CN102321184A - The application technology as the second resource of fresh Rhizome of Peltate Yam - Google Patents
The application technology as the second resource of fresh Rhizome of Peltate Yam Download PDFInfo
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- CN102321184A CN102321184A CN201110224940A CN201110224940A CN102321184A CN 102321184 A CN102321184 A CN 102321184A CN 201110224940 A CN201110224940 A CN 201110224940A CN 201110224940 A CN201110224940 A CN 201110224940A CN 102321184 A CN102321184 A CN 102321184A
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Abstract
The present invention is that the fresh Rhizome of Peltate Yam of a kind of usefulness carries out the application technology as the second resource that saponin produces, and relates to the medical material production field, it is characterized in that at first using starch production machinery production starch, obtains Mierocrystalline cellulose simultaneously; Isolated saponin(e (glucoside)-albumen in the starch production process-Serlabo ternary complex obtains vegetable-protein, Serlabo and saponin(e through further separating; With the saponin(e hydrolysis, directly obtain saponin; Produce rhamnosyl with the saponin(e hydrolyzed solution; Wash ginger waste water because of adding yeast reuse capable of circulation in advance, repeatedly be used for the starch production operation after the reuse; Starch production wastewater is handled with yeast and through repeatedly reuse, is used to extract water-solubility saponin, is processed into granulated feed then.The material that exists in the Rhizome of Peltate Yam still keeps native state in the production process overwhelming majority, is convenient to recycling, has reduced the sour consumption in producing simultaneously, and whole process of production does not have waste water to efflux, and does not also have the waste residue outward transport.
Description
Technical field
The present invention relates to the medical material production field, is the application technology as the second resource of a kind of fresh Rhizome of Peltate Yam (cadmium yellow ginger).
Background technology
Rhizome of Peltate Yam (
Dioscorea zingiberensisC. H. Wright) cry again yellow ginger, pillow root, coptis ginseng, yellow ginger, wild Jerusalem artichoke, Dioscorea nipponica Mak. Ningpo Yam Rhizome, mute limit ginger.Be mainly used in and produce diosgenin (turmeric saponin, saponin).
Turmeric saponin, molecular formula are C
27H
42O
3, be-the white powder crystallization, tasteless, be soluble in the organic solvents such as gasoline, ethanol, water insoluble.With the saponin be raw material can synthesizing hydrogenated KE (Hydrocortisone), prednisone (retrocortine; Prednisone), Norethisterone (Norethisterone), fluocinolone acetonide (fluocinonide; Fluocinolone Acetonide), midbody such as all kinds of steroid drugss such as DEXAMETHASONE BP98 (Dexamethasone) and pitocin or medicine are nearly thousand kinds; Though China's starting is later, also can synthesize 100 multiple products.Like diene alcohol ketone acetic ester (Dehydropregnenolone Acetate), Progesterone (Progesterone), dehydroepiandros-sterone (Dehydroepiandrosterone), acetic acid dehydroepiandros-sterone (Dehydroepiandrosterone Acetate) etc.Therefore the world of medicine claims that yellow ginger is " a medicinal gold ".Except that satisfying domestic needs, saponin more than 120 countries and regions such as U.S.A, moral, method, day of always being in great demand.
Since over half a century, Chinese and overseas scholars had carried out many researchs around improving saponin yield and reducing cost before this, and nearly 40 years begin to pay attention to comprehensive utilization of resources and Pollution abatement, carried out diversified exploration.For example, carried out the research of yellow ginger comprehensive utilization in 1989.Fresh ginger slice at 105 ℃ of drying 4 h, was pulverized 65 mesh sieves.With yellow ginger powder 24 h that are soaked in water, add 10 ~ 15 times of water gagings, leave standstill 3 h, tell supernatant, repetitive scrubbing 10 times.Supernatant concentration is extracted perhexiline.Throw out is the milk of starch that contains dioscin.Milk of starch at 100 ℃ of following boiling l h, is added the appropriate amount of starch enzyme, transfer pH to 6, at 90 ℃ of liquefaction 1 ~ 3 h; Use the iodine fluid inspection, after the apparent red-brown, normal-pressure sterilization 30 min transfer pH 4 ~ 4.5; Add an amount of saccharifying enzyme, more than 60 ℃ of insulation 24 h, normal-pressure sterilization 30 min.Filter, tell liquid glucose and sugared slag.The hydrolysis of sugar hydrochloric acid for dreg, gasoline extraction gets turmeric saponin.Liquid glucose adds gac, zeyssatite respectively, and 90 ℃ of decolourings, refining 30 min cross and filter pure Glucose Liquid, are used for the Prednisone acetate mold fermentation, and it is plentiful to cultivate mycelial growth, and oxidation period, transformation efficiency reached the control samples level.Pollution problem obtains part and reduces, but regrettably, this technology does not know it is from which kind of reason, fails in industrial production big area to promote.
