CN102276758B - Method for comprehensively utilizing insect Chinese medicine dregs - Google Patents
Method for comprehensively utilizing insect Chinese medicine dregs Download PDFInfo
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- CN102276758B CN102276758B CN2011102280056A CN201110228005A CN102276758B CN 102276758 B CN102276758 B CN 102276758B CN 2011102280056 A CN2011102280056 A CN 2011102280056A CN 201110228005 A CN201110228005 A CN 201110228005A CN 102276758 B CN102276758 B CN 102276758B
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Abstract
The invention relates to a method for comprehensively utilizing insect Chinese medicine dregs. Chitin of the insect Chinese medicine dregs is recovered by an acid-alkali method; chitosan is prepared; melanin is prepared from waste acid solution and waste alkali solution in the preparation process of the chitin; in addition, in the preparation process of the chitin and the melanin, side products such as calcium, lipid, protein, amino acid and the like are recovered to serve as raw materials of medicinal auxiliary materials, health-care products, feed and the like. By the method, the insect Chinese medicine dregs are utilized reasonably and completely; and sustainable development of Chinese medicines is promoted.
Description
Technical field
The present invention relates to a kind of method of comprehensive utilization of the insects Chinese medicine dregs of a decoction, particularly a kind of method of comprehensive utilization of the crustaceans insect Chinese medicine dregs of a decoction.
Background technology
Insect is the biological group of most species, quantity maximum in the biology on the earth, discover that insects Chinese medicine generally contains a large amount of chitins, chitosan, calcium carbonate, calcium phosphate, salt, protein, amino acid, lipid, pigment etc., contains abundant chitin in its body wall.Insects Chinese medicine has the effect of good dispelling wind and removing obstruction in the collateral, promoting blood circulation and removing blood stasis, relievng spasm by subduing liver-wind, is the kind commonly used of Chinese materia medica from ancient times always, is widely used in the treatment of clinical each section.Modern Chang Yishui carries or the mode of alcohol extracting is extracted effective constituent in these insects medicinal materials, as protein, lipid etc., removes slag then and takes or carry out follow-up preparation processing, the medicinal material utilization of this mode is very little, not only thing is use up its usefulness, and the dregs of a decoction have become refuse, the processing trouble.As everyone knows, along with the trend of " back to nature " and the people increase to the healthy products demand, unprecedented growth has appearred in the social demand amount of natural resources of Chinese medicinal materials, make some kinds because excessively excavating or indiscriminate mining and serious waste, utilize insufficiently, cause the minimizing rapidly of resource so that exhausted, greatly restricted the tremendous development of Chinese materia medica, therefore, must strengthen the exploitation of Chinese medicine reasonable resources and comprehensive utilization.
At present, existing research report extracts protein, amino acid, lipid from insect, but these insects medicinal materials are through still having multiple composition with the value recycled such as a large amount of chitins, pigment, protein, fat and calcium in the dregs of a decoction after extracting, these compositions account for 50% of protentomon class medicinal material weight, if discard, not only cause the wasting of resources, also increased the difficulty of dregs of a decoction dischargings simultaneously, be unfavorable for environmental protection.
Summary of the invention
The present invention unclogs and readjusts on other basis of the contained material type of the insects Chinese medicine dregs of a decoction in system, according to character and the purposes of each component, provides a kind of method that fully utilizes the insects Chinese medicine dregs of a decoction.At first, adopt acid-base method, chitin extraction and prepare chitosan from the insects Chinese medicine dregs of a decoction, chitosan can be used as pharmaceutical adjunct or industrial chemicals, carries out the exploitation of medicine, food, healthcare products, Chemicals etc.; Secondly, utilize the spent acid waste lye that produces in the preparation process to prepare melanochrome, can be used as staining agent, be used for industry or Chemicals; Again, resistates contains abundant fatty acid calcium or sodium soap, protein and amino acid etc. in the preparation process, can be used as fodder additives or healthcare products raw material.
For reaching the purpose of the above-mentioned comprehensive utilization insects Chinese medicine dregs of a decoction, the present invention has adopted following steps:
A. be raw material with the crustaceans insect dregs of a decoction, it carried out acid extraction obtain acid extraction liquid and acid extraction filter residue;
B. described acid extraction filter residue is carried out alkaline extraction and obtain alkali extracting solution and alkaline extraction filter residue;
C. with described alkaline extraction filter residue decolouring bleaching, filter, drying obtains chitin;
D. described chitin being joined concentration is 10～18molL
-1In the strong base solution, solid-to-liquid ratio is 1: 5～50, reacts 4～10 hours down at 80～140 ℃, filters, and is washed to neutrality, with filter residue and drying, obtains chitosan.
