CN108948124A - A kind of preparation method of Tea Saponin - Google Patents
A kind of preparation method of Tea Saponin Download PDFInfo
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- CN108948124A CN108948124A CN201810864405.8A CN201810864405A CN108948124A CN 108948124 A CN108948124 A CN 108948124A CN 201810864405 A CN201810864405 A CN 201810864405A CN 108948124 A CN108948124 A CN 108948124A
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- Prior art keywords
- tea
- filtrate
- tea saponin
- seed cake
- extraction
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J63/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by expansion of only one ring by one or two atoms
- C07J63/008—Expansion of ring D by one atom, e.g. D homo steroids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/20—Carbocyclic rings
- C07H15/24—Condensed ring systems having three or more rings
- C07H15/256—Polyterpene radicals
Abstract
The invention discloses a kind of preparation methods of Tea Saponin, include the following steps: step 1, raw material chooses and processing;Step 2, extraction filtering;Step 3 is concentrated by evaporation;Step 4 turns extraction decoloration;Step 5, evaporation drying;Step 6, abstraction purification;Step 7, distillation crystallization;Step 8, transhipment save;Wherein in above-mentioned step one, choosing fresh leached tea oil slag and tea seed cake is raw material, it will be infected with the leached tea oil slag and tea seed cake for having soil and going mouldy in raw material to reject from raw material, put the raw materials into pulverizer, so that leached tea oil slag and tea seed cake are ground into scoriform object;Wherein in above-mentioned step two, a certain amount of tea seed cake powder is weighed, distilled water is added, is placed in loop type extractor;The present invention, has carried out secondary use to leached tea oil slag and tea seed cake, has reduced production cost, and during preparation, and easy to operate, good impurity removing effect effectively raises the purity of Tea Saponin.
Description
Technical field
The present invention relates to Tea Saponin technical field, specially a kind of preparation method of Tea Saponin.
Background technique
Tea Saponin also known as tea saponin are a kind of glycoside compounds by extracting in tea tree seed, are that a kind of performance is good
Good natural surfactant, it can be widely applied to light industry, chemical industry, pesticide, feed, cultivation, weaving, oil recovery, mining, building materials
It abluent, insecticides adjuvant, feed addictive, crab shrimp aquaculture protective agent, is spun with fields, manufacture emulsifiers such as expressway constructions
Knit auxiliary agent, oilfield foaming agent, mining flotation agent and air entrained concrete foam stabilizer and concrete admixture.
When preparing Tea Saponin, preparation method in the prior art is that preparation is extracted from tea tree seed, tea tree kind
The price of son costly, considerably increases production cost, and during preparation, preparation method in the prior art,
Operating procedure is complicated miscellaneous, and impurity-eliminating effect is poor, causes Tea Saponin purity obtained lower, seriously affects the quality of Tea Saponin,
Therefore, it is necessary for designing a kind of preparation method of Tea Saponin.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of Tea Saponin, to solve mentioned above in the background art ask
Topic.
