CN104926915A - One-step method for separating pectin, chlorophyll and tigogenin in sisal pressed liquid - Google Patents
One-step method for separating pectin, chlorophyll and tigogenin in sisal pressed liquid Download PDFInfo
- Publication number
- CN104926915A CN104926915A CN201510227364.8A CN201510227364A CN104926915A CN 104926915 A CN104926915 A CN 104926915A CN 201510227364 A CN201510227364 A CN 201510227364A CN 104926915 A CN104926915 A CN 104926915A
- Authority
- CN
- China
- Prior art keywords
- extraction
- tigogenin
- pectin
- raw material
- ethanolic soln
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J71/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton is condensed with a heterocyclic ring
- C07J71/0005—Oxygen-containing hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0045—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Galacturonans, e.g. methyl ester of (alpha-1,4)-linked D-galacturonic acid units, i.e. pectin, or hydrolysis product of methyl ester of alpha-1,4-linked D-galacturonic acid units, i.e. pectinic acid; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Molecular Biology (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
The invention discloses a one-step method for separating pectin, chlorophyll and tigogenin in sisal pressed liquid. According to the invention, pectin in the sisal pressed liquid is separated with a flocculent precipitation method, and commercial pectin is obtained through a chemical treatment; a supernatant is concentrated, ethanol is recovered, and a paste is obtained; the dried and crushed paste is adopted as an extract material, and is subjected to Soxhlet extraction; a solvent is recovered, and chlorophyll is obtained; chlorophyll is adopted as a raw material, and water-soluble chlorophyll sodium copper salt is obtained; the extraction residue is adopted as a raw material, and steps such as hydrolysis, neutralization, filtration, washing, drying, extraction, cooling and drying are carried out, such that tigogenin is obtained. With the method provided by the invention, acid dose in tigogenin production can be reduced, environment pollution caused by tigogenin production can be controlled, pectin and chlorophyll resources in sisal are fully utilized, and tigogenin production cost is reduced.
Description
Technical field
The invention belongs to medicine material production field, be specifically related to adopt single stage method to be separated the method for pectin, chlorophyll and tigogenin in sisal hemp pressed liquor.
Background technology
The herbaceous plant that sisal hemp is a kind of Agavaceae Agave, perennial, meat, drought are raw.Originate in the Mexican Long Jiadan peninsula, formal name used at school is: Agave Sisalana Perrine.English name: Sisal.Another name: you are numb for western yarn.Sisal hemp is a kind of leaf fibres crop, and sisal hemp leaf is sword shape, hard and long and narrow, and blade is generally long is 100cm ~ 140cm, wide 13cm ~ 15cm, grayish green to blue-greenish colour.Sisal hemp has happiness temperature, drought-enduring feature, is suitable for the torrid zone, the cultivation of subtropics wide geographic area.There are the states such as Mexico, Brazil, Tanzania in main product country, at Chinese primary growth in the Lezhou Peninsula and some areas of Guangxi.
Sisal leaves obtains fiber and juice after squeezing, and sisal fibers cell is elongate structure, and lumen is large and grow, wall thickness, has fiber long, and color and luster is pure white, strong but pliable in texture, high resilience, pulling force is strong, abrasion-resistant, acid and alkali-resistance, corrosion-resistant, the feature of not easily skidding, due to seawater immersion erosion resisting, often make the apparatus such as fishnet, vessel line.Be widely used in the causes such as fishery, navigation, industrial and mineral, transport, oil field, and for weaving the daily necessities such as sisal hemp carpet, artwork.Containing the composition such as chlorophyll, pectin, sisal hemp saponin(e in juice, chlorophyll is a class most important pigment relevant with photosynthesis, there is hematopoiesis, VITAMIN be provided, removing toxic substances, the multiple use such as disease-resistant, be also the main source of natural pigment.Pectin is one group of polygalacturonic acid, has good gelationization and stable emulsifying effect, has been widely used in food, medicine, daily use chemicals and textile industry.Sisal hemp saponin(e obtains tigogenin through hydrolysis reaction, and tigogenin (Sisalgenin, Tigogenin) is the basic raw material of synthesizing steroid hormone medicine, have the title of " medical gold " and " hormone is female ", can Some substitute diosgenin.The derived product monoene utilizing tigogenin to produce, can synthesize more than the 120 kind of hormone medicines such as Betamethasone Valerate.
In addition, tigogenin is also widely used in the industries such as food, makeup and livestock industry, is the most general, the topmost basic material in biology,drug and chemical industry field, and its production technology belongs to the new pharmaceutical engineering that country supports and encourages development.
Around the comprehensive exploitation of sisal hemp, people have done large quantifier elimination.Chen Yanfang etc. adopt optimization of orthogonal test method, determine the optimum extraction condition of sisal hemp pectin.Discovery take concentration as the oxalic acid-ammonium oxalate buffered soln of 2.2mol/L is extraction agent, with sisal hemp cream for raw material, is 0.1g/mL at solid-liquid ratio, temperature is extract 90min under the condition of 80 DEG C, regulate pH to be 4.0, can obtain with alcohol settling the low-ester pectin that gamma value is 23%, its productive rate 14.87%.Zhou Yin etc. adopt conventional sulfuric acid heating and refluxing extraction method, extract tigogenin crude extract, with wide aperture resin separation purification tigogenin, and determine best purifying technique condition.Find by D-101 resin isolation effect better, optimal separation purifying process condition is, eluate concentration is 70% ethanol, consumption 100ml, and with this understanding, tigogenin yield is 79.1% to elution speed 0.6ml/min, and purity is 71.6.Liao Qing etc. for raw material with sisal hemp fiber crops cream, adopt vitriol oil acid hydrolyzation to prepare hydrolyzate, have investigated hydrolysis time, h 2 so 4 concentration, numb cream and vitriol oil mass ratio to the impact being hydrolyzed yield and hydrolyzate content.Take high performance liquid chromatography as detection means, determined the optimum process condition of hydrolysis by single factor test and orthonormal design of experiments: hydrolysis time 8h, h 2 so 4 concentration 15%, numb cream and vitriol oil mass ratio 1: 1.Hydrolyzate yield 68.56% with this understanding, hydrolyzate content 12.55%.Deng Chujin etc. adopt supercritical CO
2total saponins in extraction process extraction sisal hemp, has inquired into extraction temperature, pressure, time to the impact of percentage extraction, has determined supercritical CO
2the optimum process condition of extraction is: extraction temperature 45 DEG C, extracting pressure 35MPa, entrainment agent consumption 20%, extraction time 120min; Under this condition, in sisal hemp, the percentage extraction of total saponins is 1.74%.Deng Tianfa etc. adopt tlc (TLC) from 31 strain object bacterial strains, high performance liquid chromatography (HPLC), sifting out at the beginning of morphological observation and ITS sequence assay method can the bacterial strain of enzymolysis sisal hemp saponin(e, finds that aspergillus niger, Neurospora and mould all have stronger enzymolysis sisal hemp saponin(e and the ability of the free tigogenin of release.
More than study the production aspect mainly concentrating on pectin, saponin, and be all with sisal hemp cream for raw material, reclaim product relatively all more single.
