract and the first extraction residue;

further heating and extracting the first extraction residue with 20% ethanol water solution 8000L at 80 deg.C for 180min, maintaining the temperature for 2 hr, and collecting the second extractive solution and the second extraction residue;

dissolving the second extraction residue in 20 vol% ethanol solution 5000L, ultrasonic extracting at 40 deg.C and 25KHz for 20min, maintaining the temperature for 1 hr, and collecting the third extractive solution and the third extraction residue;

and the third extraction residue is the product I.

Mixing the first extract, the second extract and the third extract, heating and concentrating until the volume fraction of ethanol is 1%, then adding water until the volume of the solution is 2000L, then adding concentrated hydrochloric acid with the mass fraction of 36% until the final mass fraction of hydrochloric acid in the diluent is 0.1%, and uniformly stirring to obtain an acidified extract for later use; balancing the macroporous resin column D101 with 0.1% hydrochloric acid aqueous solution by mass fraction, wherein the volume of the macroporous resin bed is 1000L, then loading the acidified extract to the balanced macroporous resin column D101 at a flow rate of 3BV/h, and collecting the effluent.

After the sample loading is finished, eluting the macroporous resin column D101 by using 0.1 percent hydrochloric acid aqueous solution by mass fraction, wherein the elution volume is 4BV, the flow rate is 2BV/h, collecting eluent, combining the eluent with the effluent, concentrating under reduced pressure, adding calcium hydroxide to adjust the pH value to 8, then adding ferric trichloride until the final concentration of the ferric trichloride in the concentrated solution is 0.8g/L, precipitating inorganic elements, and carrying out centrifugal filtration to obtain precipitate and filtrate; and crushing the precipitate by using freeze-dried powder to obtain a product II, concentrating the filtrate until the solid content is 25%, and drying and crushing to obtain a product III.

Continuously eluting the macroporous resin column D101 by using an ethanol aqueous solution with the volume fraction of 60 percent, wherein the elution volume is 3BV, and the flow rate is 0.8 BV/h; and collecting eluent, concentrating the eluent until the solid content is 30%, and then carrying out spray drying to obtain a product IV.

Continuously eluting the macroporous resin column D101 by using 70 percent ethanol water solution with the volume fraction of 1BV and the flow rate of 0.5 BV/h; collecting eluent, concentrating the eluent until the solid content is 35%, and then drying and crushing the eluent to obtain a product V.

Continuously eluting the macroporous resin column D101 by using an ethanol aqueous solution with the volume fraction of 95 percent, wherein the elution volume is 4BV, and the flow rate is 1.8 BV/h; collecting eluent, concentrating the eluent until the solid content is 28%, drying in the shade and crushing to obtain a product six.

Examples of the experiments

The products obtained in examples 1 to 3 and comparative examples 1 to 2 were examined and identified, and the results are shown in Table 1 below.

Wherein, the determination of the arsenic content is carried out by adopting an atomic fluorescence spectrophotometer according to GB5009.11-2014 national food safety standard-the determination method of total arsenic and inorganic arsenic in food;

the cadmium content is measured by adopting an atomic absorption spectrophotometer according to GB 5009.15-2014 national food safety standard-method for measuring cadmium in food;

the content of amino acid is determined by using a total amino acid (T-AA) determination kit (colorimetric method) of Nanjing institute of bioengineering research, Ltd;

the sugar content is measured by adopting a phenol-sulfuric acid colorimetric method;

detecting the content of other inorganic elements except arsenic and cadmium by adopting an inductively coupled plasma mass spectrometer (ICP-MS) and an inductively coupled plasma emission spectrometer (ICP-OES) according to GB 5009.268-2016 national food safety standard-a method for determining multiple elements in food;

detecting the content of total polyphenol according to the detection method of the content of tea polyphenol and catechins in tea leaves in GBT 8313-2018;

the saponin and the terpenoid are measured by liquid chromatography or gas chromatography and mass spectrum one by one and accumulated calculation; wherein, the detector of the liquid chromatogram or the gas chromatogram is ultraviolet, evaporative light scattering or a photoelectric array.

TABLE 1 results for each product obtained in examples 1-3 and comparative examples 1-2

Note: the content of substances in each product in the table is the mass percent of the total weight of each product; wherein, the measurement conditions of the data are as follows: the products were dried to a moisture content of 6%.

