CN103965283B - A kind of separation method of high purity diosgenin - Google Patents
A kind of separation method of high purity diosgenin Download PDFInfo
- Publication number
- CN103965283B CN103965283B CN201410145370.4A CN201410145370A CN103965283B CN 103965283 B CN103965283 B CN 103965283B CN 201410145370 A CN201410145370 A CN 201410145370A CN 103965283 B CN103965283 B CN 103965283B
- Authority
- CN
- China
- Prior art keywords
- diosgenin
- dioscin
- filter residue
- crude product
- extraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of separation method of high purity diosgenin, belong to medicine material production technical field, adopt ultrasonic assistant sodium lauryl sulphate abstraction technique, utilize the solublization of sodium lauryl sulphate, first dioscin is extracted from Rhizome of Peltate Yam, flocculation technique is adopted to be separated from extraction liquid by dioscin again, obtain dioscin crude product, dioscin crude product, through hydrolysis, filtration, washing, drying, refluxing extraction and crystallisation by cooling, obtains diosgenin crude product.Then diosgenin crude product is added in warm water in batches and carry out precision processing, obtain the diosgenin after precision processing.Precision processing operation of the present invention overcomes the shortcoming of diosgenin separation and purification difficulty, and the purity of the diosgenin after precision processing can reach more than 98.5%.
Description
Technical field
The invention belongs to medicine material production technical field, be specifically related to a kind of separation method of high purity diosgenin.
Background technology
Around pollution problem and the Cost Problems of producing diosgenin, people have carried out a large amount of research work, achieve some achievements.Before 2003, China generally adopts pre fermentation-acidolysis process to produce diosgenin, and this technique is compared with classical acid direct hydrolysis technique, and the productive rate of diosgenin increases, but substantially suitable with traditional technology by acid amount, therefore pollute substantially identical with traditional technology.In research process, it is found that and cause the acid of diosgenin production process greatly, COD value in waste water, the root that BOD value is high are: the dioscin in Rhizome of Peltate Yam is while being hydrolyzed to diosgenin, and the starch in Rhizome of Peltate Yam, Mierocrystalline cellulose are hydrolyzed to carbohydrate (monose, disaccharides, trisaccharide and polysaccharide).In order to reduce the consumption of acid, Li Xiang etc. are on the basis analyzing starch, Mierocrystalline cellulose, xylogen, dioscin equal distribution and character in Rhizome of Peltate Yam, adopt wet grinding mill sizing process, starch, Mierocrystalline cellulose, xylogen, dioscin are separated, decrease the consumption of acid to a certain extent, reduce the COD value of waste water, BOD value, colourity etc., reclaim the starch in Rhizome of Peltate Yam, Mierocrystalline cellulose.2003 under the support of national environmental protection project, this technology is used for the suitability for industrialized production of diosgenin by Environmental Protection Agency of Shaanxi Province, build up in Shangluo Prefecture to be separated into main diosgenin cleaner production model enterprise-adret Jinchuan Feng Xing chemical industry limited liability company, from running condition, the consumption of this technology acid, coal, gasoline is respectively 10% ~ 15%, 25% ~ 50% and 30% ~ 35% of traditional technology, wastewater discharge is 90% of traditional technology, the COD value of waste water, BOD value are 10% of traditional technology, in recyclable Rhizome of Peltate Yam 20% ~ 25% starch.But because this operational path is longer, facility investment is large, and cost is high, and contain silt etc. due to the starch reclaimed, limit the application of reclaiming starch.
In order to reduce the production cost of diosgenin, ultrasonic technology, on the basis of traditional ethanol abstraction technique, is introduced in the research of dioscin extraction, has been saved the extraction time of dioscin widely by LinliQiu etc., improve the extraction efficiency of dioscin, add the yield of diosgenin.But because in extraction process, ethanol loss is comparatively large, poor stability etc. constrain applying of this technology.Liu Shuxing etc. tensio-active agent is used for dioscin extraction research in, found that, when diosgenin yield is constant, tensio-active agent add the volume fraction significantly reducing ethanol.
Be extraction agent with Surfactant SDS, take flocculation technique as the consumption that the process for producing diosgenin of core effectively reduces acid in diosgenin production process, decrease pollution, reduce cost.But often there is the phenomenon that diosgenin crystal is wrapped up by lauryl alcohol (oily matter), this phenomenon causes diosgenin separation difficulty, the diosgenin product obtained often purity is not high.
Summary of the invention
In order to overcome the defect that above-mentioned prior art exists, the object of the present invention is to provide a kind of separation method of high purity diosgenin, the method is simple to operate, environmental friendliness, effectively can solve the problem of diosgenin separation and purification difficulty.