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 method adopting single stage method to be separated pectin, chlorophyll and tigogenin in sisal hemp pressed liquor, the present invention can reduce the consumption of acid when tigogenin is produced, and controls tigogenin and produces pollution on the environment; Make full use of pectin in sisal hemp, chlorophyll resource, reduce the production cost of tigogenin.
For achieving the above object, the present invention adopts following technical scheme:
Adopt single stage method to be separated a method for pectin, chlorophyll and tigogenin in sisal hemp pressed liquor, comprise the following steps:
1) pectin is separated: obtain sisal leaves pressed liquor by squeezing, and in sisal leaves pressed liquor, add ethanol while stirring to no longer producing flocks, then centrifugation, obtains supernatant liquor and flocks, take flocks as raw material production pectin;
2) chlorophyllous separation: with step 1) in the supernatant liquor that obtains be raw material, paste A is obtained by the vacuum concentration ethanol reclaimed wherein, porphyrize or pulverizing after paste A drying are obtained paste powder, with paste powder for raw material extracts, be cooled to room temperature separation after extraction and be extracted liquid and bits, take extraction liquid as raw material, paste B is obtained by the vacuum concentration extraction agent reclaimed wherein, with paste B for raw material, obtain sodium copper chlorophyllin through saponification, copper generation, salt-forming reaction;
3) preparation of tigogenin: with step 2) in the bits that obtain be raw material, add sulfuric acid according to the ratio of Zha ﹕ sulfuric acid=1 ﹕ 1 to be hydrolyzed, after hydrolysis, be cooled to room temperature, add neutralizing agent while stirring and be neutralized to neutrality, then filter and obtain filter residue, wash filter residue removing SO with water
2 4 -rear drying, by dried filter residue porphyrize, with the filter residue of porphyrize for raw material extracts, reclaim the extraction agent in extraction liquid by vacuum concentration, the extraction liquid reclaiming extraction agent is cooled to crystallization to be formed, then crystallization is filtered out and be drying to obtain tigogenin.
Further, step 1) in the rotating speed of centrifugation be 3000r/min, the time is 12 ~ 15min; Step 2) in by vacuum concentration reclaim ethanol and reclaim extraction agent time vacuum tightness be 0.08 ~ 0.09MPa, temperature is 40 ~ 50 DEG C; Step 3) in by vacuum concentration reclaim extraction agent time vacuum tightness be 0.08 ~ 0.09MPa, temperature is 40 ~ 50 DEG C.
Further, step 1) in take flocks as the method for raw material production pectin be: take flocks as raw material, add hydrochloric acid to be hydrolyzed reaction, hydrolyzed solution filters, clarification is rear concentrated, add activated carbon decolorizing after concentrated, then filter, in filtrate, add ethanolic soln, pectin and precipitating out, then obtain pectin after press filtration, washing with alcohol, vacuum-drying, pulverizing.
Further, concentration of hydrochloric acid is 0.05 ~ 0.1mol/L, the add-on of hydrochloric acid is 8 ~ 10 times of flocks quality, the temperature of hydrolysis reaction is 80 ~ 85 DEG C, and the time is 1.5 ~ 2h, and being concentrated into mass fraction of solids after hydrolyzed solution filtration, clarification is 3 ~ 5%, temperature when adding gac is 80 ~ 85 DEG C, bleaching time is 10 ~ 15min, and the volume fraction of the ethanolic soln added in filtrate is 75 ~ 95%, makes the volume fraction of ethanol reach 45 ~ 50% after adding ethanolic soln.
Further, step 2) in extraction process extraction agent used be ethanol, acetone, ether or chloroform, extraction conditions is: with the speed of 4 ~ 6/s backflow 6 ~ 8h; Step 3) in extraction process extraction agent used be sherwood oil, extraction conditions is: with the speed of 4 ~ 6/s backflow 6 ~ 8h.
Further, step 2) in paste B for raw material, through saponification, copper generation, the process that salt-forming reaction obtains sodium copper chlorophyllin is: with paste B for raw material, add sodium hydroxide ethanolic soln, adjust ph be after 10.5 ~ 11.5 at 55 ~ 60 DEG C saponification 1 ~ 2h, after saponification completely, vacuum concentration to volume is original 1/4 ~ 1/3, use petroleum ether extraction again, after extraction, lower floor's salt acid for adjusting pH is neutral, add excess sulfuric acid copper ethanolic soln, be carry out copper generation reaction after 2 ~ 3 with salt acid for adjusting pH again, leave standstill after reaction and be cooled to room temperature, precipitate in collected at room temperature, precipitation is first used hot wash, then with ethanolic soln washing to alcohol layer be light green, be light green with petroleum ether to petroleum ether layer again, then filter, be 11 ~ 12 by filter residue sodium hydroxide ethanolic soln adjust ph, refilter, by dry after filter residue absolute ethanol washing, obtain sodium copper chlorophyllin.
Further, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 5 ~ 8%; Petroleum ether extraction 3 ~ 4 times are used after vacuum concentration; Hydrochloric acid massfraction used is 5 ~ 8%; In copper sulfate ethanolic soln used, the massfraction of copper sulfate is 5 ~ 10%; The temperature of copper generation reaction is 50 ~ 60 DEG C, and the time is 1 ~ 2h; First using the hot wash 2 ~ 3 times of 50 ~ 60 DEG C after collecting precipitation, is then light green with the ethanolic soln washing that volume fraction is 30 ~ 40% to alcohol layer; Finally adopt absolute ethanol washing filter residue 2 ~ 3 times, then dry at 50 ~ 60 DEG C.
Further, step 3) in the concentration of sulfuric acid be 1.5mol/L, the temperature of hydrolysis is 105 ~ 110 DEG C, and the time is 6 ~ 8h; Step 3) in the sodium hydroxide of neutralizing agent used to be concentration be 2mol/L.
Further, step 3) in only reclaim when to be reclaimed in extraction liquid extraction agent by vacuum concentration 70 ~ 80% extraction agent; Step 3) in the extraction liquid reclaiming extraction agent to be cooled to the cooling temperature that crystallization formed be 5 ~ 10 DEG C, the time is 2 ~ 3h; Step 3) in crystallization is filtered out after, first utilize sherwood oil to wash, be then drying to obtain tigogenin.