Further, when using when containing the melanic crustaceans insect dregs of a decoction as raw material, the inventive method also comprises the steps:
E. in step B gained alkali extracting solution, add a certain amount of steps A gained acid extraction liquid, the pH value is transferred to 2～6, placed 1～24 hour, carry out solid-liquid separation again, the gained solid, with absolute ethanol washing to elutant near after colourless, being washed to water lotion pH value is 4～7, is drying to obtain melanochrome then; Gained liquid adds the calcium agent of dregs of a decoction weight 0.5～20%, and through concentrating, drying obtains containing the mixture of fatty acid calcium, sodium soap, protein, amino acid and calcium chelate thereof or its arbitrary combination, can be used as fodder additives or healthcare products raw material.
In a specific examples, the step of described acid extraction is:
Be raw material with the insects Chinese medicine dregs of a decoction, adding concentration is 0.3～2.0molL
-1Hydrochloric acid, obtain solid-to-liquid ratio and be 1: 5～50 mixture a;
Described mixture a was extracted 10～60 minutes down at 50～100 ℃, at room temperature placed then 8～24 hours;
Mixture a filtration after placing is obtained acid extraction liquid and acid extraction filter residue.
In a specific examples, the step of described alkaline extraction is:
Adding concentration in the acid extraction filter residue that steps A obtains is 1～8molL
-1Sodium hydroxide solution, obtain solid-to-liquid ratio and be 1: 5～50 mixture b;
Described mixture b was extracted 1～12 hour down at 70～100 ℃;
Mixture b after extracting is filtered, obtain alkali extracting solution and alkaline extraction filter residue.
In a specific examples, the step of described decolouring bleaching is:
In the alkaline extraction filter residue, add concentration and be 0.5～10% oxygenant, obtain solid-to-liquid ratio and be 1: 5～50 mixture c;
Mixture c was at room temperature decoloured 10～120 minutes, filter, filter residue is 0.5～10% reductant solution again with concentration, and solid-to-liquid ratio is 1: 5～50, bleaches 5～60 minutes down at 40～80 ℃.
Preferably, before described acid extraction, earlier the insects Chinese medicine dregs of a decoction are pulverized, and crossed 20 mesh sieves.
Preferably, described crustaceans insect is dung beetle, Formica fusca, Ground Beetle, Stink Bug, gadfly, Chinese blister beetle, foreign worm.
Beneficial effect of the present invention comprises at least:
1, improved the comprehensive utilization value of insects medicinal material, efficient recovery the multiple useful component in the insects medicinal material dregs of a decoction;
2, solved environmental protection and economic problems, present most investigators are often directly discarded with the acid ﹠ alkali liquid that produces in the dregs of a decoction behind the extracting effective components and the production, enter environment, caused very big pollution and waste.The present invention adopts acid-base method to reclaim from the insects Chinese medicine dregs of a decoction to have prepared chitosan, melanochrome, animal-feed etc., thereby has solved the environmental protection and economy problem of the insect dregs of a decoction effectively, for exemplary role has been played in the comprehensive utilization of the Chinese medicine dregs of a decoction;
3, comprehensive utilization process of the present invention is simple, need not specific installation, and cost is low.
Description of drawings
Fig. 1 is crustaceans insect Chinese medicine dregs of a decoction comprehensive utilization process schema of the present invention.
Embodiment
The objective of the invention is to propose the method for comprehensive utilization of the Chinese medicine dregs of a decoction of a kind of crustaceans insect, the useful matter recycling in the Chinese medicine dregs of a decoction not only can be able to be avoided causing the waste of resource by present method, also reduce the difficulty of the discarded discharging of the dregs of a decoction.