Have patent of invention to claim, adopt ethanol to do to extract solvent, directly extract saponin through reflux, can overcome the shortcoming of doing the solvent extraction saponin with gasoline, have operational safety, technology is simple, the advantage that extraction yield is high.In fact, just replaced the gasoline in the traditional technology with ethanol.
Someone is an experiment material with the Yunnan yellow ginger, has carried out brown windsor soap aglycon Study on extraction, from pH value, the return velocity of fermentation time, hydrolysis time, extract the influence of brown windsor soap aglycon extraction yield is studied.Conclusion is: 48 h that ferment, hydrolysis 4 h, extract pH can obtain the optimum extraction rate for nearly neutral, return velocity is 25 min/ time.But its technical process (yellow ginger root stock → selection → cleaning → drying → pulverize → sieve → ferment → hydrolysis → filtration, washing → oven dry filter residue → extracting → drying → finished product) is almost completely the same with traditional technical process.Only replace hydrochloric acid, replaced gasoline with sherwood oil with sulfuric acid.The pollution condition technology with traditional basically is identical.
In addition, following research report is still arranged, but all also fail to get into the industrial applications stage.
Elder generation's separating starch acid hydrolyzation again: after making yellow ginger starch and fibrous residue separates with machinery, starch utilizes separately, hydrolysis fiber slag only, and acid consumption reduces significantly.But contain saponin(e in the slag, contain saponin(e in the starch yet, the saponin recovery is not high, and starch quality is also poor, is difficult to promote.
Double-enzyme method:, starch is transformed saccharogenesis with glycase, saccharifying enzyme (two enzyme).Can be subdivided into 2 kinds of methods again: the one, yellow ginger elder generation high temperature steaming adds double enzymes saccharification after making starch pasting, but includes saponin(e enzyme high temperature deactivation, and sugar utilizes back (generally making wine), and water liquid contains saponin(e have to be with slag acidification hydrolization more together.The one, add two enzymes under the normal temperature, do not heat, but two enzyme dosage to be big, and to contain saponin(e in the slag, filtrating also contains saponin(e, and saponin yield is low.
Membrane separation process: with sugar or after drinking saponin(e is separated earlier, can reduce the acidolysis amount with film, but that solution contains colloid is heavy, needs condition of high voltage with the sugar system, simultaneously film be prone to blocked, the costing an arm and a leg of film, cost is high, the difficult popularization.
Enzyme-membrane separation process: use enzyme that fiber, starch degradation in the yellow ginger are polysaccharide, and polysaccharide fermentation is produced L-type lactic acid.Make filter residue subtract 80%-90%, with the also corresponding minimizing 80% ~ 90% of acid amount than former technology filter residue amount.Acidolysis consumes steam and also reduces 80% ~ 90%; Acid solution is reusable after adopting membrane technique to handle; In the acid slag alkali with after do not wash, directly extract saponin by traditional technology oven dry back.But the Gonna breakthrough because the blockage problem of the cost of enzyme and film, film is still needed is also failed to get into industrialization promotion and is used.