The present invention is achieved through the following technical solutions:
A separation method for high purity diosgenin, comprise roughing out and precision processing two step, described roughing out concrete operation step is:
1) Rhizome of Peltate Yam pulverized is immersed in sodium dodecyl sulfate solution, after lixiviate 2 ~ 4h, ultrasonic extraction, then centrifugal, obtain dioscin extraction liquid and filter residue;
2) by filter residue continuation sodium dodecyl sulfate solution ultrasonic extraction, then centrifugal, the dioscin extraction liquid that the centrifugal extraction liquid that obtains and step 1) obtain is merged, obtains the total extraction liquid of dioscin;
3) by the total extraction liquid of dioscin: the flocculating agent A aqueous solution=100:(4 ~ 10) volume ratio, in the total extraction liquid of dioscin, add massfraction is 0.8% ~ 1.2% flocculating agent A aqueous solution, after Micelle formation stop stir, after leaving standstill 5 ~ 20min, filter, obtain filter residue 1 and filtrate 1, then add the flocculating agent B aqueous solution that massfraction is 2% ~ 6% to filtrate 1, at 40 ~ 50 DEG C, after leaving standstill 1 ~ 3h, centrifugal, obtain filtrate 2 and filter residue 2, merge filter residue 1 and filter residue 2, obtain dioscin crude product;
Wherein, described flocculating agent A, in massfraction, comprises the chitosan of 95% ~ 100%, the xanthan gum of 0% ~ 5%; Described flocculating agent B, in massfraction, comprises the bar-shaped wilkinite of 55 ~ 60%, the bentonite clarifying agent of 40 ~ 45%;
4) ratio of 2.5 ~ 3mL sulfuric acid is added in every g dioscin crude product, dioscin crude product being joined concentration is in the sulfuric acid of 1.3 ~ 1.8mol/L, at 105 ~ 108 DEG C, after hydrolysis 4 ~ 6h, cooled by hydrolyzed solution and neutralize rear filtration, washing filter residue is rear dry in neutrality to effluent liquid, then by the filter residue of drying after refluxing extraction, cooling, crystallization, obtain diosgenin crude product;
Described precision processing concrete operation step is:
(1) in diosgenin crude product, instilling temperature is in the water of 60 ~ 90 DEG C, stirs, and then centrifugal, reject upper water and oily matter, obtain diosgenin;
(2) by after the diosgenin repeating step (1) of purifying operation 2 ~ 4 times, the diosgenin with moisture is carried out drying, obtains high purity diosgenin.
In precision processing operation, the temperature of diosgenin crude product and instillation is the usage ratio of the water of 60 ~ 90 DEG C is 1g:(5 ~ 10) mL.
Centrifugal in precision processing operation described in step (1) is under the condition of 2500 ~ 3000r/min, centrifugal 5 ~ 10min.
Drying in precision processing operation carries out at 60 ~ 70 DEG C.
Step 1) in roughing out operation is according to 1g:(8 ~ 10) ratio of mL, immerses the Rhizome of Peltate Yam after pulverizing in sodium dodecyl sulfate solution.
Ultrasonic extraction described in roughing out operation is under ultrasonic frequency is 25.8KHz, extraction 25 ~ 30min.
Roughing out operation described in centrifugal be under the condition of 2000 ~ 4000r/min, centrifugal 8 ~ 15min.
The concentration of the sodium dodecyl sulfate solution described in roughing out operation is 25.8 × 10
-3mol/L.
Neutralization in roughing out operation described in step 4) is under agitation, adds the Na that massfraction is 18% ~ 22%
2cO
3solution; Described drying temperature is 50 ~ 60 DEG C.
Refluxing extraction in roughing out operation described in step 4) is specially: after being wrapped up by the filter residue filter paper of drying, be placed in apparatus,Soxhlet's, add the sherwood oil of container 4/5 volume, with the speed refluxing extraction 4 ~ 6h of 4 ~ 6 per second.
Compared with prior art, the present invention has following useful technique effect:
The present invention adopts ultrasonic assistant sodium lauryl sulphate abstraction technique, utilize the solublization of sodium lauryl sulphate, first dioscin is extracted from Rhizome of Peltate Yam, flocculation technique is adopted to be separated from extraction liquid by dioscin again, obtain dioscin crude product, dioscin crude product, through hydrolysis, filtration, washing, drying, refluxing extraction and crystallisation by cooling, obtains diosgenin crude product.Then add in warm water in diosgenin crude product and carry out precision processing, obtain the diosgenin after precision processing.