Fig. 1 shows the schema of the inventive method, and as shown in the figure, the inventive method can adopt following steps to obtain chitosan from the dregs of a decoction:
A. be raw material with the crustaceans insect dregs of a decoction, it carried out acid extraction obtain acid extraction liquid and acid extraction filter residue;
B. described acid extraction filter residue is carried out alkaline extraction and obtain alkali extracting solution and alkaline extraction filter residue;
C. with described alkaline extraction filter residue decolouring bleaching, filter, drying obtains chitin;
D. described chitin being joined concentration is 10～18molL
-1In the strong base solution, solid-to-liquid ratio is 1: 5～50, reacts 4～10 hours down at 80～140 ℃, filters, and is washed to neutrality, with filter residue and drying, obtains chitosan.
In addition, when use contains the melanic crustaceans insect dregs of a decoction as raw material of the present invention, utilize method of comprehensive utilization of the present invention from the dregs of a decoction, to reclaim and comprise chitosan and melanic useful matter.Wherein, except using above-mentioned steps A～D to obtain the chitosan, also comprise: in step B gained alkali extracting solution, add a certain amount of steps A gained acid extraction liquid, the pH value is transferred to 2～6, placed 1～24 hour, carry out solid-liquid separation again, separate back gained solid, with absolute ethanol washing to elutant near after colourless, being washed to water lotion pH value is 4～7, drying obtains melanochrome then; Separate back gained liquid, add calcium agent or directly concentrated, drying obtains containing the mixture of fatty acid calcium, sodium soap, protein, amino acid and calcium chelate thereof any or its arbitrary combination, can be used as fodder additives or healthcare products raw material.
The dregs of a decoction of mentioning in the methods of the invention refer to, the filter residue that medicinal material is obtained after the mixed solvent of water or organic solvent or water and organic solvent arbitrary proportion extracts.For example, the present invention can use the crustaceans insect to pulverize by the filtrate after the mixed solvent extraction of water or organic solvent or water and organic solvent arbitrary proportion as the dregs of a decoction.
Crustaceans insect used in the present invention refers to a kind of insect that contains chitin, and for example, the crustaceans insect that can be used as dregs of a decoction raw material of the present invention includes but not limited to: dung beetle, Formica fusca, Ground Beetle, Stink Bug, gadfly, Chinese blister beetle, foreign worm.Especially, can for example, the insects Chinese medicine dregs of a decoction can be pulverized earlier with carrying out follow-up steps such as soda acid extraction behind the insect dregs of a decoction crushing screening again, and used after crossing 20 mesh sieves.
In the methods of the invention, described extraction can be that intermittent type stirs by for example immersion, continuously stirring, and ultrasonic, modes such as diacolation or heating are carried out.In addition, the acid that is suitable for acid extraction includes but not limited to: hydrochloric acid, Hydrogen bromide, nitric acid; The alkali that is suitable for alkaline extraction includes but not limited to: sodium hydroxide, potassium hydroxide, hydrated barta.
In the methods of the invention, decolouring bleaching can be carried out redox with Oxidizing and Reducing Agents in regular turn by the alkaline extraction filter residue that alkaline extraction is obtained and carries out.Wherein, optional usefulness for example potassium permanganate, hydrogen peroxide, hypochlorous acid or bromine water as oxygenant; Optional usefulness for example sulfurous gas, oxalic acid, S-WAT or sodium bisulfite as reductive agent.
The employed highly basic of step D refers to that the pH value greater than 7 and the person that can almost completely not dissociate, includes but not limited to: sodium hydroxide, potassium hydroxide, hydrated barta in the aqueous solution.
Employed calcium agent is for example made up arbitrarily for calcium oxide, calcium hydroxide, calcium carbonate, calcium chloride or its in the step e.
Below utilize specific embodiments of the invention further to set forth the present invention and reach the technique means that predetermined goal of the invention is taked.
The preparation of embodiment 1 dung beetle chitosan
A. be raw material with the dung beetle dregs of a decoction, adding concentration is 1.0molL
-1Hydrochloric acid, obtain solid-to-liquid ratio and be 1: 20 mixture a; Described mixture a was soaked about 30 minutes down at 80～90 ℃, at room temperature placed then about 10 hours; Mixture a filtration after placing is obtained acid extraction liquid and acid extraction filter residue.
B. adding concentration in the acid extraction filter residue that steps A obtains is 4.0molL
-1Sodium hydroxide solution, obtain solid-to-liquid ratio and be 1: 20 mixture b; Described mixture b was soaked about 8 hours down at 80～90 ℃; Mixture b after soaking is filtered, obtain alkali extracting solution and alkaline extraction filter residue.