Adopt single stage method to be separated a method for pectin, chlorophyll and tigogenin in sisal hemp pressed liquor, comprise the following steps:
1) pectin is separated: adopt mechanical expression method to obtain sisal leaves pressed liquor, ethanol is added while stirring to no longer producing flocks in sisal leaves pressed liquor, then centrifugation 15min under the condition of 3000r/min, obtain supernatant liquor and flocks, take flocks as raw material, add the hydrochloric acid that concentration is 0.06mol/L, wherein the add-on of hydrochloric acid is 10 times of flocks quality, 1.5h is hydrolyzed at 80 DEG C, hydrolyzed solution filters, being concentrated into mass fraction of solids after clarification is 3%, at 80 DEG C, activated carbon decolorizing 10min is added after concentrated, then filter, in filtrate, add volume fraction is 95% ethanolic soln, the volume fraction of ethanol is made to reach 50% after adding ethanolic soln, pectin and precipitating are out, then through press filtration, washing with alcohol, vacuum-drying, pectin is obtained after pulverizing,
2) chlorophyllous separation: with step 1) in the supernatant liquor that obtains be raw material, be 0.085MPa in vacuum tightness, temperature is obtain paste A by the vacuum concentration ethanol reclaimed wherein under the condition of 45 DEG C, by paste A at 85 DEG C after dry 6h porphyrize or pulverizing obtain paste powder, with paste powder for raw material, be that extraction agent extracts with ethanol, extraction conditions is: with the speed of 4/s backflow 6h, be cooled to room temperature separation after extraction and be extracted liquid and bits, take extraction liquid as raw material, be 0.085MPa in vacuum tightness, temperature is obtain paste B by the vacuum concentration extraction agent reclaimed wherein under the condition of 45 DEG C, with paste B for raw material, add sodium hydroxide ethanolic soln, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 5%, adjust ph be after 11 at 60 DEG C saponification 1h, after saponification completely, vacuum concentration to volume is original 1/3, use petroleum ether extraction again 3 times, after extraction, lower floor's massfraction is the salt acid for adjusting pH of 5% is neutral, add excess sulfuric acid copper ethanolic soln, in copper sulfate ethanolic soln used, the massfraction of copper sulfate is 5%, be at 50 DEG C, carry out copper generation reaction 1h after 2 with the salt acid for adjusting pH that massfraction is 5% again, leave standstill after reaction and be cooled to room temperature, precipitate in collected at room temperature, precipitation is first used the hot wash 2 times of 50 DEG C, then with volume fraction be 30% ethanolic soln washing to alcohol layer be light green, be light green with petroleum ether to petroleum ether layer again, then filter, be 11 by filter residue sodium hydroxide ethanolic soln adjust ph, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 5%, refilter, by filter residue with dry at 50 DEG C after absolute ethanol washing 2 times, obtain sodium copper chlorophyllin,
3) preparation of tigogenin: with step 2) in the bits that obtain be raw material, add sulfuric acid according to the ratio of Zha ﹕ 1.5mol/L sulfuric acid=1 ﹕ 1 and be hydrolyzed 7h at 108 DEG C, room temperature is cooled to after hydrolysis, the sodium hydroxide adding 2mol/L is while stirring neutralized to neutrality, then filter and obtain filter residue, with the removing of 500mL moisture 3 washing filter residues
after under the condition of 80 DEG C dry 8h, by dried filter residue porphyrize, with the filter residue of porphyrize for raw material, be that extraction agent extracts with sherwood oil, extraction conditions is: with the speed of 5/s backflow 7h, the extraction agent of in extraction liquid 70% is reclaimed by vacuum concentration, 2h is kept after the extraction liquid mixture of ice and water reclaiming extraction agent is cooled to 5 DEG C, tigogenin crystallization is formed, then crystallization is filtered out, first 40mL sherwood oil is utilized to wash at twice, then dry 2h under the condition of 80 DEG C, obtain fusing point 196 ~ 204 DEG C, purity is the tigogenin of 96%.
Compared with prior art, the present invention has following useful technique effect:
The present invention utilizes the pectin in sisal hemp pressed liquor, sisal hemp saponin(e, chlorophyllous different properties, and employing flocculent precipitation isolates the pectin in sisal hemp pressed liquor, obtains commodity pectin through chemical treatment; Concentrated supernatant, reclaims ethanol, obtains paste, and with the paste after gained drying, pulverizing for extract, adopt the extraction of soxhlet extraction method, recycling design, obtains chlorophyll, as raw material, obtains water miscible chlorophyll iron (copper) sodium salt; Bits after extraction are raw material, pass through hydrolysis, neutralization, filtration, washing, drying, extraction, cooling and drying and other steps successively and obtain tigogenin.Compared with prior art have the following advantages: 1, disposable substep obtains pectin, chlorophyll and tigogenin, reasonably make use of the activeconstituents in sisal hemp pressed liquor, turn waste into wealth.2, before the hydrolysis of sisal hemp saponin(e, eliminate the pectin in sisal hemp pressed liquor, chlorophyll in advance, improve the concentration of sisal hemp saponin(e, decrease sisal hemp saponin(e be hydrolyzed into tigogenin and tigogenin extraction time acid, organic solvent consumption, control pollution, reduce cost, improve the purity of tigogenin.
Further, take sherwood oil as extraction agent, the purity of tigogenin can reach 92 ~ 98%, overcomes the many and alcoholic extract of oil lime method, oil silica gel method auxiliary material and follows the example of the shortcoming that purity is low, foreign matter content is high.
Embodiment
Below embodiments of the present invention are described in further detail:
Adopt single stage method to be separated a method for pectin, chlorophyll and tigogenin in sisal hemp pressed liquor, comprise the following steps:
1) pectin is separated: adopt mechanical expression method to obtain sisal leaves pressed liquor, ethanol is added while stirring to no longer producing flocks in sisal leaves pressed liquor, then centrifugation 12 ~ 15min under the condition of 3000r/min, obtain supernatant liquor and flocks, take flocks as raw material, add the hydrochloric acid that concentration is 0.05 ~ 0.1mol/L, wherein the add-on of hydrochloric acid is 8 ~ 10 times of flocks quality, 1.5 ~ 2h is hydrolyzed at 80 ~ 85 DEG C, hydrolyzed solution filters, being concentrated into mass fraction of solids after clarification is 3 ~ 5%, at 80 ~ 85 DEG C, activated carbon decolorizing 10 ~ 15min is added after concentrated, then filter, in filtrate, add volume fraction is 75 ~ 95% ethanolic solns, the volume fraction of ethanol is made to reach 45 ~ 50% after adding ethanolic soln, pectin and precipitating are out, then through press filtration, washing with alcohol, vacuum-drying, pectin is obtained after pulverizing,
2) chlorophyllous separation: with step 1) in the supernatant liquor that obtains be raw material, be 0.08 ~ 0.09MPa in vacuum tightness, temperature is obtain paste A by the vacuum concentration ethanol reclaimed wherein under the condition of 40 ~ 50 DEG C, by paste A at 80 ~ 100 DEG C after dry 6h porphyrize or pulverizing obtain paste powder, with paste powder for raw material, with ethanol, acetone, ether or chloroform are that extraction agent extracts, extraction conditions is: with the speed of 4 ~ 6/s backflow 6 ~ 8h, be cooled to room temperature separation after extraction and be extracted liquid and bits, take extraction liquid as raw material, be 0.08 ~ 0.09MPa in vacuum tightness, temperature is obtain paste B by the vacuum concentration extraction agent reclaimed wherein under the condition of 40 ~ 50 DEG C, with paste B for raw material, add sodium hydroxide ethanolic soln, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 5 ~ 8%, adjust ph be after 10.5 ~ 11.5 at 55 ~ 60 DEG C saponification 1 ~ 2h, after saponification completely, vacuum concentration to volume is original 1/4 ~ 1/3, use petroleum ether extraction again 3 ~ 4 times, after extraction, lower floor's massfraction is the salt acid for adjusting pH of 5 ~ 8% is neutral, add excess sulfuric acid copper ethanolic soln, in copper sulfate ethanolic soln used, the massfraction of copper sulfate is 5 ~ 10%, be at 50 ~ 60 DEG C, carry out copper generation reaction 1 ~ 2h after 2 ~ 3 with the salt acid for adjusting pH that massfraction is 5 ~ 10% again, leave standstill after reaction and be cooled to room temperature, precipitate in collected at room temperature, precipitation is first used the hot wash 2 ~ 3 times of 50 ~ 60 DEG C, then with volume fraction be 30 ~ 40% ethanolic soln washing to alcohol layer be light green, be light green with petroleum ether to petroleum ether layer again, then filter, be 11 ~ 12 by filter residue sodium hydroxide ethanolic soln adjust ph, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 5 ~ 8%, refilter, by filter residue with dry at 50 ~ 60 DEG C after absolute ethanol washing 2 ~ 3 times, obtain sodium copper chlorophyllin,