To achieve the above object, the invention provides the following technical scheme:
A kind of preparation method of Tea Saponin includes the following steps: step 1, and raw material chooses and processing;Step 2, extracted
Filter;Step 3 is concentrated by evaporation;Step 4 turns extraction decoloration;Step 5, evaporation drying;Step 6, abstraction purification;Step 7 is steamed
Evaporate crystallization;Step 8, transhipment save;
Wherein in above-mentioned step one, choosing fresh leached tea oil slag and tea seed cake is raw material, and contamination in raw material is had mud
Soil and the leached tea oil slag and tea seed cake that go mouldy are rejected from raw material, are putted the raw materials into pulverizer so that leached tea oil slag with
Tea seed cake is ground into scoriform object;
Wherein in above-mentioned step two, a certain amount of tea seed cake powder is weighed, distilled water is added, is placed in loop type extractor
In, after being soaked for a period of time, Tea Saponin leaching liquid is obtained, the filtrate that extraction obtains is used into filtered through gauze while hot, the filter that will be obtained
Slag continues plus distilled water carries out water bath with thermostatic control extraction again, then uses filtered through gauze while hot, operates repeatedly three times, the filtrate that will be obtained
Merge, adds flocculant in filtrate after merging, separated impurity with Tea Saponin filtrate using suction filtration machine;
Wherein in above-mentioned step three, filtrate obtained in step 2 is placed in the de- dryer of disc type Multideck and is carried out
Depressurize evaporation at constant temperature, until filtrate be it is thick so that filtrate disc type Multideck take off dryer in be concentrated, obtain
Filtrate is concentrated;
Wherein in above-mentioned step four, concentration filtrate obtained in step 3 is placed in separatory funnel, addition is suitable
Amount ethyl alcohol is extracted, and extract liquor is obtained, and repeats appeal operation, and three times, the extract liquor being obtained by extraction three times is closed for extraction
And liquid extracted is placed in beaker, after a small amount of active carbon is added, the liquid heating in beaker is boiled, is being heated
During boiling, liquid is stirred, after the completion of stirring, is filtered to remove active carbon by the method for filtering;
Wherein in above-mentioned step five, by filtrate obtained in step 4 be placed in disc type Multideck take off dryer in into
Row decompression evaporation at constant temperature, until filtrate sets thick filtrate to going out the ethanol evaporation in filtrate for thick stopping
It in surface container, is put into high speed centrifugation drying machine and is dried, during drying, it is ensured that be constant temperature item in drying machine
Part obtains thick Tea Saponin after dry;
Wherein in above-mentioned step six, thick Tea Saponin obtained in step 5 is placed in surface container, dichloro is used
Ethane, into extraction, obtains solids to thick Tea Saponin, repeats extraction process three times, will obtain solids mixing three times, and pour into just
In butanol solution, so that butanol solution carries out the processing of split-phase abstraction purification to solids, after the completion of purifying, obtain mixing molten
Liquid;
Wherein in above-mentioned step seven, mixed solution obtained in step 6 is subjected to distillation processing, removes n-butanol,
Secondary solid object is obtained, methanol mixed solvent is added into secondary solid object and carries out frozen recrystallization under conditions of pH is 5, is obtained
To after crystallization, crystallization is filtered, high-purity tea saponin is made;
Wherein in above-mentioned step eight, Tea Saponin obtained in step 7 is cooled down, is placed on shady and cool drying
It is sealed preservation under environment, avoids direct sunlight.
According to the above technical scheme, in the step 1, the grinding particle size of leached tea oil slag and tea seed cake is l-3mm.
According to the above technical scheme, in the step 2, soaking time 10-15min, flocculant is that a kind of aluminum sulfate is molten
Liquid.
According to the above technical scheme, in the step 3, the temperature of evaporation at constant temperature is 80-90 DEG C.
According to the above technical scheme, in the step 4, the concentration of ethyl alcohol is 75-85%, and the mixing time of decoloration is 2-
3min。
According to the above technical scheme, in the step 5, the temperature of evaporation at constant temperature is 55 DEG C, and the temperature in drying machine is
50-60℃。
According to the above technical scheme, in the step 7, the proportion of first alcohol and water is 8:2 in methanol mixed solvent.
Compared with prior art, the beneficial effects of the present invention are:
1. choosing fresh leached tea oil slag and tea seed cake is raw material, the tea seed for having soil and going mouldy will be infected in raw material
The dregs of rice and tea seed cake are rejected from raw material, are putted the raw materials into pulverizer, so that leached tea oil slag and tea seed cake are ground into scoriform object,
It avoids using tea tree seed, secondary use has been carried out to leached tea oil slag and tea seed cake, has greatly reduced production cost;
2. operating procedure is easily understood during preparation, by filtrate add flocculant, ethyl alcohol, n-butanol and
Methanol solution, and during preparation, repeatedly extracted, can effectively impurity be filtered and be removed, cleaned
Effect is good, improves the purity of Tea Saponin, greatly improves the quality of Tea Saponin.