C. in the alkaline extraction filter residue, add concentration and be 5.0% potassium permanganate solution, obtain solid-to-liquid ratio and be 1: 30 mixture c; Mixture c was at room temperature decoloured about 60 minutes, filter, add concentration in the filter residue again and be 2.5% oxalic acid, making its solid-to-liquid ratio is 1: 30, and 60 ℃ of about 20 minutes of bleachings down, more after filtration, drying obtains chitin.
D. in the gained chitin, add 10molL
-1Sodium hydroxide solution, solid-to-liquid ratio are 1: 25, react about 8 hours down at 110～120 ℃, filter, and filter residue washes with water to neutrality, and drying obtains chitosan.
The preparation of embodiment 2 dung beetle chitosans, melanochrome and fodder additives etc.
A. be raw material with the dung beetle dregs of a decoction, adding concentration is 0.3molL
-1Hydrochloric acid, obtain solid-to-liquid ratio and be 1: 50 mixture a; Described mixture a was soaked about 10 minutes down at 50～55 ℃, at room temperature placed then about 14 hours; Mixture a filtration after placing is obtained acid extraction liquid and acid extraction filter residue.
B. adding concentration in the acid extraction filter residue that steps A obtains is 1.0molL
-1Sodium hydroxide, obtain solid-to-liquid ratio and be 1: 50 mixture b; Make described mixture b about 1 hour of 70～75 ℃ of following heating edge stir process; Mixture b after handling is filtered, obtain alkali extracting solution and alkaline extraction filter residue.
C. the alkaline extraction filter residue is added to concentration and is that to obtain solid-to-liquid ratio in 0.5% the potassium permanganate solution be 1: 30 mixture c; Mixture c is at room temperature decoloured, the control potassium permanganate solution becomes brown by red-purple during decolouring, shows that oxidation is complete, stopped reaction, filter, it is 2% sodium sulfite solution that filter residue adds concentration again, and making its solid-to-liquid ratio is 1: 50,50～55 ℃ of about 60 minutes of bleachings down, see its color and approach white, then after filtration, drying namely gets chitin.
D. the gained chitin being joined concentration is 16molL
-1Sodium hydroxide solution in, solid-to-liquid ratio is 1: 15,80～85 ℃ of down about 10 hours of reactions, filters, filter residue washes with water to neutrality, drying obtains chitosan.
E. in step B gained alkali extracting solution, add a certain amount of steps A gained acid extraction liquid, the pH value transferred to be about 3, placed about 1 hour, carry out solid-liquid separation again, solid after the separation with absolute ethanol washing to elutant near after colourless, the pH value that is washed to water lotion is about 4, is drying to obtain melanochrome then; The calcium chloride that adds dregs of a decoction weight 15% in the liquid after separation stirs, and through concentrating, drying namely gets the mixture of materials such as containing protein, amino acid, fatty acid calcium, sodium soap, calcium amino acid chelate, can be prepared as a kind of fodder additives or healthcare products.
The preparation of embodiment 3 Formica fusca chitosans, melanochrome and fodder additives etc.
A. be raw material with the Formica fusca dregs of a decoction, adding concentration is 1.3molL
-1Hydrochloric acid, obtain solid-to-liquid ratio and be 1: 5 mixture a; Described mixture a was soaked about 30 minutes down at 80～85 ℃, at room temperature placed then about 12 hours; Mixture a filter paper filtering with after placing obtains acid extraction liquid and acid extraction filter residue.
B. adding concentration in the acid extraction filter residue that steps A obtains is 4.0molL
-1Sodium hydroxide solution, obtain solid-to-liquid ratio and be 1: 30 mixture b; Make described mixture b about 6 hours of 90～95 ℃ of following intermittent type stir process; Mixture b after handling is filtered, obtain alkali extracting solution and alkaline extraction filter residue.
C. the alkaline extraction filter residue is added to concentration and is that to obtain solid-to-liquid ratio in 3% the hydrogen peroxide be 1: 10 mixture c; Mixture c was at room temperature decoloured about 30 minutes, filter, filter residue is 2.0% oxalic acid bleaching again with concentration, and solid-to-liquid ratio is 1: 20, bleaches about 5 minutes down at 80 ℃, more after filtration, is washed to neutrality, and drying obtains chitin.