3) preparation of tigogenin: with step 2) in the bits that obtain be raw material, add sulfuric acid according to the ratio of Zha ﹕ 1.5mol/L sulfuric acid=1 ﹕ 1 and be hydrolyzed 6 ~ 8h at 105 ~ 110 DEG C, room temperature is cooled to after hydrolysis, the sodium hydroxide adding 2mol/L is while stirring neutralized to neutrality, then filter and obtain filter residue, wash filter residue removing with water
after under the condition of 80 ~ 100 DEG C dry 6 ~ 8h, by dried filter residue porphyrize, with the filter residue of porphyrize for raw material, be that extraction agent extracts with sherwood oil, extraction conditions is: with the speed of 4 ~ 6/s backflow 6 ~ 8h, the extraction agent of in extraction liquid 70 ~ 80% is reclaimed by vacuum concentration, 2 ~ 3h is kept after the extraction liquid mixture of ice and water reclaiming extraction agent is cooled to 5 ~ 10 DEG C, tigogenin crystallization is formed, then crystallization is filtered out, first utilize sherwood oil to wash, then under the condition of 80 ~ 100 DEG C, namely dry 1 ~ 2h obtains tigogenin.
Containing the pectin of about 17% in sisal hemp pressed liquor, pectin is a kind of foodstuff additive very well, has the effects such as thickening, stable, suspension, emulsification, flavouring.Pectin in sisal hemp pressed liquor, if not being separated in advance, very easily causing in last part technology and is separated (filtration) operational difficulty, and filtrate is muddy, contaminate environment.With sisal hemp pressed liquor for raw material, utilize pectin to be insoluble to the character of ethanol, adopt and add the method for ethanol while stirring, realize the separation of pectin in sisal hemp pressed liquor, to be separated the pectin that obtains for raw material, the pectin of different gamma value can be obtained.
Containing a large amount of chlorophyll in sisal hemp pressed liquor, chlorophyll is a class most important pigment relevant with photosynthesis.Chlorophyll in higher plant chloroplast(id) mainly contains chlorophyll a and chlorophyll b two kinds.They are water insoluble, and are dissolved in organic solvent, as ethanol, acetone, ether, chloroform etc.Chlorophyll a molecular formula: C
55h
72o
5n
4mg; Chlorophyll b molecular formula: C
55h
70o
6n
4mg.In color, chlorophyll a is blue-greenish colour, and chlorophyll b is yellow-green colour.By chemical property, chlorophyll is the ester of CHLOROPHYLLINE, saponification reaction can occur.CHLOROPHYLLINE is two carboxylic acids, and one of them carboxyl is by the esterification of methyl alcohol institute, and another is by the esterification of leaf-alcohol institute.
Chlorophyll molecule contains " head " of a porphyrin ring and " tail " of a phytol.Magnesium atom occupy the central authorities of porphyrin ring, is partial to positively charged, and the nitrogen-atoms be connected with it is then partial to electronegative, and thus porphyrin has polarity, is hydrophilic, can with protein bound.The diterpene that leaf-alcohol is made up of four isoprene units is the aliphatic chain of a lipophilic, which determines chlorophyllous fat-soluble.
Magnesium atom in porphyrin ring can by hydrogen ion, cupric ion, iron ion replace.Use acid treatment blade, hydrogen ion easily enters chloroplast(id), and displacement magnesium atom forms de-magnesium pheophytin, makes blade be brown.De-magnesium pheophytin easily again with copper (iron) ionic bond, form copper (iron) for chlorophyll, color is than original more stable, more soluble in water.
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment 1
1) pectin is separated: adopt mechanical expression method to obtain sisal leaves pressed liquor, ethanol is added while stirring to no longer producing flocks in sisal leaves pressed liquor, then centrifugation 15min under the condition of 3000r/min, obtain supernatant liquor and flocks, take flocks as raw material, add the hydrochloric acid that concentration is 0.06mol/L, wherein the add-on of hydrochloric acid is 10 times of flocks quality, 1.5h is hydrolyzed at 80 DEG C, hydrolyzed solution filters, being concentrated into mass fraction of solids after clarification is 3%, at 80 DEG C, activated carbon decolorizing 10min is added after concentrated, then filter, in filtrate, add volume fraction is 95% ethanolic soln, the volume fraction of ethanol is made to reach 50% after adding ethanolic soln, pectin and precipitating are out, then through press filtration, washing with alcohol, vacuum-drying, pectin is obtained after pulverizing,
2) chlorophyllous separation: with step 1) in the supernatant liquor that obtains be raw material, be 0.085MPa in vacuum tightness, temperature is obtain paste A by the vacuum concentration ethanol reclaimed wherein under the condition of 45 DEG C, by paste A at 85 DEG C after dry 6h porphyrize or pulverizing obtain paste powder, with paste powder for raw material, be that extraction agent extracts with ethanol, extraction conditions is: with the speed of 4/s backflow 6h, be cooled to room temperature separation after extraction and be extracted liquid and bits, take extraction liquid as raw material, be 0.085MPa in vacuum tightness, temperature is obtain paste B by the vacuum concentration extraction agent reclaimed wherein under the condition of 45 DEG C, with paste B for raw material, add sodium hydroxide ethanolic soln, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 5%, adjust ph be after 11 at 60 DEG C saponification 1h, after saponification completely, vacuum concentration to volume is original 1/3, use petroleum ether extraction again 3 times, after extraction, lower floor's massfraction is the salt acid for adjusting pH of 5% is neutral, add excess sulfuric acid copper ethanolic soln, in copper sulfate ethanolic soln used, the massfraction of copper sulfate is 5%, be at 50 DEG C, carry out copper generation reaction 1h after 2 with the salt acid for adjusting pH that massfraction is 5% again, leave standstill after reaction and be cooled to room temperature, precipitate in collected at room temperature, precipitation is first used the hot wash 2 times of 50 DEG C, then with volume fraction be 30% ethanolic soln washing to alcohol layer be light green, be light green with petroleum ether to petroleum ether layer again, then filter, be 11 by filter residue sodium hydroxide ethanolic soln adjust ph, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 5%, refilter, by filter residue with dry at 50 DEG C after absolute ethanol washing 2 times, obtain sodium copper chlorophyllin,
3) preparation of tigogenin: with step 2) in the bits that obtain be raw material, add sulfuric acid according to the ratio of Zha ﹕ 1.5mol/L sulfuric acid=1 ﹕ 1 and be hydrolyzed 7h at 108 DEG C, room temperature is cooled to after hydrolysis, the sodium hydroxide adding 2mol/L is while stirring neutralized to neutrality, then filter and obtain filter residue, with the removing of 500mL moisture 3 washing filter residues
after under the condition of 80 DEG C dry 8h, by dried filter residue porphyrize, with the filter residue of porphyrize for raw material, be that extraction agent extracts with sherwood oil, extraction conditions is: with the speed of 5/s backflow 7h, the extraction agent of in extraction liquid 70% is reclaimed by vacuum concentration, 2h is kept after the extraction liquid mixture of ice and water reclaiming extraction agent is cooled to 5 DEG C, tigogenin crystallization is formed, then crystallization is filtered out, first 40mL sherwood oil is utilized to wash at twice, then dry 2h under the condition of 80 DEG C, obtain fusing point 196 ~ 204 DEG C, purity is the tigogenin of 96%.