Direct method of isolation: cadmium yellow ginger is through cleaning, pulverize, be with water mill carefully to 60 ~ 100 orders; Sieve,, isolate fiber with the rotating vane pressure filter in 110 ~ 130 mesh sieve holes; Remaining mixture is added CaO under 10 ~ 25 ℃ of conditions, deposition 2 ~ 4 h, mixture is divided into two-layer up and down, and lower floor is a starch, and the upper strata is for containing soap mixture, separating starch; Acid hydrolysis is cleaned, oven dry, uses No. 120 gasoline or ethanol or acetone or supercritical extraction again, saponin.But, also fail on producing, to promote because water-soluble saponin loss problem does not solve.
So still continue to use following two kinds of methods in the industrial production:
The common advantage of above-mentioned two kinds of methods is that production unit is simple, and production cost is also low.In addition, the saponin yield of spontaneous fermentation-acid hydrolyzation is high.
But the drawback of above-mentioned two kinds of methods is that to be disabled acid-hydrolyzed material too many.Considerably beyond the saponin(e that must be hydrolyzed, the aqueous saponin that pharmaceutical value is very high has become saponin to the material that starch contained therein, Mierocrystalline cellulose etc. did not originally need hydrolysis in the yellow ginger rhizome on content, and rhamnosyl has also become pollutent.Sour consumption is very big in the production process, and simultaneously these materials change into the condenses that carbohydrate such as water-soluble glucose, methyl furfural, hydroxymethylfurfural and verivate and nitrogenous substances thereof generate.This has not only increased wastewater flow rate; The COD of waste water is greatly increased, and the condenses of carbohydrate and nitrogenous substances generation simultaneously is a coloring matter, and the colourity of waste water is greatly increased; What is more important; These condensess stable higher is difficult to biochemical degradation especially, increased the difficulty of waste water end treatment.
With existing Rhizome of Peltate Yam saponin production technique, in process of production, starch is hydrolyzed into for pollutent.Every production 1 t saponin needs nearly 140 t of fresh Rhizome of Peltate Yam, about 35% technical hydrochloric acid, 20 t or industrial sulphuric acid 6 t; Produce about waste water 500 t, and the COD of waste water is up to 30000 mg/l, BOD is up to 8000 mg/l; Waste water ph is in 1.0 ~ 2.5 scopes, and COD exceeds standard more than 300 times in its waste water, and colourity exceeds standard more than 200 times; And be stronger acidity, and also there is not special effective treatment craft to enable qualified discharge at present, environment has been caused extremely serious pollution.
Turmeric saponin industrial advantage district by chance also is the water conservation district of divert water from the south to the north project work centerline.Yellow ginger pollutes extremely whole nation concern, and pollution problem becomes the bottleneck that restriction yellow ginger industry develops in a healthy way.
Water source in order to ensure " south water to north " is not polluted by the turmeric saponin factory effluent, and is free from environmental pollution again in order to guarantee the nearly 600,000,000 yuan yellow ginger mainstay industry sustainable development of annual income.NGO yellow ginger processing enterprise.Successively invest more than 700 ten thousand yuan, the waste water that processing causes has been administered, got certain effect.But the cost of pollution treatment is too high, and administering 1 t waste water needs cost Renminbi more than 6 yuan, also is difficult to reach first discharge standard, and enterprise can't bear the heavy load, and many enterprises are compelled to be closed down.
Summary of the invention
Technical problem to be solved by this invention is: how effectively to utilize the saponin(e that contains in the yellow ginger rhizome (all by dry weight basis) about 5%, about 2% soluble sugar, about 1.5% pigment, about 1% grease, about 1% protein, about 42% starch, about 40% Mierocrystalline cellulose.
The invention provides a kind of with short production cycle, with acid amount less, superior product quality, and obtain the Rhizome of Peltate Yam application technology as the second resource of starch, Mierocrystalline cellulose, Serlabo, vegetable-protein, diosgenin, rhamnosyl, water-solubility saponin, 7 kinds of sub products of granulated feed simultaneously.
Compare with existing processes, the present invention has following major advantage:
One of which, realized recycling: the sub product in the saponin producing process (Mierocrystalline cellulose, starch, Serlabo, vegetable-protein, water-solubility saponin) all keeps native state, can be used as the raw material of producing other products.