The data in the table show that the resource method of the hyper-enriched plant biomass provided by the invention can effectively separate, collect and utilize the soluble organic components and the harmful inorganic elements in the hyper-enriched plant biomass as resources, wherein the main components in the product I are lignin and cellulose, the content of the harmful inorganic elements is very low, and the product I can be used for composting, pyrolysis, combustion and the like within a limited range; harmful inorganic elements are mainly concentrated in the product II and can be used for smelting heavy metals; the soluble organic components are further separated from the third product to the sixth product and are respectively used for dietary supplement and nutriment; anti-oxidation, anti-bacterial, anti-tumor and anti-inflammatory; bacteriostasis and anti-tumor; expelling parasites and resisting oxidation. From the experimental data of example 1 and comparative example 1, it can be seen that too high a proportion of alcohol in the alcohol extraction step affects the extraction of active substances, and the content of harmful inorganic elements in product one is very high, which is not beneficial to resource treatment, the content and yield of active ingredients in product three are low, and the yield is reduced although the proportion of active ingredients in products four to six is high. As can be seen from the experimental data of example 1 and comparative example 2, the ratio of alcohol in the alcohol extraction step is too low, and the yield of the product four to the product six and the content of the effective components in the product six are greatly reduced.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims

1. A resource utilization method of hyper-enriched plant biomass is characterized by comprising the following steps: pretreating hyper-enriched plant, extracting with alcohol and separating with resin column to obtain six products; the alcohol extraction step comprises at least 2 times of alcohol extraction, wherein the volume fraction of the alcohol solution adopted in the first alcohol extraction is 35-75%, and the volume fraction of the alcohol solution adopted in the subsequent alcohol extraction is 35-95%;

2. The resource utilization method of the biomass of the super-enriched plants as claimed in claim 1, wherein in the alcohol extraction step, the mass-volume ratio of the dry weight of the super-enriched plants to the alcohol solution in the first alcohol extraction is 1: 6-10;

in the subsequent alcohol extraction, the mass-volume ratio of the dry weight of the hyper-enriched plant to the alcohol solution is 1: 4-8.

3. The resource utilization method of the biomass of the super-enriched plants as claimed in claim 1 or 2, wherein the alcohol extraction is heating extraction and/or ultrasonic extraction;

4. The resource utilization method of the biomass of the hyper-enriched plants as claimed in claim 3, wherein the extraction residue obtained after the alcohol extraction is product one;

wherein the volume-mass ratio of the volume of the resin bed to the dry weight of the hyper-enrichment plants is 0.8-1.4:1, and the sample loading flow rate is 1-3 BV/h.

5. The resource utilization method of the hyper-enriched plant biomass as claimed in claim 4, wherein the loaded resin column is eluted by acidic aqueous solution to obtain eluent, the eluent and the loaded effluent are combined and are filtered after being subjected to chemical precipitation treatment to obtain solid precipitate and filtrate, and the solid precipitate is a product II; concentrating and drying the filtrate to obtain a third product;

6. The resource utilization method of the hyper-enriched plant biomass as claimed in claim 4 or 5, wherein the resin column is a neutral, nonpolar or weak polar macroporous resin column; preferably, the macroporous resin column is any one of D101, AB-8, H-60, XDA-1, D101b, LSA-20, LSA-30, HP-10, XDA-5 or XDA-6.

7. The resource utilization method of the hyper-enriched plant biomass as claimed in any one of claims 4 to 6, wherein the acidification of the extracting solution after concentration and dilution and the acidification of the resin column both adopt volatile acid;

preferably, the volatile acid is any one of acetic acid, formic acid and hydrochloric acid; the mass fraction of the acid in the acidified concentrated diluted extract, the mass fraction of the acid in the acidic aqueous solution used for acidifying the resin column and the mass fraction of the acid in the acidic aqueous solution used for eluting the resin column were all 0.1%.

8. The resource utilization method of the super-enriched plant biomass as claimed in claim 7, wherein the resin column after being eluted by the acidic aqueous solution is sequentially eluted by 35-50% by volume of the alcoholic solution to obtain the eluent, which is then concentrated and dried to obtain the fourth product, the alcoholic solution with 65-70% by volume is used for eluting to obtain the eluent, which is then concentrated and dried to obtain the fifth product, and the alcoholic solution with 90-95% by volume is used for eluting to obtain the eluent, which is then concentrated and dried to obtain the sixth product;

9. The resource method of the hyper-enriched plant biomass as claimed in claim 8, wherein the elution volume of the 35-50% volume fraction alcoholic solution is 2-4BV, and the flow rate is 0.5-1.2 BV/h;

10. The resource utilization method of the biomass of the super-enriched plants as claimed in any one of claims 1 to 9, wherein the pretreatment is to crush and homogenize fresh super-enriched plants, or cut or crush dried super-enriched plants;

and/or the fresh super-enriched plants are harvested to be pretreated within three days, and the dried super-enriched plants are dried within five days.