Embodiment 2
1) pectin is separated: adopt mechanical expression method to obtain sisal leaves pressed liquor, ethanol is added while stirring to no longer producing flocks in sisal leaves pressed liquor, then centrifugation 12min under the condition of 3000r/min, obtain supernatant liquor and flocks, take flocks as raw material, add the hydrochloric acid that concentration is 0.05mol/L, wherein the add-on of hydrochloric acid is 8 times of flocks quality, 2h is hydrolyzed at 85 DEG C, hydrolyzed solution filters, being concentrated into mass fraction of solids after clarification is 5%, at 85 DEG C, activated carbon decolorizing 15min is added after concentrated, then filter, in filtrate, add volume fraction is 75% ethanolic soln, the volume fraction of ethanol is made to reach 45% after adding ethanolic soln, pectin and precipitating are out, then through press filtration, washing with alcohol, vacuum-drying, pectin is obtained after pulverizing,
2) chlorophyllous separation: with step 1) in the supernatant liquor that obtains be raw material, be 0.09MPa in vacuum tightness, temperature is obtain paste A by the vacuum concentration ethanol reclaimed wherein under the condition of 40 DEG C, by paste A at 80 DEG C after dry 6h porphyrize or pulverizing obtain paste powder, with paste powder for raw material, be that extraction agent extracts with acetone, extraction conditions is: with the speed of 6/s backflow 6h, be cooled to room temperature separation after extraction and be extracted liquid and bits, take extraction liquid as raw material, be 0.09MPa in vacuum tightness, temperature is obtain paste B by the vacuum concentration extraction agent reclaimed wherein under the condition of 40 DEG C, with paste B for raw material, add sodium hydroxide ethanolic soln, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 8%, adjust ph be after 11.5 at 60 DEG C saponification 2h, after saponification completely, vacuum concentration to volume is original 1/4, use petroleum ether extraction again 4 times, after extraction, lower floor's massfraction is the salt acid for adjusting pH of 8% is neutral, add excess sulfuric acid copper ethanolic soln, in copper sulfate ethanolic soln used, the massfraction of copper sulfate is 10%, be at 60 DEG C, carry out copper generation reaction 2h after 3 with the salt acid for adjusting pH that massfraction is 10% again, leave standstill after reaction and be cooled to room temperature, precipitate in collected at room temperature, precipitation is first used the hot wash 3 times of 60 DEG C, then with volume fraction be 40% ethanolic soln washing to alcohol layer be light green, be light green with petroleum ether to petroleum ether layer again, then filter, be 12 by filter residue sodium hydroxide ethanolic soln adjust ph, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 8%, refilter, by filter residue with dry at 60 DEG C after absolute ethanol washing 3 times, obtain sodium copper chlorophyllin,
3) preparation of tigogenin: with step 2) in the bits that obtain be raw material, add sulfuric acid according to the ratio of Zha ﹕ 1.5mol/L sulfuric acid=1 ﹕ 1 and be hydrolyzed 6h at 105 DEG C, room temperature is cooled to after hydrolysis, the sodium hydroxide adding 2mol/L is while stirring neutralized to neutrality, then filter and obtain filter residue, with moisture 3 washing filter residues removing of 600mL
after under the condition of 90 DEG C dry 6h, by dried filter residue porphyrize, with the filter residue of porphyrize for raw material, be that extraction agent extracts with sherwood oil, extraction conditions is: with the speed of 4/s backflow 8h, the extraction agent of in extraction liquid 80% is reclaimed by vacuum concentration, 3h is kept after the extraction liquid mixture of ice and water reclaiming extraction agent is cooled to 10 DEG C, tigogenin crystallization is formed, then crystallization is filtered out, first utilize sherwood oil to wash, then dry 1.5h under the condition of 90 DEG C, obtain fusing point 197 ~ 204 DEG C, purity is the tigogenin of 96.8%.
Embodiment 3
1) pectin is separated: adopt mechanical expression method to obtain sisal leaves pressed liquor, ethanol is added while stirring to no longer producing flocks in sisal leaves pressed liquor, then centrifugation 12min under the condition of 3000r/min, obtain supernatant liquor and flocks, take flocks as raw material, add the hydrochloric acid that concentration is 0.1mol/L, wherein the add-on of hydrochloric acid is 9 times of flocks quality, 1.5h is hydrolyzed at 80 DEG C, hydrolyzed solution filters, being concentrated into mass fraction of solids after clarification is 4%, at 80 DEG C, activated carbon decolorizing 12min is added after concentrated, then filter, in filtrate, add volume fraction is 80% ethanolic soln, the volume fraction of ethanol is made to reach 47% after adding ethanolic soln, pectin and precipitating are out, then through press filtration, washing with alcohol, vacuum-drying, pectin is obtained after pulverizing,
2) chlorophyllous separation: with step 1) in the supernatant liquor that obtains be raw material, be 0.08MPa in vacuum tightness, temperature is obtain paste A by the vacuum concentration ethanol reclaimed wherein under the condition of 50 DEG C, by paste A at 90 DEG C after dry 6h porphyrize or pulverizing obtain paste powder, with paste powder for raw material, be that extraction agent extracts with ether, extraction conditions is: with the speed of 5/s backflow 8h, be cooled to room temperature separation after extraction and be extracted liquid and bits, take extraction liquid as raw material, be 0.08MPa in vacuum tightness, temperature is obtain paste B by the vacuum concentration extraction agent reclaimed wherein under the condition of 50 DEG C, with paste B for raw material, add sodium hydroxide ethanolic soln, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 6%, adjust ph be after 10.5 at 57 DEG C saponification 1.5h, after saponification completely, vacuum concentration to volume is original 1/3, use petroleum ether extraction again 4 times, after extraction, lower floor's massfraction is the salt acid for adjusting pH of 7% is neutral, add excess sulfuric acid copper ethanolic soln, in copper sulfate ethanolic soln used, the massfraction of copper sulfate is 8%, be at 55 DEG C, carry out copper generation reaction 1.5h after 2 with the salt acid for adjusting pH that massfraction is 7% again, leave standstill after reaction and be cooled to room temperature, precipitate in collected at room temperature, precipitation is first used the hot wash 2 times of 505 DEG C, then with volume fraction be 35% ethanolic soln washing to alcohol layer be light green, be light green with petroleum ether to petroleum ether layer again, then filter, be 11 by filter residue sodium hydroxide ethanolic soln adjust ph, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 6%, refilter, by filter residue with dry at 55 DEG C after absolute ethanol washing 3 times, obtain sodium copper chlorophyllin,
3) preparation of tigogenin: with step 2) in the bits that obtain be raw material, add sulfuric acid according to the ratio of Zha ﹕ 1.5mol/L sulfuric acid=1 ﹕ 1 and be hydrolyzed 8h at 110 DEG C, room temperature is cooled to after hydrolysis, the sodium hydroxide adding 2mol/L is while stirring neutralized to neutrality, then filter and obtain filter residue, with moisture 3 washing filter residues removing of 550mL
after under the condition of 100 DEG C dry 6h, by dried filter residue porphyrize, with the filter residue of porphyrize for raw material, be that extraction agent extracts with sherwood oil, extraction conditions is: with the speed of 6/s backflow 8h, the extraction agent of in extraction liquid 75% is reclaimed by vacuum concentration, 2.5h is kept after the extraction liquid mixture of ice and water reclaiming extraction agent is cooled to 8 DEG C, tigogenin crystallization is formed, then crystallization is filtered out, first utilize sherwood oil to wash, then dry 2h under the condition of 90 DEG C, obtain fusing point 196 ~ 204 DEG C, purity is the tigogenin of 96.4%.