Detailed description of the invention
Fig. 1 is preparation method flow chart of the invention;
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Referring to Fig. 1, the present invention provides a kind of preparation method of Tea Saponin, include the following steps: step 1, raw material is chosen
With processing;Step 2, extraction filtering;Step 3 is concentrated by evaporation;Step 4 turns extraction decoloration;Step 5, evaporation drying;Step
Six, abstraction purification;Step 7, distillation crystallization;Step 8, transhipment save;
Wherein in above-mentioned step one, choosing fresh leached tea oil slag and tea seed cake is raw material, and contamination in raw material is had mud
Soil and the leached tea oil slag and tea seed cake that go mouldy are rejected from raw material, are putted the raw materials into pulverizer so that leached tea oil slag with
Tea seed cake is ground into scoriform object;
Wherein in above-mentioned step two, a certain amount of tea seed cake powder is weighed, distilled water is added, is placed in loop type extractor
In, after being soaked for a period of time, Tea Saponin leaching liquid is obtained, the filtrate that extraction obtains is used into filtered through gauze while hot, the filter that will be obtained
Slag continues plus distilled water carries out water bath with thermostatic control extraction again, then uses filtered through gauze while hot, operates repeatedly three times, the filtrate that will be obtained
Merge, adds flocculant in filtrate after merging, separated impurity with Tea Saponin filtrate using suction filtration machine;
Wherein in above-mentioned step three, filtrate obtained in step 2 is placed in the de- dryer of disc type Multideck and is carried out
Depressurize evaporation at constant temperature, until filtrate be it is thick so that filtrate disc type Multideck take off dryer in be concentrated, obtain
Filtrate is concentrated;
Wherein in above-mentioned step four, concentration filtrate obtained in step 3 is placed in separatory funnel, addition is suitable
Amount ethyl alcohol is extracted, and extract liquor is obtained, and repeats appeal operation, and three times, the extract liquor being obtained by extraction three times is closed for extraction
And liquid extracted is placed in beaker, after a small amount of active carbon is added, the liquid heating in beaker is boiled, is being heated
During boiling, liquid is stirred, after the completion of stirring, is filtered to remove active carbon by the method for filtering;
Wherein in above-mentioned step five, by filtrate obtained in step 4 be placed in disc type Multideck take off dryer in into
Row decompression evaporation at constant temperature, until filtrate sets thick filtrate to going out the ethanol evaporation in filtrate for thick stopping
It in surface container, is put into high speed centrifugation drying machine and is dried, during drying, it is ensured that be constant temperature item in drying machine
Part obtains thick Tea Saponin after dry;
Wherein in above-mentioned step six, thick Tea Saponin obtained in step 5 is placed in surface container, dichloro is used
Ethane, into extraction, obtains solids to thick Tea Saponin, repeats extraction process three times, will obtain solids mixing three times, and pour into just
In butanol solution, so that butanol solution carries out the processing of split-phase abstraction purification to solids, after the completion of purifying, obtain mixing molten
Liquid;
Wherein in above-mentioned step seven, mixed solution obtained in step 6 is subjected to distillation processing, removes n-butanol,
Secondary solid object is obtained, methanol mixed solvent is added into secondary solid object and carries out frozen recrystallization under conditions of pH is 5, is obtained
To after crystallization, crystallization is filtered, high-purity tea saponin is made;
Wherein in above-mentioned step eight, Tea Saponin obtained in step 7 is cooled down, is placed on shady and cool drying
It is sealed preservation under environment, avoids direct sunlight.
According to the above technical scheme, in step 1, the grinding particle size of leached tea oil slag and tea seed cake is l-3mm, destroys plant
Cell wall, the Tea Saponin in cake of camellia oleifera seeds and tea seed cake can be made to touch leaching agent quickly, be conducive to improve extraction velocity.