Advantage of the present invention is mainly reflected in:
1, the present invention take Surfactant SDS as extraction agent, avoids the use (organic solvent of the prior art, as alcohol extraction dioscin) of organic solvent, reduces cost, decrease pollution, add the security of operating process;
2, the present invention substitutes traditional hot beneficiation technologies with flocculation technique, prevent in dioscin enrichment (concentrating) process, (sodium lauryl sulphate, dioscin are tensio-active agent to cause the loss of dioscin because bubbling, therefore very easily bubble when vacuum concentration), reduce the energy consumption in dioscin enrichment process, ensure that the cleaner production of diosgenin under low cost, prove that flocculence occupies very large advantage than traditional hot concentration method on cost through test of many times;
3, the present invention adopts homemade flocculating agent A and flocculating agent B, there is good flocculating effect, flocculating agent A composition comprises chitosan and xanthan gum, containing a certain amount of amido in chitosan molecule, for cationic flocculant, with the dioscin micelle generation electrostatic neutralizing effect of negatively charged in extraction liquid, dioscin micelle is impelled to flocculate; Xanthan gum adds in dioscin extraction liquid, can form the spiral interpolymer of superjunction crossed belt shape, forms the reticulated structure of fragile similar glue; When the concentration of xanthan gum is higher, this reticulated structure can support the form of solid particulate in extraction liquid, drop and bubble, demonstrates very strong stable emulsifying effect and higher suspension ability.When the concentration of xanthan gum is lower, this reticulated structure can catch the flocs unit that dioscin micelle in extraction liquid and chitosan are formed, and accelerates the flocculation of dioscin;
Flocculating agent B comprises bar-shaped wilkinite finings and bentonite clarifying agent, wilkinite is a kind of material of vesicular structure, there is very strong adsorption, on the one hand, can sorption extraction liquid by chitosan (xanthan gum) absorption (flocculation) dioscin, on the other hand, because wilkinite proportion is comparatively large, the flocculation of dioscin can be accelerated.Bar-shaped wilkinite and bentonite clarifying agent are distinguish to some extent in nature, and bar-shaped wilkinite specific surface area is large, high adsorption capacity, in dioscin flocculation process, can adsorb not by the dioscin of chitosan, xanthan gum flocculation.Bentonite clarifying agent specific surface area is relatively little, and adsorptive power is relatively weak, but density is relatively large, used in combination with bar-shaped wilkinite, can accelerate the separation of dioscin in extraction liquid.
4, compared with traditional technology, decrease the consumption of acid during dioscin hydrolysis, reduce COD value in waste water, BOD value, ammonia nitrogen, solid content, thus saved cost for wastewater treatment.
5, precision processing of the present invention operation overcomes that to adopt with Surfactant SDS be extraction agent, is that the diosgenin clean preparation method gained diosgenin of core is wrapped up by lauryl alcohol (oily matter) with flocculation technique, the shortcoming of diosgenin separation and purification difficulty, the purity of the diosgenin after precision processing can reach more than 98.5%.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and the explanation of the invention is not limited.
Lauryl alcohol is white or colourless oil liquid, tool flowery odour, fusing point 24 DEG C, boiling point 255-259 DEG C, relative density 0.8201g/cm
3(24 DEG C), flash-point 126.7 DEG C, water insoluble, glycerine, is dissolved in propylene glycol, ethanol, benzene, chloroform, ether.
Diosgenin is white or micro-yellow crystalline powder, fusing point 195 DEG C, boiling point 527.1 DEG C, relative density 1.13g/cm
3(25 DEG C), flash-point 272.6 DEG C, water insoluble, be soluble in the organic solvents such as gasoline, ethanol, chloroform.
As can be seen from above-mentioned character, lauryl alcohol is very similar to the chemical property of diosgenin, adopts chemical method separating difficulty larger.The boiling point of lauryl alcohol and diosgenin differs greatly, and lauryl alcohol is 255-259 DEG C, and diosgenin is 527.1 DEG C, and distillation under vacuum can be adopted to be separated, but vacuum distillation equipment investment is large, and the production cost of diosgenin certainly will be caused to rise.Fusing point, the Relatively density contrast of lauryl alcohol and diosgenin are also comparatively large, and the fusing point of lauryl alcohol is 24 DEG C, and relative density is 0.8201g/cm
3(24 DEG C), and the fusing point of diosgenin is 195 DEG C, relative density is 1.13g/cm
3(25 DEG C).If the oily matter of the lauryl alcohol with hot-water cure parcel diosgenin, because lauryl alcohol fusing point is low, relative density is little, therefore be suspended on the water surface, diosgenin fusing point is high, and relative density is large, water insoluble again, therefore in underwater, the oily matter of diosgenin crystal and lauryl alcohol simply, effectively can be separated by the inventive method.