Embodiment 4
1) pectin is separated: adopt mechanical expression method to obtain sisal leaves pressed liquor, ethanol is added while stirring to no longer producing flocks in sisal leaves pressed liquor, then centrifugation 13min under the condition of 3000r/min, obtain supernatant liquor and flocks, take flocks as raw material, add the hydrochloric acid that concentration is 0.08mol/L, wherein the add-on of hydrochloric acid is 10 times of flocks quality, 2h is hydrolyzed at 80 DEG C, hydrolyzed solution filters, being concentrated into mass fraction of solids after clarification is 5%, at 80 DEG C, activated carbon decolorizing 15min is added after concentrated, then filter, in filtrate, add volume fraction is 85% ethanolic soln, the volume fraction of ethanol is made to reach 50% after adding ethanolic soln, pectin and precipitating are out, then through press filtration, washing with alcohol, vacuum-drying, pectin is obtained after pulverizing,
2) chlorophyllous separation: with step 1) in the supernatant liquor that obtains be raw material, be 0.08MPa in vacuum tightness, temperature is obtain paste A by the vacuum concentration ethanol reclaimed wherein under the condition of 45 DEG C, by paste A at 100 DEG C after dry 6h porphyrize or pulverizing obtain paste powder, with paste powder for raw material, be that extraction agent extracts with chloroform, extraction conditions is: with the speed of 6/s backflow 7h, be cooled to room temperature separation after extraction and be extracted liquid and bits, take extraction liquid as raw material, be 0.08MPa in vacuum tightness, temperature is obtain paste B by the vacuum concentration extraction agent reclaimed wherein under the condition of 45 DEG C, with paste B for raw material, add sodium hydroxide ethanolic soln, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 7%, adjust ph be after 11 at 60 DEG C saponification 2h, after saponification completely, vacuum concentration to volume is original 1/4, use petroleum ether extraction again 3 times, after extraction, lower floor's massfraction is the salt acid for adjusting pH of 7% is neutral, add excess sulfuric acid copper ethanolic soln, in copper sulfate ethanolic soln used, the massfraction of copper sulfate is 7%, be at 60 DEG C, carry out copper generation reaction 1h after 2 with the salt acid for adjusting pH that massfraction is 7% again, leave standstill after reaction and be cooled to room temperature, precipitate in collected at room temperature, precipitation is first used the hot wash 3 times of 50 DEG C, then with volume fraction be 30% ethanolic soln washing to alcohol layer be light green, be light green with petroleum ether to petroleum ether layer again, then filter, be 12 by filter residue sodium hydroxide ethanolic soln adjust ph, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 7%, refilter, by filter residue with dry at 60 DEG C after absolute ethanol washing 3 times, obtain sodium copper chlorophyllin,
3) preparation of tigogenin: with step 2) in the bits that obtain be raw material, add sulfuric acid according to the ratio of Zha ﹕ 1.5mol/L sulfuric acid=1 ﹕ 1 and be hydrolyzed 6h at 108 DEG C, room temperature is cooled to after hydrolysis, the sodium hydroxide adding 2mol/L is while stirring neutralized to neutrality, then filter and obtain filter residue, with moisture 3 washing filter residues removing of 500mL
after under the condition of 100 DEG C dry 7h, by dried filter residue porphyrize, with the filter residue of porphyrize for raw material, be that extraction agent extracts with sherwood oil, extraction conditions is: with the speed of 4/s backflow 8h, the extraction agent of in extraction liquid 75% is reclaimed by vacuum concentration, 3h is kept after the extraction liquid mixture of ice and water reclaiming extraction agent is cooled to 6 DEG C, tigogenin crystallization is formed, then crystallization is filtered out, first utilize sherwood oil to wash, then dry 1h under the condition of 100 DEG C, obtain fusing point 196 ~ 204 DEG C, purity is the tigogenin of 96.3%.
Claims (10)
1. adopt single stage method to be separated a method for pectin, chlorophyll and tigogenin in sisal hemp pressed liquor, it is characterized in that, comprise the following steps:
1) pectin is separated: obtain sisal leaves pressed liquor by squeezing, and in sisal leaves pressed liquor, add ethanol while stirring to no longer producing flocks, then centrifugation, obtains supernatant liquor and flocks, take flocks as raw material production pectin;
2) chlorophyllous separation: with step 1) in the supernatant liquor that obtains be raw material, paste A is obtained by the vacuum concentration ethanol reclaimed wherein, porphyrize or pulverizing after paste A drying are obtained paste powder, with paste powder for raw material extracts, be cooled to room temperature separation after extraction and be extracted liquid and bits, take extraction liquid as raw material, paste B is obtained by the vacuum concentration extraction agent reclaimed wherein, with paste B for raw material, obtain sodium copper chlorophyllin through saponification, copper generation, salt-forming reaction;
3) preparation of tigogenin: with step 2) in the bits that obtain be raw material, add sulfuric acid according to the ratio of Zha ﹕ sulfuric acid=1 ﹕ 1 to be hydrolyzed, after hydrolysis, be cooled to room temperature, add neutralizing agent while stirring and be neutralized to neutrality, then filter and obtain filter residue, wash filter residue removing with water
rear drying, by dried filter residue porphyrize, with the filter residue of porphyrize for raw material extracts, reclaim the extraction agent in extraction liquid by vacuum concentration, the extraction liquid reclaiming extraction agent is cooled to crystallization to be formed, then crystallization is filtered out and be drying to obtain tigogenin.