D. the gained chitin being joined concentration is 14molL
-1Potassium hydroxide solution in, solid-to-liquid ratio is 1: 40,110～115 ℃ of down about 6 hours of reactions, use filter paper filtering through being washed to neutral back again, drying obtains chitosan under 60～65 ℃.
E. in step B gained alkali extracting solution, add a certain amount of steps A gained acid extraction liquid, the pH value transferred to be about 4, placed about 8 hours, carry out solid-liquid separation again, the gained solid, with absolute ethanol washing to elutant near after colourless, be washed to water lotion pH value and be about 6, lyophilize namely gets melanochrome then; Gained liquid, the calcium oxide that adds dregs of a decoction weight 20%, in 50～55 ℃ of following normal pressures or concentrating under reduced pressure, dry down in 60～65 ℃ again, namely get the mixture of materials such as containing protein, amino acid, fatty acid calcium, sodium soap, calcium amino acid chelate, can be prepared as a kind of fodder additives or healthcare products.
The preparation of embodiment 4 Ground Beetle chitosans, melanochrome, fodder additives etc.
A. be raw material with the Ground Beetle dregs of a decoction, cross 20 mesh sieves after crushed, the sieve powder is standby.
B. adding concentration in above-mentioned sieve powder is 2.0molL
-1Hydrochloric acid, obtain solid-to-liquid ratio and be 1: 30 mixing b; Described mixture b was soaked about 60 minutes down at 95～100 ℃, at room temperature placed then about 24 hours; Mixture b filter paper filtering with after placing obtains acid extraction liquid and acid extraction filter residue.
C. adding concentration in the acid extraction filter residue that step B obtains is 8.0molL
-1Sodium hydroxide solution, obtain solid-to-liquid ratio and be 1: 10 mixture c; Described mixture c was soaked about 12 hours down at 95～100 ℃; Mixture c after soaking is filtered with filter cloth again, obtain alkali extracting solution and alkaline extraction filter residue.
D. in above-mentioned alkaline extraction filter residue, add concentration and be 10% hydrogen peroxide, obtain solid-to-liquid ratio and be 1: 50 mixture d; Mixture d was at room temperature decoloured about 120 minutes, filter, filter residue is 5.0% oxalic acid bleaching again with concentration, and solid-to-liquid ratio is 1: 50, bleaches about 15 minutes down at 75～80 ℃, is washed to neutrality, and more after filtration, drying obtains chitin.
E. the gained chitin being joined concentration is 18molL
-1Potassium hydroxide solution in, solid-to-liquid ratio is 1: 30,130～140 ℃ of down about 4 hours of reactions, filters with filter cloth through being washed to neutral back again, in 60～65 ℃ of dryings down, obtains chitosan.
F. in step C gained alkali extracting solution, add a certain amount of step B gained acid extraction liquid, the pH value transferred to be about 6, placed about 24 hours, carry out solid-liquid separation again, the gained solid, with absolute ethanol washing to elutant near after colourless, be washed to water lotion to there not being the alcohol flavor, be that ethanol content is lower than 1000ppm, preferably be lower than 500ppm, under 30～50 ℃, be drying to obtain melanochrome then; Gained liquid, the calcium hydroxide that adds dregs of a decoction weight 5%, in 50～55 ℃ of following normal pressures or concentrating under reduced pressure, dry down in 60～65 ℃ again, namely get the mixture of materials such as containing protein, amino acid, fatty acid calcium, sodium soap, calcium amino acid chelate, can be prepared as a kind of fodder additives or healthcare products.
The preparation of embodiment 5 Stink Bug chitosans, melanochrome, fodder additives etc.
A. be raw material with the Stink Bug dregs of a decoction, cross 20 mesh sieves after crushed, the sieve powder is standby.
B. adding concentration in above-mentioned sieve powder is 1.5molL
-1Hydrochloric acid, obtain solid-to-liquid ratio and be 1: 15 mixing b; Described mixture b was soaked about 20 minutes down at 75～80 ℃, at room temperature placed then about 20 hours; Mixture b after placing is filtered with filter cloth, obtain acid extraction liquid and acid extraction filter residue.
C. adding concentration in the acid extraction filter residue that step B obtains is 6.0molL
-1Sodium hydroxide, obtain solid-to-liquid ratio and be 1: 40 mixture c; Make described mixture c about 12 hours of 95～100 ℃ of following stir process; Mixture c after handling is filtered with filter cloth again, obtain alkali extracting solution and alkaline extraction filter residue.