Embodiment 1
A flocculation extracting method for diosgenin, comprises roughing out and fine-treatment step:
Roughing out:
1) first getting 100g granularity is 80 object Rhizome of Peltate Yam, and adding 1000mL concentration is 25.8 × 10
-3in the sodium dodecyl sulfate solution of mol/L, at soaking at room temperature 2h, then under ultrasonic frequency is 25.8KHz, ultrasonic extraction 30min, centrifugation, obtains dioscin extraction liquid 1 and Rhizome of Peltate Yam filter residue; By Rhizome of Peltate Yam filter residue: Rhizome of Peltate Yam filter residue joins in dodecyl sulphate solution by the solid-liquid ratio of sodium lauryl sulphate=1g:8mL, under identical ultrasound condition, ultrasonic extraction, centrifugation, obtains extraction liquid 2 and filter residue; And then by filter residue: filter residue adds in sodium lauryl sulphate by the solid-liquid ratio of sodium lauryl sulphate=1g:5mL, ultrasonic extraction under the same terms, then collected by centrifugation extraction liquid 3, then merges extraction liquid 1, extraction liquid 2 and extraction liquid 3 and obtains the total extraction liquid of dioscin.
2) according to adding the ratio that 5mL massfraction is the self-control flocculating agent A aqueous solution of 0.8% in 100mL extraction liquid, in the total extraction liquid of dioscin, rapid stirring limit, limit dropwise adds the flocculating agent A aqueous solution, stop stirring after Micelle formation, after leaving standstill 10min, micelle major part is sunk, few part floats, middle layer clarification bright (now the ζ of system approximates 0), filter, obtain filter residue 1 and filtrate, give in filtrate again and add the self-control flocculating agent B aqueous solution through immersion treatment that massfraction is 5% while stirring, after gel group is fully formed, stop stirring, at 40 DEG C, leave standstill 1h, centrifugation 10min at 3,000 rpm, obtain filter residue 2, merge filter residue 1 and filter residue 2, obtain dioscin crude product,
Wherein, described flocculating agent A, in massfraction, comprises the chitosan of 95%, the xanthan gum of 5%; Described flocculating agent B, in massfraction, comprises the bar-shaped wilkinite finings (the special finings of grape wine) of 60%, the fruit juice clarifier (bentonite clarifying agent) of 40%.
3) according to dioscin crude product: the ratio of sulfuric acid=1g:2.5mL, to the sulfuric acid adding 1.5mol/L in dioscin crude product, at 108 DEG C, be hydrolyzed 4h, cooling hydrolyzed solution, to room temperature, under agitation, slowly adds the Na of 20%
2cO
3solution neutralizes, and filters, with water repeatedly lotion filter residue to without SO
4 2-, at 50 DEG C, dry filter residue is to constant weight.
4) wrap with the filter residue of filter paper by dry gained, be placed in the soxhlet's extractor of 100mL, add the sherwood oil of about 80mL, with the speed of 4/s backflow 4h, after recovery part sherwood oil, crystallisation by cooling, obtains diosgenin crude product;
Precision processing:
(1) get 1g diosgenin crude product, in diosgenin crude product, dropwise add the hot water that 10mL temperature is 90 DEG C, after the water surface having oily matter occur, centrifugal 10min under 3000r/min, reject upper water and oily matter, obtain diosgenin;
(2) operation 2 times of repeating step (1), obtains the diosgenin with moisture, then at 60 DEG C, is dried to constant weight, and obtain the Powdered diosgenin of white, purity is 98.9%.
Embodiment 2
A flocculation extracting method for diosgenin, comprises the following steps:
Roughing out:
1) first getting 100g granularity is 80 object Rhizome of Peltate Yam, and adding 800mL concentration is 25.8 × 10
-3in the sodium dodecyl sulfate solution of mol/L, at room temperature soak 3h, under ultrasonic frequency is 25.8KHz, ultrasonic extraction 30min, centrifugation, obtains dioscin extraction liquid 1 and Rhizome of Peltate Yam filter residue; By Rhizome of Peltate Yam filter residue: Rhizome of Peltate Yam filter residue joins in dodecyl sulphate solution by the solid-liquid ratio of sodium lauryl sulphate=1g:10mL, under identical ultrasound condition, ultrasonic extraction, centrifugation, obtains extraction liquid 2 and filter residue; And then by filter residue: filter residue adds in sodium lauryl sulphate by the solid-liquid ratio of sodium lauryl sulphate=1g:7mL, ultrasonic extraction under the same terms, then collected by centrifugation extraction liquid 3, then merges extraction liquid 1, extraction liquid 2 and extraction liquid 3 and obtains the total extraction liquid of dioscin
2) according to adding the ratio that 4mL massfraction is the self-control flocculating agent A of 1% in 100mL extraction liquid, in the total extraction liquid of dioscin, rapid stirring limit, limit dropwise adds the flocculating agent A aqueous solution, stop stirring after Micelle formation, after leaving standstill 20min, micelle major part is sunk, few part floats, middle layer clarification bright (now the ζ of system approximates 0), filter, obtain filter residue 1 and filtrate, give in filtrate again and add the flocculating agent B aqueous solution that massfraction is 4% while stirring, at 40 DEG C, after leaving standstill 3h, centrifugation under 3000rpm/10min, obtain filtrate and filter residue 2, merge filter residue 1 and filter residue 2, obtain dioscin crude product,
Wherein, described flocculating agent A, in massfraction, comprises the chitosan of 97%, the xanthan gum of 3%; Described flocculating agent B, in massfraction, comprises the bar-shaped wilkinite finings (the special finings of grape wine) of 55%, the fruit juice clarifier (bentonite clarifying agent) of 45%.