2. a kind of method adopting single stage method to be separated pectin, chlorophyll and tigogenin in sisal hemp pressed liquor according to claim 1, is characterized in that, step 1) in the rotating speed of centrifugation be 3000r/min, the time is 12 ~ 15min; Step 2) in by vacuum concentration reclaim ethanol and reclaim extraction agent time vacuum tightness be 0.08 ~ 0.09MPa, temperature is 40 ~ 50 DEG C; Step 3) in by vacuum concentration reclaim extraction agent time vacuum tightness be 0.08 ~ 0.09MPa, temperature is 40 ~ 50 DEG C.
3. a kind of method adopting single stage method to be separated pectin, chlorophyll and tigogenin in sisal hemp pressed liquor according to claim 1, it is characterized in that, step 1) in take flocks as the method for raw material production pectin be: take flocks as raw material, add hydrochloric acid to be hydrolyzed reaction, hydrolyzed solution filters, clarification is rear concentrated, activated carbon decolorizing is added after concentrated, then filter, ethanolic soln is added in filtrate, pectin and precipitating out, then obtain pectin after press filtration, washing with alcohol, vacuum-drying, pulverizing.
4. a kind of pectin adopted in single stage method separation sisal hemp pressed liquor according to claim 3, the method of chlorophyll and tigogenin, it is characterized in that, concentration of hydrochloric acid is 0.05 ~ 0.1mol/L, the add-on of hydrochloric acid is 8 ~ 10 times of flocks quality, the temperature of hydrolysis reaction is 80 ~ 85 DEG C, time is 1.5 ~ 2h, hydrolyzed solution filters, being concentrated into mass fraction of solids after clarification is 3 ~ 5%, temperature when adding gac is 80 ~ 85 DEG C, bleaching time is 10 ~ 15min, the volume fraction of the ethanolic soln added in filtrate is 75 ~ 95%, the volume fraction of ethanol is made to reach 45 ~ 50% after adding ethanolic soln.
5. a kind of method adopting single stage method to be separated pectin, chlorophyll and tigogenin in sisal hemp pressed liquor according to claim 1, it is characterized in that, step 2) in extraction process extraction agent used be ethanol, acetone, ether or chloroform, extraction conditions is: with the speed of 4 ~ 6/s backflow 6 ~ 8h; Step 3) in extraction process extraction agent used be sherwood oil, extraction conditions is: with the speed of 4 ~ 6/s backflow 6 ~ 8h.
6. a kind of pectin adopted in single stage method separation sisal hemp pressed liquor according to claim 1, the method of chlorophyll and tigogenin, it is characterized in that, step 2) in paste B for raw material, through saponification, copper generation, the process that salt-forming reaction obtains sodium copper chlorophyllin is: with paste B for raw material, add sodium hydroxide ethanolic soln, adjust ph be after 10.5 ~ 11.5 at 55 ~ 60 DEG C saponification 1 ~ 2h, after saponification completely, vacuum concentration to volume is original 1/4 ~ 1/3, use petroleum ether extraction again, after extraction, lower floor's salt acid for adjusting pH is neutral, add excess sulfuric acid copper ethanolic soln, be carry out copper generation reaction after 2 ~ 3 with salt acid for adjusting pH again, leave standstill after reaction and be cooled to room temperature, precipitate in collected at room temperature, precipitation is first used hot wash, then with ethanolic soln washing to alcohol layer be light green, be light green with petroleum ether to petroleum ether layer again, then filter, be 11 ~ 12 by filter residue sodium hydroxide ethanolic soln adjust ph, refilter, by dry after filter residue absolute ethanol washing, obtain sodium copper chlorophyllin.
7. a kind of method adopting single stage method to be separated pectin, chlorophyll and tigogenin in sisal hemp pressed liquor according to claim 6, it is characterized in that, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 5 ~ 8%; Petroleum ether extraction 3 ~ 4 times are used after vacuum concentration; Hydrochloric acid massfraction used is 5 ~ 8%; In copper sulfate ethanolic soln used, the massfraction of copper sulfate is 5 ~ 10%; The temperature of copper generation reaction is 50 ~ 60 DEG C, and the time is 1 ~ 2h; First using the hot wash 2 ~ 3 times of 50 ~ 60 DEG C after collecting precipitation, is then light green with the ethanolic soln washing that volume fraction is 30 ~ 40% to alcohol layer; Finally adopt absolute ethanol washing filter residue 2 ~ 3 times, then dry at 50 ~ 60 DEG C.
8. a kind of method adopting single stage method to be separated pectin, chlorophyll and tigogenin in sisal hemp pressed liquor according to claim 1, it is characterized in that, step 3) in the concentration of sulfuric acid be 1.5mol/L, the temperature of hydrolysis is 105 ~ 110 DEG C, and the time is 6 ~ 8h; Step 3) in the sodium hydroxide of neutralizing agent used to be concentration be 2mol/L.
9. a kind of method adopting single stage method to be separated pectin, chlorophyll and tigogenin in sisal hemp pressed liquor according to claim 1, it is characterized in that, step 3) in only reclaim when to be reclaimed in extraction liquid extraction agent by vacuum concentration 70 ~ 80% extraction agent; Step 3) in the extraction liquid reclaiming extraction agent to be cooled to the cooling temperature that crystallization formed be 5 ~ 10 DEG C, the time is 2 ~ 3h; Step 3) in crystallization is filtered out after, first utilize sherwood oil to wash, be then drying to obtain tigogenin.