D. in above-mentioned alkaline extraction filter residue, add concentration and be 3% potassium permanganate solution, obtain solid-to-liquid ratio and be 1: 10 mixture d; Mixture d was at room temperature decoloured about 60 minutes, filter, filter residue is 3.0% oxalic acid bleaching again with concentration, and solid-to-liquid ratio is 1: 25, bleaches about 20 minutes down at 70～75 ℃, is washed to neutrality, uses filter paper filtering again, and is dry under 75～80 ℃, obtains chitin.
E. the gained chitin being joined concentration is 10molL
-1Sodium hydroxide solution in, solid-to-liquid ratio is 1: 5,100～105 ℃ of down about 10 hours of reactions, use filter paper filtering through being washed to neutral back again, drying obtains chitosan under 60～65 ℃.
F. in step C gained alkali extracting solution, add a certain amount of step B gained acid extraction liquid, the pH value transferred to be about 5, placed about 12 hours, carry out solid-liquid separation again, the gained solid, with absolute ethanol washing to elutant near after colourless, be washed to water lotion to pH value and be about 7, namely get melanochrome in 30～50 ℃ of following vacuum-dryings then; Gained liquid in 50～55 ℃ of following concentrating under reduced pressure, again in 55～60 ℃ of following vacuum-dryings, namely gets the mixture of materials such as containing protein, amino acid, sodium soap, can be used as fodder additives or healthcare products raw material.
The preparation of embodiment 6 Chinese blister beetle chitosans, melanochrome, fodder additives etc.
A. be raw material with the Chinese blister beetle dregs of a decoction, cross 20 mesh sieves after crushed, the sieve powder is standby.
B. adding concentration in above-mentioned sieve powder is 0.8molL
-1Hydrochloric acid, obtain solid-to-liquid ratio and be 1: 35 mixing b; Described mixture b was soaked about 40 minutes down at 75～80 ℃, at room temperature placed then about 20 hours; Mixture b filter paper filtering with after placing obtains acid extraction liquid and acid extraction filter residue.
C. adding concentration in the acid extraction filter residue that step B obtains is 4.0molL
-1Sodium hydroxide solution, obtain solid-to-liquid ratio and be 1: 20 mixture c; Described mixture c was soaked about 10 hours down at 85～90 ℃; Mixture c after soaking is used filter paper filtering again, obtain alkali extracting solution and alkaline extraction filter residue.
D. above-mentioned alkaline extraction filter residue is added to concentration and is that to obtain solid-to-liquid ratio in 1.0% the potassium permanganate be 1: 30 mixture d; Mixture d was at room temperature decoloured about 90 minutes, filter, filter residue is 10.0% S-WAT bleaching again with concentration, solid-to-liquid ratio is 1: 20, bleaches 45 minutes down at 40～45 ℃, is washed to neutrality, use filter paper filtering again, dry under 75～80 ℃, obtain chitin.
E. the gained chitin being joined concentration is 14molL
-1Sodium hydroxide solution in, solid-to-liquid ratio is 1: 25,120～125 ℃ of down about 8 hours of reactions, use filter paper filtering through being washed to neutral back again, drying obtains chitosan under 60～65 ℃.
F. in step C gained alkali extracting solution, add a certain amount of step B gained acid extraction liquid, the pH value transferred to be about 3, placed 12 hours, carry out solid-liquid separation again, the gained solid, with absolute ethanol washing to elutant near after colourless, be washed to water lotion pH value and be about 4, under 30～50 ℃, be drying to obtain melanochrome then; Gained liquid, the calcium chloride that adds dregs of a decoction weight 5%, concentrate down in 55～60 ℃, dry in 55～60 ℃ of far infrared drying ovens again, namely get the mixture of materials such as containing protein, amino acid, fatty acid calcium, sodium soap, calcium amino acid chelate, can be used as fodder additives or healthcare products raw material.
The preparation of embodiment 7 foreign worm chitosans, melanochrome, fodder additives etc.
A. be raw material with the foreign worm dregs of a decoction, adding concentration is 1.5molL
-1Hydrochloric acid, obtain solid-to-liquid ratio and be 1: 30 mixture a; Described mixture a was soaked about 60 minutes down at 80～85 ℃, at room temperature placed then about 12 hours; Mixture a filter paper filtering with after placing obtains acid extraction liquid and acid extraction filter residue.
