CN100509964C - Method for preparing rdish red pigment and radish phenyl-isosulfo cyanate - Google Patents
Method for preparing rdish red pigment and radish phenyl-isosulfo cyanate Download PDFInfo
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- CN100509964C CN100509964C CNB2006100541099A CN200610054109A CN100509964C CN 100509964 C CN100509964 C CN 100509964C CN B2006100541099 A CNB2006100541099 A CN B2006100541099A CN 200610054109 A CN200610054109 A CN 200610054109A CN 100509964 C CN100509964 C CN 100509964C
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Abstract
The present invention relates to a preparation method of radish red pigment and isosulfocyanate. The present invention relates to a preparation method of a natural plant red pigment and isosulfocyanatThis invention relates to a method for preparing red coloring mater of radish and isosulfocyanide, which takes radishes of e. The present invention uses Xinlimei radishes as raw material. Through crushing heating operation, ultrafiltration operation, extractive separation operation, vacuum concentration operation, freeze racted and separated, vacuum concentrated and frozen and dried to prepare red coloring matter of radishes, during the process, the collected extraction solution of isosulfocyanide is added with dilutedrying operation, etc., the radish red pigment is prepared. In the process of preparing the radish red pigment, diluted alkali liquid is added to collected isosulfocyanate extraction liquid for revers alkali water to be counter-extracted and separated to exchange anions to prepare the isosulfocyanide and the renewed extraction agent and the anion exchange resin can be used again. e extraction separation, anion exchange, etc., and the isosulfocyanate is prepared. Simultaneously, a regeneration extraction agent and anion exchange resin can be used again. The present invention mainly has the characteristics that resources are comprehensively utilized, the discharge of waste and waste water is reduced, the present invention is good for protecting the environment and saving resources and energy sources, the preparation technology is simple, equipment is simple, etc. The quality of the radish red pigment and the radish isosulfocyanate which are prepared according to the method of the present invention is high, the radish red pigment and the radish isosulfocyanate can be used as a natural additive agent of food, and the market competitiveness is strong. The present invention can be widely used in coloring of food, functional food which has the antitumoral effect, etc.
Description
One. technical field
The invention belongs to natural pigment technical field in the foodstuff additive, particularly the preparation method of natural phant haematochrome and radish lsothiocyanates.
Two. background technology
Radish red pigment belongs to natural plant pigment, has nontoxic, biodegradable, sufficient raw and characteristics such as inexpensive, can be widely used in the painted of food such as beverage, cake, candy, jelly.But be present in the lsothiocyanates in the radish red pigment, cause that because of there being intensive to be flavor property peculiar smell is arranged in the radish red pigment, thereby influence the quality of food.
Lsothiocyanates is the hydrolysate of cress composition sinigrin.In recent years, discover that this material has very strong antitumous effect, antagonism lung cancer, mammary cancer, skin carcinoma etc. have obvious effects, are a kind of potential functional food additives; Have antibacterium and fungi again and kill the effect of cress insect; Also have the growth hormone metabolism of regulating plant, thus the effect of coordinate plant growth.
The existing method for preparing the free from extraneous odour radish red pigment, as the Chinese patent publication number is CN1226586 " taking off flavor radish red pigment and preparation method thereof ", " a kind of method of utilizing turnip with red inside to extract the natural edible radish red pigment " of CN1241599, " preparation method of radish red pigment " of CN1510086, it all is raw material with the turnip with red inside, through cleaning, section (silk), the acidic aqueous solution lixiviate, and use zymin, oxidation inhibitor or eluent or flocculation agent are handled, also process is again adsorbed and is separated, last concentrate drying powdering finished product, though the look valency of its product is better than standard GB 6718-86, but be 60 only, still have peculiar smell and purity not high in the product; Particularly in process of production, not utilize resources synthetically, the not regeneration of various preparation, this had not only wasted resource but also contaminate environment; Especially the method for CN1510086 is a concentrate drying at high temperature, and its thickening temperature is up to 40～80 ℃, and drying temperature is especially up to 180～220 ℃, and this is many power consumptions but also unfavorable safety in production etc. not only.