Two, the saponin quality is high: owing to there is not the interference of Mierocrystalline cellulose and starch and other materials in the hydrolytic process, hydrolysis reaction is thorough, does not almost have side reaction, and the content of saponin is high in the hydrolyzate.
Three, the consumption of acid is few: because a hydrolyzing saponin, every production 1 t saponin only consumes 0.3 t industrial sulphuric acid or 1 t technical hydrochloric acid, is 5% of traditional technology.
Four, production cost is low: after hydrolyzate neutralization, washing, the drying, need only need not carry out recrystallization with organic solvent extraction or critical carbon dioxide extraction, can obtain high-quality saponin product.Acid, gasoline, consumption of ethanol are few, and production cost and traditional technology remain basically stable.
Five, do not have waste water and solid waste: in the whole process of production except that a small amount of yellow ginger with soil be converted into the silt outward transport; There are not other solid waste to produce; Pollutants in sewage exists with the form of crude substance; Therefore the biodegradability of waste water is strong, and its intractability is equivalent to the intractability of sewage, is easy to qualified discharge.Can be used for papermaking or production CMC 99.5 or production gac after the Mierocrystalline cellulose slag drying or directly be used for the yellow ginger plantation, increase the soil organism.
Six, produce required equipment and be mainly starch-making equipment, be beneficial to popularization; Equipment component is traditional saponin production unit, helps the transformation of old factory.
Description of drawings
Fig. 1 is the detailed process flow figure that Rhizome of Peltate Yam carries out the application technology as the second resource of saponin production
Claims (9)
1. the application technology as the second resource of fresh Rhizome of Peltate Yam (cadmium yellow ginger) is characterized in that producing starch, Mierocrystalline cellulose, vegetable-protein, Serlabo, diosgenin, rhamnosyl, water-solubility saponin (glucoside) and granulated feed with cadmium yellow ginger successively; Wash the ginger waste water circulation; Water-solubility saponin is from what extract with the starch wastewater after the reuse repeatedly, and starch wastewater extracts water-solubility saponin and is processed into granulated feed later on.
2. produce the method for starch with cadmium yellow ginger, it is characterized in that cleaning (what add for the first time is the yeast suspension, and what add later on all is reuse wash waters) to cadmium yellow ginger feeding paddle formula cleaning machine with 0.01% yeast suspension or reuse water; Add by 3 times of amounts cleaning fresh ginger and to contain 0.01% yeast suspension or reuse water (what add for the first time is the yeast suspension; What add later on is starch processing reuse water); Insert overflow washing type potato class powder-making machine, starch rotational flow station, remove sand-decolour-remove slag clearing machine, vacuum hydroextractor, separate obtaining Mierocrystalline cellulose slag, starch, saponin(e-albumen-Serlabo ternary complex and starch processing reuse water.
3. obtain the method for vegetable-protein, it is characterized in that saponin(e-albumen-Serlabo ternary complex is pumped into extractor, use extraction using alcohol, residue obtains vegetable-protein after reclaiming ethanol, can make food and fodder additives raw material; Ethanol extract is used to produce Serlabo.
4. obtain the method for yellow ginger Serlabo, it is characterized in that ethanol extract is extracted with No. 120 industrial napthas, the gasoline layer obtains Serlabo after reclaiming solvent, can make the healthcare products raw material; Alcohol layer is used to produce diosgenin.
5. obtain the method for diosgenin, it is characterized in that the alcohol layer solution of ethanol extract after with No. 120 solvent oils extractions is reclaimed ethanol with alcohol distillation column, obtain moisture saponin(e, it is 1 mol/L that the adding vitriol oil makes its concentration, in 0.21 MPa (2.1 kg/cm
2) i.e. 132 ℃ of following hydrolysis 2 h, use the vacuum filter suction filtration, filtrating is used to produce rhamnosyl; Filter residue is suspended in water or the neutralizer (water is used neutralizer later on for the first time), with saturated sodium hydroxide solution neutralization, uses the vacuum filter suction filtration again, with disc type continuous drier drying, is lower than 5% to water cut; With No. 120 industrial naptha recrystallizations, reclaim gasoline, obtain diosgenin.