B. adding concentration in the acid extraction filter residue that steps A obtains is 4.0molL
-1Sodium hydroxide solution in to obtain solid-to-liquid ratio be 1: 30 mixture b; Described mixture b was soaked about 6 hours down at 90～95 ℃; Mixture b after soaking is used filter paper filtering again, obtain alkali extracting solution and alkaline extraction filter residue.
C. the alkaline extraction filter residue is added to concentration and is that to obtain solid-to-liquid ratio in 2% the hydrogen peroxide be 1: 20 mixture c; Mixture c was at room temperature decoloured about 30 minutes, filter, filter residue is 2.5% oxalic acid bleaching again with concentration, and solid-to-liquid ratio is 1: 30, bleaches about 15 minutes down at 70 ℃, more after filtration, is washed to neutrality, and drying obtains chitin.
D. the gained chitin being joined concentration is 16molL
-1Sodium hydroxide solution in, solid-to-liquid ratio is 1: 30,100～105 ℃ of down about 6 hours of reactions, use filter paper filtering through being washed to neutral back again, drying obtains chitosan under 60～65 ℃.
E. in step B gained alkali extracting solution, add a certain amount of steps A gained acid extraction liquid, the pH value transferred to be about 2, placed about 8 hours, carry out solid-liquid separation again, the gained solid, with absolute ethanol washing to elutant near after colourless, be washed to water lotion to pH value and be about 5, under 30～50 ℃, be drying to obtain melanochrome then; Gained liquid in 45～50 ℃ of following normal pressures or concentrating under reduced pressure, again in 55～60 ℃ of vacuum-dryings, namely gets the mixture of materials such as fatty acids sodium, protein, amino acid, can be prepared as a kind of fodder additives or healthcare products.
The preparation of embodiment 8 dung beetle chitosans, melanochrome, fodder additives etc.
A. be raw material with the dung beetle dregs of a decoction, cross 20 mesh sieves after crushed, the sieve powder is standby.
B. adding concentration in above-mentioned sieve powder is 2.0molL
-1Hydrochloric acid in to obtain solid-to-liquid ratio be 1: 30 mixing b; Make described mixture b 95～100 ℃ of following stir abouts 30 minutes, at room temperature placed then about 24 hours; Mixture b filter paper filtering with after placing obtains acid extraction liquid and acid extraction filter residue.
C. adding concentration in the acid extraction filter residue that step B obtains is 8.0molL
-1Sodium hydroxide solution, obtain solid-to-liquid ratio and be 1: 10 mixture c; Make described mixture c 95～100 ℃ of following stir abouts 2 hours; Mixture c after placing is filtered with filter cloth again, obtain alkali extracting solution and alkaline extraction filter residue.
D. in above-mentioned alkaline extraction filter residue, add concentration and be that to obtain solid-to-liquid ratio in 10% the hydrogen peroxide be 1: 50 mixture d; Mixture d was at room temperature decoloured about 120 minutes, filter, filter residue is 0.5% oxalic acid bleaching again with concentration, and solid-to-liquid ratio is 1: 50, bleaches about 5 minutes down at 80 ℃, is washed to neutrality, and more after filtration, drying obtains chitin.
E. the gained chitin being joined concentration is 18molL
-1Sodium hydroxide solution in, solid-to-liquid ratio is 1: 20,130～140 ℃ of down about 4 hours of reactions, use filter paper filtering through being washed to neutral back again, drying obtains chitosan under 60～65 ℃.
F. in step C gained alkali extracting solution, add a certain amount of step B gained acid extraction liquid, the pH value transferred to be about 6, placed about 24 hours, carry out solid-liquid separation again, the gained solid, with absolute ethanol washing to elutant near after colourless, be washed to water lotion and be neutral, lyophilize namely gets melanochrome then; Gained liquid, the calcium carbonate of adding dregs of a decoction weight 1% concentrates down in 55～60 ℃, and is dry in 55～60 ℃ of far infrared drying ovens again, namely gets the mixture of materials such as fatty acids sodium, protein, amino acid, can be prepared as a kind of fodder additives or healthcare products.
The above only is the preferred embodiments of the present invention, be not that the present invention is done any pro forma restriction, any those skilled in the art, in the scope that does not break away from technical solution of the present invention, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention,, all still belong in the scope of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment does according to technical spirit of the present invention.