According to the above technical scheme, in step 2, soaking time 10-15min, flocculant is that a kind of aluminum sulfate is molten
Liquid, flocculant can remove the unstable impurity of tannin, protein, wax etc. in leaching liquor.
According to the above technical scheme, in step 3, the temperature of evaporation at constant temperature is 80-90 DEG C, depressurizes evaporation at constant temperature, both may be used
So that filtrate rapid concentration, and make Tea Saponin will not be by high temperature.
According to the above technical scheme, in step 4, the concentration of ethyl alcohol is 75-85%, and Tea Saponin is in 95% ethyl alcohol
Solubility is very high, and the solubility in cold water is lower, so Tea Saponin is transferred in ethyl alcohol, and other impurity dissolve in ethanol
It spends lower, is left in subnatant;The mixing time of decoloration is 2-3min, can be improved the adsorption effect of active carbon.
According to the above technical scheme, in step 5, the temperature of evaporation at constant temperature is 55 DEG C, and the temperature in drying machine is 50-
60 DEG C, it can be improved rate of drying.
According to the above technical scheme, in step 7, the proportion of first alcohol and water is 8:2 in methanol mixed solvent, is conducive to
Improve purification effect.
Based on above-mentioned, it is an advantage of the current invention that it is raw material that the present invention, which chooses fresh leached tea oil slag and tea seed cake, by raw material
The middle leached tea oil slag and tea seed cake for having soil and going mouldy of being infected with is rejected from raw material, is putted the raw materials into pulverizer, is made
Leached tea oil slag and tea seed cake are ground into scoriform object, the grinding particle size of leached tea oil slag and tea seed cake is l-3mm, destroys the cell of plant
Wall can make the Tea Saponin in cake of camellia oleifera seeds and tea seed cake touch leaching agent quickly, be conducive to improve extraction velocity;Weigh one
Distilled water is added in quantitative tea seed cake powder, is placed in loop type extractor, after being soaked for a period of time, soaking time 10-15min,
Tea Saponin leaching liquid is obtained, the filtrate that extraction obtains is used into filtered through gauze while hot, obtained filter residue is continued to add distilled water again
Water bath with thermostatic control extraction is carried out, then uses filtered through gauze while hot, operates repeatedly three times, obtained filtrate is merged, filter after merging
Flocculant is added in liquid, flocculant is a kind of aluminum sulfate solution, and flocculant can be by tannin, protein, wax etc. in leaching liquor
Unstable impurity removes, and is separated impurity with Tea Saponin filtrate using suction filtration machine;Obtained filtrate is placed in disc type Multideck to take off
Decompression evaporation at constant temperature is carried out in dryer, the temperature of evaporation at constant temperature is 80-90 DEG C, depressurizes evaporation at constant temperature, both filtrate can be made fast
Speed concentration, but make Tea Saponin will not by high temperature, until filtrate be it is thick so that filtrate is in disc type Multideck
It is concentrated in de- dryer, obtains concentration filtrate;Obtained concentration filtrate is placed in separatory funnel, ethanol in proper amount is added
It is extracted, the concentration of ethyl alcohol is 75-85%, and solubility of the Tea Saponin in 95% ethyl alcohol is very high, and the dissolution in cold water
Spend lower, so Tea Saponin is transferred in ethyl alcohol, and solubility is lower in ethanol for other impurity, is left in subnatant, obtains
Extract liquor, repeats appeal operation, and extraction three times, the extract liquor being obtained by extraction three times is merged, liquid extracted is put
It is placed in a beaker, after a small amount of active carbon is added, the liquid heating in beaker is boiled, during heating is boiled, stirs liquid
The mixing time of body, decoloration is 2-3min, can be improved the adsorption effect of active carbon, after the completion of stirring, passes through the method for filtering
Active carbon is filtered to remove;Obtained filtrate is placed in the de- dryer of disc type Multideck and carries out decompression evaporation at constant temperature, constant temperature
The temperature of evaporation is 55 DEG C, until filtrate is thick stopping, to the ethanol evaporation in filtrate be gone out, by thick filtrate
It is placed in surface container, is put into high speed centrifugation drying machine and is dried, during drying, it is ensured that be constant temperature in drying machine
Condition, the temperature in drying machine are 50-60 DEG C, can be improved rate of drying, obtain thick Tea Saponin after dry;The thick tea that will be obtained
Saponin is placed in surface container, obtains solids into extraction to thick Tea Saponin with dichloroethanes, repeats extraction process three times,