3) according to dioscin crude product: the ratio of sulfuric acid=1g:3mL, to the sulfuric acid adding 1.3mol/L in dioscin crude product, at 105 DEG C, be hydrolyzed 4h, cooling hydrolyzed solution, to room temperature, under agitation, slowly adds the Na of 18%
2cO
3solution neutralizes, and filters, with water repeatedly lotion filter residue to without SO
4 2-, at 55 DEG C, dry filter residue is to constant weight.
4) wrap with the filter residue of filter paper by dry gained, be placed in the soxhlet's extractor of 100mL, add the sherwood oil of about 80mL, with the speed of 5/s backflow 5h, after recovery part sherwood oil, crystallisation by cooling, obtains diosgenin crude product;
Precision processing
(1) get 1g diosgenin crude product, in diosgenin crude product, dropwise add the hot water that 8mL temperature is 70 DEG C, after the water surface having oily matter occur, centrifugal 8min under 3000r/min, reject upper water and oily matter, obtain diosgenin;
(2) operation 3 times of repeating step (1), obtains the diosgenin with moisture, then at 70 DEG C, is dried to constant weight, and obtain the Powdered diosgenin of white, purity is 99.3%.
Embodiment 3
A flocculation extracting method for diosgenin, comprises the following steps:
Roughing out:
1) first getting 100g granularity is 100 object Rhizome of Peltate Yam, and adding 900mL concentration is 25.8 × 10
-3in the sodium dodecyl sulfate solution of mol/L, at room temperature soak 4h, under ultrasonic frequency is 25.8KHz, ultrasonic extraction 30min, centrifugation obtains dioscin extraction liquid 1 and Rhizome of Peltate Yam filter residue; By Rhizome of Peltate Yam filter residue: Rhizome of Peltate Yam filter residue joins in dodecyl sulphate solution by the solid-liquid ratio of sodium lauryl sulphate=1g:9mL, under identical ultrasound condition, ultrasonic extraction, centrifugation, obtains extraction liquid 2 and filter residue; And then by filter residue: filter residue adds in sodium lauryl sulphate by the solid-liquid ratio of sodium lauryl sulphate=1g:6mL, ultrasonic extraction under the same terms, then collected by centrifugation extraction liquid 3, then merges extraction liquid 1, extraction liquid 2 and extraction liquid 3 and obtains the total extraction liquid of dioscin.
2) according to adding the ratio that 6mL massfraction is the self-control flocculating agent A aqueous solution of 1.2% in 100mL extraction liquid, in the total extraction liquid of dioscin, rapid stirring limit, limit dropwise adds the flocculating agent A aqueous solution, stop stirring after Micelle formation, after leaving standstill 15min, micelle major part is sunk, few part floats, middle layer clarification bright (now the ζ of system approximates 0), filter, obtain filter residue 1 and filtrate, give in filtrate again and add the self-control flocculating agent B aqueous solution through immersion treatment that massfraction is 5% while stirring, at 50 DEG C, after leaving standstill 1h, centrifugation under 3000rpm/10min, obtain filtrate and filter residue 2, merge filter residue 1 and filter residue 2, obtain dioscin crude product
Wherein, described flocculating agent A is chitosan; Described flocculating agent B, in massfraction, comprises the bar-shaped wilkinite finings (the special finings of grape wine) of 58%, the fruit juice clarifier (bentonite clarifying agent) of 42%.
3) according to dioscin crude product: the ratio of sulfuric acid=1g:2.8mL, to the sulfuric acid adding 1.8mol/L in dioscin crude product, at 108 DEG C, be hydrolyzed 6h, cooling hydrolyzed solution, to room temperature, under agitation, slowly adds the Na of 22%
2cO
3solution neutralizes, and filters, with water repeatedly lotion filter residue to without SO
4 2-, at 60 DEG C, dry filter residue is to constant weight.