Claims (7)
1. a method of comprehensive utilization that contains the melanic crustaceans insect Chinese medicine dregs of a decoction comprises the steps:
A. be raw material to contain the melanic crustaceans insect dregs of a decoction, it carried out acid extraction obtain acid extraction liquid and acid extraction filter residue;
B. described acid extraction filter residue is carried out alkaline extraction and obtain alkali extracting solution and alkaline extraction filter residue;
C. with step B gained alkaline extraction filter residue decolouring bleaching, filter, drying obtains chitin;
D. described chitin being joined concentration is 10～18mo1L
-1Strong base solution in, solid-to-liquid ratio is 1: 5～50,80～140 ℃ of down reactions 4～10 hours, filters, and is washed to neutrality, with filter residue and drying, obtains chitosan;
E. the acid extraction liquid that adds a certain amount of steps A gained in step B gained alkali extracting solution transfers to 2～6 with the pH value, placed 1～24 hour, carry out solid-liquid separation again, separate back gained solid, with absolute ethanol washing to elutant near after colourless, being washed to water lotion pH value is 4～7, and drying obtains melanochrome then; Separate back gained liquid, add calcium agent or directly concentrated, drying obtains containing the mixture of fatty acid calcium, sodium soap, protein, amino acid and calcium chelate thereof or its arbitrary combination.
2. method according to claim 1 is characterized in that, the step of described acid extraction is:
Be raw material with the insects Chinese medicine dregs of a decoction, adding concentration is 0.3～2.0mo1L
-1Hydrochloric acid, obtain solid-to-liquid ratio and be 1: 5～50 mixture a;
Described mixture a was extracted 10～60 minutes down at 50～100 ℃, at room temperature placed then 8～24 hours;
Mixture a filtration after placing is obtained acid extraction liquid and acid extraction filter residue.
3. method according to claim 1 is characterized in that, the step of described alkaline extraction is:
Adding concentration in the acid extraction filter residue that steps A obtains is 1～8mo1L
-1Sodium hydroxide solution, obtain solid-to-liquid ratio and be 1: 5～50 mixture b;
Described mixture b was extracted 1～12 hour down at 70～100 ℃;
Mixture b after extracting is filtered, obtain alkali extracting solution and alkaline extraction filter residue.
4. method according to claim 1 is characterized in that, the step of described decolouring bleaching is:
In the alkaline extraction filter residue, add concentration and be 0.5～10% oxidizing agent solution, obtain solid-to-liquid ratio and be 1: 5～50 mixture c;
Mixture c was at room temperature decoloured 10～120 minutes, filter, filter residue is 0.5～10% reductant solution again with concentration, and solid-to-liquid ratio is 1: 5～50, bleaches 5～60 minutes down at 40～80 ℃.
5. method according to claim 1 is characterized in that, further is included in described acid extraction and earlier the insects Chinese medicine dregs of a decoction is pulverized before, and cross 20 mesh sieves.
6. method according to claim 1 is characterized in that, described calcium agent is that calcium oxide, calcium hydroxide, calcium carbonate, calcium chloride or its make up arbitrarily.
7. method according to claim 1 is characterized in that, described crustaceans insect is dung beetle, Ground Beetle, Stink Bug, Chinese blister beetle or foreign worm.
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| US8815539B1 (en) | 2013-06-06 | 2014-08-26 | River Road Research, Inc. | Methods for producing melanin and inorganic fertilizer from fermentation leachates |
| CN103497535B (en) * | 2013-10-10 | 2016-03-30 | 西南科技大学 | A kind of extracting method of Animal melanin and the application of extraction product thereof |
| CN104431329A (en) * | 2014-12-16 | 2015-03-25 | 凉山州先科现代农业开发有限公司 | Green compound feed prepared from periplaneta americana L. waste residue and preparation method of green compound feed |
| CN109370254A (en) * | 2018-12-29 | 2019-02-22 | 桂林医学院 | A method of preparing High color values ant melanin from silky ant |
| CN112029014A (en) * | 2020-09-24 | 2020-12-04 | 山东汉方制药有限公司 | Method for extracting chitosan from centipede dregs |
| CN112998128A (en) * | 2021-03-18 | 2021-06-22 | 廊坊梅花生物技术开发有限公司 | Method for producing feed by using corn sugar residues |
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