6. obtain the method for rhamnosyl; It is characterized in that the filtrating hydro-oxidation barium dust that obtains with the vacuum filter suction filtration after the saponin(e hydrolysis is neutralized to pH 7.0; Centrifugal remove barium sulfate precipitate after, add saccharomycetes to make fermentation 24 h by 0.1% consumption, centrifugal again; What obtain is precipitated as yeast cell, is used to prepare the yeast suspension; Supernatant concentration obtains the rhamnosyl crystallization, is used to produce essence and flavoring agent.
7. wash water reuse method: clean with paddle formula cleaning machine that cadmium yellow ginger is effusive to contain saccharomycetic wash water, remove by filter foreign material such as silt, yellow ginger coring through settling tank after, be back to matting, be used for starch production after the reuse repeatedly.
8. obtain the method for water-solubility saponin, it is characterized in that starch is processed the waste water that produces in the course of processing,, use n-butanol extraction, reclaim propyl carbinol, obtain aqueous saponin, as the raw material of producing perhexiline through after about 10 reuses; The propyl carbinol surplus aqueous solution that comes together is used for the processing granular feed.
9. granulated feed working method: the propyl carbinol surplus aqueous solution that comes together directly is machined to granulated feed with spraying drying.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702301A (en) * | 2012-06-22 | 2012-10-03 | 邵阳市长源生物科技有限公司 | Novel process for extracting diosgenin |
| CN103059095A (en) * | 2013-01-07 | 2013-04-24 | 李玉山 | Green extraction technology for comprehensive and efficient utilization of Dioscorea zingiberensis resource |
| CN103755776A (en) * | 2014-01-22 | 2014-04-30 | 于华忠 | Method for extracting saponin and rhamnose from yellow ginger |
| CN104798989A (en) * | 2015-04-28 | 2015-07-29 | 防城港市雅美好饲料有限公司 | Preparation method of special pre-gelatinized starch for feed |
| CN108129290A (en) * | 2017-12-25 | 2018-06-08 | 武汉三江航天固德生物科技有限公司 | A kind of method of sulfate radical in removal lactic acid |
| CN111269953A (en) * | 2020-04-27 | 2020-06-12 | 武汉纺织大学 | Method for preparing bacterial cellulose by using waste polyester fabric |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702301A (en) * | 2012-06-22 | 2012-10-03 | 邵阳市长源生物科技有限公司 | Novel process for extracting diosgenin |
| CN103059095A (en) * | 2013-01-07 | 2013-04-24 | 李玉山 | Green extraction technology for comprehensive and efficient utilization of Dioscorea zingiberensis resource |
| CN103059095B (en) * | 2013-01-07 | 2016-03-16 | 李玉山 | A kind of green extraction of yellow ginger resource comprehensive efficiency utilization |
| CN103755776A (en) * | 2014-01-22 | 2014-04-30 | 于华忠 | Method for extracting saponin and rhamnose from yellow ginger |
| CN103755776B (en) * | 2014-01-22 | 2016-03-30 | 北京泛球生物科技有限公司 | A kind of method of turmeric extracted saponin and rhamnosyl |
| CN104798989A (en) * | 2015-04-28 | 2015-07-29 | 防城港市雅美好饲料有限公司 | Preparation method of special pre-gelatinized starch for feed |
| CN108129290A (en) * | 2017-12-25 | 2018-06-08 | 武汉三江航天固德生物科技有限公司 | A kind of method of sulfate radical in removal lactic acid |
| CN108129290B (en) * | 2017-12-25 | 2021-01-22 | 武汉三江航天固德生物科技有限公司 | Method for removing sulfate radical in lactic acid |
| CN111269953A (en) * | 2020-04-27 | 2020-06-12 | 武汉纺织大学 | Method for preparing bacterial cellulose by using waste polyester fabric |
| CN111269953B (en) * | 2020-04-27 | 2022-02-25 | 武汉纺织大学 | Method for preparing bacterial cellulose by using waste polyester fabric |
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