4) wrap with the filter residue of filter paper by dry gained, be placed in the soxhlet's extractor of 100mL, add the sherwood oil of about 80mL, with the speed of 6/s backflow 4h, after recovery part sherwood oil, crystallisation by cooling, obtains diosgenin crude product;
Precision processing:
(1) get 1g diosgenin crude product, in diosgenin crude product, dropwise add the hot water that 5mL temperature is 80 DEG C, after the water surface having oily matter occur, centrifugal 5min under 3000r/min, reject upper water and oily matter, obtain diosgenin;
(2) operation 2 times of repeating step (1), obtains the diosgenin with moisture, then at 60 DEG C, is dried to constant weight, and obtain the Powdered diosgenin of white, purity is 99.1%.
Embodiment 4
A flocculation extracting method for diosgenin, comprises the following steps:
Roughing out:
1) first getting 100g granularity is 80 ~ 100 object Rhizome of Peltate Yam, and adding 1000mL concentration is 25.8 × 10
-3in the sodium dodecyl sulfate solution of mol/L, soaking at room temperature 3h, under ultrasonic frequency is 25.8KHz, ultrasonic extraction 30min, centrifugation obtains dioscin extraction liquid 1 and Rhizome of Peltate Yam filter residue; By Rhizome of Peltate Yam filter residue: Rhizome of Peltate Yam filter residue joins in dodecyl sulphate solution by the solid-liquid ratio of sodium lauryl sulphate=1g:8mL, under identical ultrasound condition, ultrasonic extraction, centrifugation, obtains extraction liquid 2 and filter residue; And then by filter residue: filter residue adds in sodium lauryl sulphate by the solid-liquid ratio of sodium lauryl sulphate=1g:5mL, ultrasonic extraction under the same terms, then collected by centrifugation extraction liquid 3, is then merged by extraction liquid 1,2,3 and obtains the total extraction liquid of dioscin.
2) according to adding the ratio that 10mL massfraction is the self-control flocculating agent A aqueous solution of 1% in 100mL extraction liquid, in the total extraction liquid of dioscin, rapid stirring limit, limit dropwise adds the flocculating agent A aqueous solution, stop stirring after Micelle formation, after leaving standstill 5min, micelle major part is sunk, few part floats, middle layer clarification bright (now the ζ of system approximates 0), filter, obtain filter residue 1 and filtrate, give in filtrate again and add the flocculating agent B aqueous solution through immersion treatment that massfraction is 4% while stirring, at 45 DEG C, after leaving standstill 2h, centrifugation under 3000rpm/10min, obtain filtrate and filter residue 2, merge and filter residue 2, obtain dioscin crude product,
Wherein, described flocculating agent A, in massfraction, comprises the chitosan of 96%, the xanthan gum of 4%; Described flocculating agent B, in massfraction, comprises the bar-shaped wilkinite finings (the special finings of grape wine) of 60%, the fruit juice clarifier (bentonite clarifying agent) of 40%.
3) according to dioscin crude product: the ratio of sulfuric acid=1g:2.8mL, to the sulfuric acid adding 1.5mol/L in dioscin crude product, at 107 DEG C, be hydrolyzed 6h, cooling hydrolyzed solution, to room temperature, under agitation, slowly adds the Na of 20%
2cO
3solution neutralizes, and filters, with water repeatedly lotion filter residue to without SO
4 2-, at 55 DEG C, dry filter residue is to constant weight.
4) wrap with the filter residue of filter paper by dry gained, be placed in the soxhlet's extractor of 100mL, add the sherwood oil of about 80mL, with the speed of 5/s backflow 4h, after recovery part sherwood oil, crystallisation by cooling, obtains diosgenin crude product;
Precision processing:
(1) get 1g diosgenin crude product, in diosgenin crude product, dropwise add the hot water that 10mL temperature is 60 DEG C, after the water surface having oily matter occur, centrifugal 8min under 2500r/min, reject upper water and oily matter, obtain diosgenin;
(2) operation 4 times of repeating step (1), obtains the diosgenin with moisture, then at 70 DEG C, is dried to constant weight, and obtain the Powdered diosgenin of white, purity is 98.5%.
In sum, the present invention is extraction agent with sodium lauryl sulphate, take flocculation technique as the consumption that the diosgenin production method of core effectively reduces acid in diosgenin production process, decreases pollution, reduces cost.Meanwhile, precision processing operation efficiently solves the phenomenon that diosgenin crystal is wrapped up by lauryl alcohol, and diosgenin, lauryl alcohol can be separated by the present invention, simple, is separated and obtains highly purified diosgenin.