Solids mixing will be obtained three times, will be poured into butanol solution, so that butanol solution carries out split-phase abstraction purification to solids
Processing, after the completion of purifying, obtains mixed solution;Obtained mixed solution is subjected to distillation processing, n-butanol is removed, obtains secondary
Solids adds methanol mixed solvent into secondary solid object and carries out frozen recrystallization under conditions of pH is 5, and methanol mixing is molten
The proportion of first alcohol and water is 8:2 in agent, is conducive to improve purification effect, after obtaining crystallization, is filtered to crystallization, is made high-purity
Spend Tea Saponin;Tea Saponin obtained is cooled down, is placed under shady and cool dry environment and is sealed preservation, avoid sunlight straight
It penetrates;The present invention has carried out secondary use to leached tea oil slag and tea seed cake, has reduced production cost, and during preparation, behaviour
Make simply, good impurity removing effect effectively raises the purity of Tea Saponin.
It should be noted that, in this document, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those
Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or equipment
Intrinsic element.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (7)
1. a kind of preparation method of Tea Saponin includes the following steps: step 1, raw material chooses and processing;Step 2, extracted
Filter;Step 3 is concentrated by evaporation;Step 4 turns extraction decoloration;Step 5, evaporation drying;Step 6, abstraction purification;Step 7 is steamed
Evaporate crystallization;Step 8, transhipment save;It is characterized by:
Wherein in above-mentioned step one, choose fresh leached tea oil slag and tea seed cake be raw material, will in raw material contamination have soil with
And the leached tea oil slag and tea seed cake to go mouldy is rejected from raw material, is putted the raw materials into pulverizer, so that leached tea oil slag and tea seed
Cake is ground into scoriform object;
Wherein in above-mentioned step two, a certain amount of tea seed cake powder is weighed, distilled water is added, is placed in loop type extractor, leaching
After steeping a period of time, Tea Saponin leaching liquid is obtained, the filtrate that extraction obtains is used into filtered through gauze while hot, obtained filter residue is continued
Add distilled water to carry out water bath with thermostatic control extraction again, then use filtered through gauze while hot, operates repeatedly three times, obtained filtrate is merged,
Flocculant is added in filtrate after merging, is separated impurity with Tea Saponin filtrate using suction filtration machine;
Wherein in above-mentioned step three, filtrate obtained in step 2 is placed in the de- dryer of disc type Multideck and is depressurized
Evaporation at constant temperature, until filtrate be it is thick so that filtrate disc type Multideck take off dryer in be concentrated, be concentrated
Filtrate;
Wherein in above-mentioned step four, concentration filtrate obtained in step 3 is placed in separatory funnel, appropriate second is added
Alcohol is extracted, and extract liquor is obtained, and repeats appeal operation, and three times, the extract liquor being obtained by extraction three times is merged for extraction, will
Liquid extracted is placed in beaker, after a small amount of active carbon is added, the liquid heating in beaker is boiled, is boiled in heating
In the process, liquid is stirred, after the completion of stirring, is filtered to remove active carbon by the method for filtering;
Wherein in above-mentioned step five, filtrate obtained in step 4 is placed in the de- dryer of disc type Multideck and is subtracted
Evaporation at constant temperature is pressed, until thick filtrate is placed in table to going out the ethanol evaporation in filtrate for thick stopping by filtrate
In surface vessel, it is put into high speed centrifugation drying machine and is dried, during drying, it is ensured that it is constant temperature in drying machine,
Thick Tea Saponin is obtained after drying;
Wherein in above-mentioned step six, thick Tea Saponin obtained in step 5 is placed in surface container, dichloroethanes is used
To thick Tea Saponin into extraction, solids is obtained, repeats extraction process three times, solids mixing will be obtained three times, pour into n-butanol
In solution, so that butanol solution carries out the processing of split-phase abstraction purification to solids, after the completion of purifying, mixed solution is obtained;
Wherein in above-mentioned step seven, mixed solution obtained in step 6 is subjected to distillation processing, n-butanol is removed, obtains
Secondary solid object adds methanol mixed solvent into secondary solid object and carries out frozen recrystallization under conditions of pH is 5, tied
After crystalline substance, crystallization is filtered, high-purity tea saponin is made;
Wherein in above-mentioned step eight, Tea Saponin obtained in step 7 is cooled down, is placed on shady and cool dry environment
Under be sealed preservation, avoid direct sunlight.