10. adopt single stage method to be separated a method for pectin, chlorophyll and tigogenin in sisal hemp pressed liquor, it is characterized in that, comprise the following steps:
1) pectin is separated: adopt mechanical expression method to obtain sisal leaves pressed liquor, ethanol is added while stirring to no longer producing flocks in sisal leaves pressed liquor, then centrifugation 15min under the condition of 3000r/min, obtain supernatant liquor and flocks, take flocks as raw material, add the hydrochloric acid that concentration is 0.06mol/L, wherein the add-on of hydrochloric acid is 10 times of flocks quality, 1.5h is hydrolyzed at 80 DEG C, hydrolyzed solution filters, being concentrated into mass fraction of solids after clarification is 3%, at 80 DEG C, activated carbon decolorizing 10min is added after concentrated, then filter, in filtrate, add volume fraction is 95% ethanolic soln, the volume fraction of ethanol is made to reach 50% after adding ethanolic soln, pectin and precipitating are out, then through press filtration, washing with alcohol, vacuum-drying, pectin is obtained after pulverizing,
2) chlorophyllous separation: with step 1) in the supernatant liquor that obtains be raw material, be 0.085MPa in vacuum tightness, temperature is obtain paste A by the vacuum concentration ethanol reclaimed wherein under the condition of 45 DEG C, by paste A at 85 DEG C after dry 6h porphyrize or pulverizing obtain paste powder, with paste powder for raw material, be that extraction agent extracts with ethanol, extraction conditions is: with the speed of 4/s backflow 6h, be cooled to room temperature separation after extraction and be extracted liquid and bits, take extraction liquid as raw material, be 0.085MPa in vacuum tightness, temperature is obtain paste B by the vacuum concentration extraction agent reclaimed wherein under the condition of 45 DEG C, with paste B for raw material, add sodium hydroxide ethanolic soln, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 5%, adjust ph be after 11 at 60 DEG C saponification 1h, after saponification completely, vacuum concentration to volume is original 1/3, use petroleum ether extraction again 3 times, after extraction, lower floor's massfraction is the salt acid for adjusting pH of 5% is neutral, add excess sulfuric acid copper ethanolic soln, in copper sulfate ethanolic soln used, the massfraction of copper sulfate is 5%, be at 50 DEG C, carry out copper generation reaction 1h after 2 with the salt acid for adjusting pH that massfraction is 5% again, leave standstill after reaction and be cooled to room temperature, precipitate in collected at room temperature, precipitation is first used the hot wash 2 times of 50 DEG C, then with volume fraction be 30% ethanolic soln washing to alcohol layer be light green, be light green with petroleum ether to petroleum ether layer again, then filter, be 11 by filter residue sodium hydroxide ethanolic soln adjust ph, in sodium hydroxide ethanolic soln used, the massfraction of sodium hydroxide is 5%, refilter, by filter residue with dry at 50 DEG C after absolute ethanol washing 2 times, obtain sodium copper chlorophyllin,
3) preparation of tigogenin: with step 2) in the bits that obtain be raw material, add sulfuric acid according to the ratio of Zha ﹕ 1.5mol/L sulfuric acid=1 ﹕ 1 and be hydrolyzed 7h at 108 DEG C, room temperature is cooled to after hydrolysis, the sodium hydroxide adding 2mol/L is while stirring neutralized to neutrality, then filter and obtain filter residue, with the removing of 500mL moisture 3 washing filter residues
after under the condition of 80 DEG C dry 8h, by dried filter residue porphyrize, with the filter residue of porphyrize for raw material, be that extraction agent extracts with sherwood oil, extraction conditions is: with the speed of 5/s backflow 7h, the extraction agent of in extraction liquid 70% is reclaimed by vacuum concentration, 2h is kept after the extraction liquid mixture of ice and water reclaiming extraction agent is cooled to 5 DEG C, tigogenin crystallization is formed, then crystallization is filtered out, first 40mL sherwood oil is utilized to wash at twice, then dry 2h under the condition of 80 DEG C, obtain fusing point 196 ~ 204 DEG C, purity is the tigogenin of 96%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510227364.8A CN104926915A (en) | 2015-05-06 | 2015-05-06 | One-step method for separating pectin, chlorophyll and tigogenin in sisal pressed liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510227364.8A CN104926915A (en) | 2015-05-06 | 2015-05-06 | One-step method for separating pectin, chlorophyll and tigogenin in sisal pressed liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104926915A true CN104926915A (en) | 2015-09-23 |
Family
ID=54114359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510227364.8A Pending CN104926915A (en) | 2015-05-06 | 2015-05-06 | One-step method for separating pectin, chlorophyll and tigogenin in sisal pressed liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104926915A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160935A (en) * | 2018-06-28 | 2019-01-08 | 广西浙缘农业科技有限公司 | A kind of method that low-cost high-efficiency extracts tigogenin and cellulose |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386622A (en) * | 2008-09-03 | 2009-03-18 | 赵雪梅 | Method for preparing sodium copper chlorophyllin in red-purple pitaya sterm |
| CN101724093A (en) * | 2008-10-31 | 2010-06-09 | 吴玉华 | Method for extracting solid pectin |
| CN104557953A (en) * | 2015-01-29 | 2015-04-29 | 陕西科技大学 | One-step method for separating pectin, chlorophyll and tigogenin in sisal hemp pressed liquor |
-
2015
- 2015-05-06 CN CN201510227364.8A patent/CN104926915A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386622A (en) * | 2008-09-03 | 2009-03-18 | 赵雪梅 | Method for preparing sodium copper chlorophyllin in red-purple pitaya sterm |
| CN101724093A (en) * | 2008-10-31 | 2010-06-09 | 吴玉华 | Method for extracting solid pectin |
| CN104557953A (en) * | 2015-01-29 | 2015-04-29 | 陕西科技大学 | One-step method for separating pectin, chlorophyll and tigogenin in sisal hemp pressed liquor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160935A (en) * | 2018-06-28 | 2019-01-08 | 广西浙缘农业科技有限公司 | A kind of method that low-cost high-efficiency extracts tigogenin and cellulose |
| CN109160935B (en) * | 2018-06-28 | 2021-04-06 | 台州中知英健机械自动化有限公司 | Method for extracting tigogenin and cellulose |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106860492B (en) | Preparation method of cannabinol compound | |
| CN102212053B (en) | Method for extracting mulberry cyanidin | |
| CN101671399B (en) | Preparation method of fucoidan sulfuric ester with high purity and high-sulfate radical content | |
| CN110294784B (en) | Method for extracting oryzanol by taking rice bran oil refined soapstock as raw material | |
| CN103232552B (en) | A kind of enzyme process prepares the method for brown alga fucosan and fucoxanthin | |
| CN101637545A (en) | Supercritical extraction method of green tea extract | |
| CN103509028B (en) | The preparation method of a kind of chlorophyll cupric acid and copper sodium | |
| CN104892785A (en) | Extraction method of seaweed polysaccharide | |
| CN104513217A (en) | Mulberry anthocyanidin extraction technology | |
| CN104326912B (en) | A kind of separation method of tobacco leaf effective constituent | |
| CN102070411B (en) | Method for refining honokiol | |
| CN104876824A (en) | Technology for separation and purification of chlorogenic acid from coffee beans | |
| CN1397545A (en) | Process for extracting 4-hydroxy-isoleucine and by-products including feungreek gum from seed of feungreek | |
| CN102267906B (en) | Extraction method for chlorogenic acid | |
| CN110305179B (en) | Method for extracting oryzanol by taking unsaponifiable matters refined from rice bran oil as raw materials | |
| CN102887821B (en) | A kind of method of extracting and separating marine microalgae broth extraction DHA | |
| CN102002083A (en) | Method for extracting high-purity rutin with flash-extraction technology | |
| CN111848362A (en) | Method for preparing high-purity cannabidiol by combining ultrasonic extraction with dynamic axial compression column system | |
| CN104557953A (en) | One-step method for separating pectin, chlorophyll and tigogenin in sisal hemp pressed liquor | |
| CN104926915A (en) | One-step method for separating pectin, chlorophyll and tigogenin in sisal pressed liquid | |
| CN107286071A (en) | It is a kind of that bilirubin and cholic acid co-production cholesterol, the method for lecithin are extracted from bile | |
| CN104055702B (en) | A kind of skin antiallergic wetting agent | |
| CN102796034B (en) | Method for preparing lutein crystal from marigold flowers | |
| CN105272989A (en) | Method for preparing chlorophyll sodium copper from mulberry leaves | |
| CN1234723C (en) | Method for extracting fucosterol from alga |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150923 |