Claims (7)
1. a separation method for high purity diosgenin, is characterized in that, comprise roughing out and precision processing two step, described roughing out concrete operation step is:
1) Rhizome of Peltate Yam pulverized is immersed in sodium dodecyl sulfate solution, after lixiviate 2 ~ 4h, ultrasonic extraction, then centrifugal, obtain dioscin extraction liquid and filter residue;
2) by filter residue continuation sodium dodecyl sulfate solution ultrasonic extraction, then centrifugal, by the centrifugal extraction liquid that obtains and step 1) the dioscin extraction liquid that obtains merges, and obtains the total extraction liquid of dioscin;
3) by the total extraction liquid of dioscin: the flocculating agent A aqueous solution=100:(4 ~ 10) volume ratio, in the total extraction liquid of dioscin, add massfraction is 0.8% ~ 1.2% flocculating agent A aqueous solution, stop stirring after Micelle formation, after leaving standstill 5 ~ 20min, filter, obtain filter residue 1 and filtrate 1, add the flocculating agent B aqueous solution that massfraction is 2% ~ 6% to again filtrate 1, at 40 ~ 50 DEG C, after leaving standstill 1 ~ 3h, centrifugal, obtain filtrate 2 and filter residue 2, merge filter residue 1 and filter residue 2, obtain dioscin crude product;
Wherein, described flocculating agent A, in massfraction, comprises the chitosan of 95% ~ 100%, the xanthan gum of 0% ~ 5%; Described flocculating agent B, in massfraction, comprises the bar-shaped wilkinite of 55 ~ 60%, the bentonite clarifying agent of 40 ~ 45%;
Described ultrasonic extraction is under ultrasonic frequency is 25.8KHz, extraction 25 ~ 30min; Described centrifugal be under the condition of 2000 ~ 4000r/min, centrifugal 8 ~ 15min;
4) ratio of 2.5 ~ 3mL sulfuric acid is added in every g dioscin crude product, dioscin crude product being joined concentration is in the sulfuric acid of 1.3 ~ 1.8mol/L, at 105 ~ 108 DEG C, after hydrolysis 4 ~ 6h, cooled by hydrolyzed solution and neutralize rear filtration, washing filter residue is rear dry in neutrality to effluent liquid, then by the filter residue of drying after refluxing extraction, cooling, crystallization, obtain diosgenin crude product;
Described precision processing concrete operation step is:
(1) in diosgenin crude product, instilling temperature is in the water of 60 ~ 90 DEG C, stirs, then under the condition of 2500 ~ 3000r/min, and centrifugal 5 ~ 10min, reject upper water and oily matter, obtain diosgenin;
(2) by after the diosgenin repeating step (1) of purifying operation 2 ~ 4 times, the diosgenin with moisture is carried out drying, obtains high purity diosgenin.
2. the separation method of a kind of high purity diosgenin according to claim 1, is characterized in that, in precision processing operation, the temperature of diosgenin crude product and instillation is the usage ratio of the water of 60 ~ 90 DEG C is 1g:(5 ~ 10) mL.
3. the separation method of a kind of high purity diosgenin according to claim 1, is characterized in that, the drying in precision processing operation carries out at 60 ~ 70 DEG C.
4. according to the separation method of a kind of high purity diosgenin in claims 1 to 3 described in any one, it is characterized in that, step 1 in roughing out operation) be according to 1g:(8 ~ 10) ratio of mL, the Rhizome of Peltate Yam after pulverizing is immersed in sodium dodecyl sulfate solution.
5. according to the separation method of a kind of high purity diosgenin in claims 1 to 3 described in any one, it is characterized in that, the concentration of the sodium dodecyl sulfate solution described in roughing out operation is 25.8 × 10
-3mol/L.
6., according to the separation method of a kind of high purity diosgenin in claims 1 to 3 described in any one, it is characterized in that, roughing out operation in step 4) described in neutralization be under agitation, add the Na that massfraction is 18% ~ 22%
2cO
3solution; Described drying temperature is 50 ~ 60 DEG C.