2. a kind of preparation method of Tea Saponin according to claim 1, it is characterised in that: in the step 1, leached tea oil slag
Grinding particle size with tea seed cake is l-3mm.
3. a kind of preparation method of Tea Saponin according to claim 1, it is characterised in that: in the step 2, when immersion
Between be 10-15min, flocculant be a kind of aluminum sulfate solution.
4. a kind of preparation method of Tea Saponin according to claim 1, it is characterised in that: in the step 3, constant temperature steams
The temperature of hair is 80-90 DEG C.
5. a kind of preparation method of Tea Saponin according to claim 1, it is characterised in that: in the step 4, ethyl alcohol
Concentration is 75-85%, and the mixing time of decoloration is 2-3min.
6. a kind of preparation method of Tea Saponin according to claim 1, it is characterised in that: in the step 5, constant temperature steams
The temperature of hair is 55 DEG C, and the temperature in drying machine is 50-60 DEG C.
7. a kind of preparation method of Tea Saponin according to claim 1, it is characterised in that: in the step 7, methanol is mixed
The proportion of first alcohol and water is 8:2 in bonding solvent.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110724595A (en) * | 2019-10-11 | 2020-01-24 | 浙江久晟油茶科技股份有限公司 | Biological polysaccharide flocculant and preparation method and application thereof |
CN111689809A (en) * | 2020-06-23 | 2020-09-22 | 重庆琥珀茶油有限公司 | Tea saponin functional organic fertilizer and preparation method thereof |
CN112194700A (en) * | 2020-10-09 | 2021-01-08 | 张利民 | Preparation method of natural high-purity tea saponin with high decontamination efficiency |
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CN103833819A (en) * | 2014-02-12 | 2014-06-04 | 安徽省华银茶油有限公司 | New technology for extraction of tea saponin from tea seed meal |
CN104530173A (en) * | 2014-12-11 | 2015-04-22 | 福建华仁油脂有限公司 | Process for extracting tea saponin from oil tea cake |
CN104961793A (en) * | 2015-06-29 | 2015-10-07 | 兰捷 | Method for extracting high-purity tea saponin from tea seed cake dregs |
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CN1068360A (en) * | 1991-07-03 | 1993-01-27 | 湖南师范大学 | From oil tea (tea-seed) grouts, extract the technology of tea oil and saponin |
CN101962396A (en) * | 2009-07-21 | 2011-02-02 | 浙江大学 | Method for preparing tea saponin from oil tea cakes, tea seed meal, tea seed oil cakes |
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CN110724595A (en) * | 2019-10-11 | 2020-01-24 | 浙江久晟油茶科技股份有限公司 | Biological polysaccharide flocculant and preparation method and application thereof |
CN111689809A (en) * | 2020-06-23 | 2020-09-22 | 重庆琥珀茶油有限公司 | Tea saponin functional organic fertilizer and preparation method thereof |
CN112194700A (en) * | 2020-10-09 | 2021-01-08 | 张利民 | Preparation method of natural high-purity tea saponin with high decontamination efficiency |
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