7. according to the separation method of a kind of high purity diosgenin in claims 1 to 3 described in any one, it is characterized in that, roughing out operation in step 4) described in refluxing extraction be specially: by the filter residue filter paper of drying wrap up after, be placed in apparatus,Soxhlet's, add the sherwood oil of container 4/5 volume, with the speed refluxing extraction 4 ~ 6h of 4 ~ 6 per second.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410145370.4A CN103965283B (en) | 2014-04-11 | 2014-04-11 | A kind of separation method of high purity diosgenin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410145370.4A CN103965283B (en) | 2014-04-11 | 2014-04-11 | A kind of separation method of high purity diosgenin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103965283A CN103965283A (en) | 2014-08-06 |
| CN103965283B true CN103965283B (en) | 2016-02-10 |
Family
ID=51235331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410145370.4A Active CN103965283B (en) | 2014-04-11 | 2014-04-11 | A kind of separation method of high purity diosgenin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103965283B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774240A (en) * | 2015-04-30 | 2015-07-15 | 陕西科技大学 | Method for extracting diosgenin through dioscin hydrolysis |
| CN105534946A (en) * | 2016-01-11 | 2016-05-04 | 陕西科技大学 | Preparation method of traditional Chinese medicine capsules |
| CN107827949B (en) * | 2017-11-07 | 2019-11-12 | 西南民族大学 | A kind of diosgenin antitumor derivative and its synthetic method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591373A (en) * | 2008-05-28 | 2009-12-02 | 河南大学 | A kind of extracting method of dioscin |
| CN101705275A (en) * | 2009-10-30 | 2010-05-12 | 陕西科技大学 | Process for producing diosgenin and method for processing peltate yam after extracting same |
-
2014
- 2014-04-11 CN CN201410145370.4A patent/CN103965283B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591373A (en) * | 2008-05-28 | 2009-12-02 | 河南大学 | A kind of extracting method of dioscin |
| CN101705275A (en) * | 2009-10-30 | 2010-05-12 | 陕西科技大学 | Process for producing diosgenin and method for processing peltate yam after extracting same |
Non-Patent Citations (1)
| Title |
|---|
| 表面活性剂提取薯蓣皂苷及薯蓣皂苷元水解工艺的研究;兀浩;《中国优秀硕士学位论文全文数据库工程科技Ⅰ集》;20131215(第S2期);28-41 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103965283A (en) | 2014-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102730696B (en) | Physical method for recovering cutting liquid, crystal silicon micro-powder and silicon carbide micro-powder from silicon wafer cutting waste mortar | |
| CN102951641B (en) | Water-saving and environmental protection-type preparation method of silicon carbide micro-powder for silicon wafer wire cutting | |
| CN102604732A (en) | Static mixed rotational flow separation and extraction process of regenerative base oil N-methyl pyrrolidone | |
| CN102600988B (en) | Foam flotation method for separating silicon powder from silicon carbide powder | |
| CN102295981B (en) | Separation method of mortar generated in silicon chip cutting | |
| CN103965283B (en) | A kind of separation method of high purity diosgenin | |
| CN107746142A (en) | Washery slag acid waste water Zero emission method in a kind of Titanium White Production By Sulfuric Acid Process | |
| CN102492151A (en) | Preparation method of cationic paddy hull flocculating agent for sludge dredging and flocculating and dewatering | |
| CN103880914A (en) | Flocculation extraction method of diosgenin | |
| CN107686203A (en) | A kind of recycling treatment process using cross current solvent extraction method to H acid producing waste waters | |
| CN104148025A (en) | Preparation of nanosilicon dioxide modified by polysaccharide and application of nanosilicon dioxide to treatment of printing and dyeing wastewater | |
| CN102276038A (en) | Polymeric ferric sulfate-carboxymethyl potato starch composite flocculant and preparation method and application thereof | |
| CN103232039A (en) | Silicon carbide filter cake cyclone purifying process | |
| CN107555659A (en) | Emulsifying liquid waste water processing unit and its technique | |
| CN107601815B (en) | Petrochemical oily sludge treating agent, and preparation method and application thereof | |
| CN102268324A (en) | Method for recovering cutting liquid, SiC powder and Si powder from waste mortar | |
| CN102153213A (en) | Two-stage centrifugal desliming technology | |
| CN102153224A (en) | Treatment technology for industrial sewage from sodium carboxymethylcellulose | |
| CN101983919B (en) | Method for producing white carbon black by polycrystalline silicon cut waste alkali-wash waste water | |
| CN103865626B (en) | A kind of anacidity alkali reclaiming process of useless machinery oil | |
| CN106241983A (en) | A kind of purification process technique of waste or used plastics wash water | |
| CN104276687B (en) | A kind of method of animal protein feed in recycling casing processing-waste | |
| CN110194516A (en) | It is a kind of handle black water flocculant and its application and slime water treatment method | |
| CN103011457B (en) | Deep dewatering conditioning method of colistin sulfate residues | |
| CN103865627A (en) | Method for recycling waste steam turbine oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180731 Address after: 725806 a group of Maping village, Maping Town, Baihe County, Ankang City, Shaanxi Patentee after: Shaanxi Yonghong Biotechnology Co., Ltd. Address before: No. 1, Weiyang District university garden, Xi'an, Shaanxi Province, Shaanxi Patentee before: Shaanxi University of Science and Technology |