The existing method for preparing the radish lsothiocyanates has following two classes:
1. distillation and extraction method
This method is after mustard seed end is pulverized, with o-2 potassium acid hydrogen potassium-potassium hydroxide hydrolysis, pass through vapor distillation again after, more for several times with extracted with diethyl ether, at last with the yellow soda ash dehydration and product.But the main weak point of this method is repeatedly to use low, volatile, the virose extracted with diethyl ether agent of boiling point in process of production, severe contamination air, harmful operator's health again; Adopt Potassium Hydrogen Phthalate-potassium hydroxide to be hydrolyzed, the mustard seed powder stock can not make full use of, and produces a large amount of residue contamination environment, is unfavorable for environment protection.And for example the Chinese patent publication number is " method that is prepared isosulfocyanate by cress " of CN1405316, is raw material with cresss such as this Yu of Ri dish, Western, Yu dish, Chinese celeries, by enzyme reaction, drying, distillation extraction product.The main weak point of this method is that raw material does not fully utilize; In process of production, need react for a long time with enzyme, thereby cause the production cycle long, production efficiency is low, the production cost height, and waste material causes environmental pollution.
2. chemical synthesis
This method is in the presence of organic solvent chloroform, second eyeball etc., with the reaction of refrigerative dithiocarbonic anhydride and Armeen or with sinteticses such as the halogen-sugar of the sugared hydroxyls of protection such as benzyl, ethanoyl and isothiocyanic acid nak responses.The main weak point of this method is to carry out radical protection and go the protecting group operation, and strict fire prevention, measure such as explosion-proof are arranged, so equipment is complicated and investment is high, the production cost height; Produce a large amount of Organic pollutants environment in process of production, influence environment protection; Do not produce plurality of impurities because of reaction is single-minded again, and be difficult for separation and purification, have a strong impact on quality product etc.
Three. summary of the invention
The objective of the invention is weak point at existing preparation radish red pigment and radish lsothiocyanates method; the preparation method of a kind of radish red pigment and radish lsothiocyanates is provided; the present invention mainly has utilize resources synthetically; reduce the discharging of refuse and waste water; help environment protection; save resources and energy, help characteristics such as safety in production.
The object of the present invention is achieved like this: the preparation method of a kind of radish red pigment and radish lsothiocyanates, with " red flesh " radish is raw material, prepares the radish red pigment dry freeze powder through broken heating, vacuum filtration, ultrafiltration, extracting and separating and lyophilize.In the process of preparation radish red pigment, to the radish lsothiocyanates extraction liquid of collecting, through diluted alkaline water reextraction separation, anionresin and wash-out, concentrate after, prepare radish lsothiocyanates product, regenerating extracting agent and anionite-exchange resin can reuse simultaneously.Its main technique flow process is as follows:
Concrete grammar step of the present invention is as foretelling:
(1) preparation of radish red pigment solution
1. the preparation of crude extract
" red flesh " radish is cleaned, after being cut into small pieces, add distilled water, the weightmeasurement ratio of its radish and distilled water is 1:10～12, be heated to 50～65 ℃ after crushed, and keep 60～90min, be penetrated in the solution from radish with the promotion radish red pigment, and impel myrosin to decompose sinigrin generation radish lsothiocyanates.Then with the squeezing of 4～10 layers of gauze till do not have juice and discharge.Remove the radish slag, filtrate is heated to boiling and keeps 10～15min,, remove throw outs such as deproteinize, at last filtrate is cooled to room temperature, just make the radish red pigment crude extract so that protein denaturation precipitation carries out diatomite filtration to filtrate then.
2. the preparation of smart extracting solution
With the 1. radish red pigment crude extract prepared of step, by the molecular weight that dams is that the ultra-filtration membrane of 6000Da～10000Da carries out ultrafiltration, after removing macromolecule carbon hydrate such as pectin, its filtrate is for the radish isothiocyanate content is 0.03～0.06%, radish red pigment content is 0.25～0.60%, ash content is 0.2～0.3% the smart extracting solution of radish red pigment.
(2) preparation of extraction agent
Be 1% HCl according to concentration: secondary octyl phenylium (being CA-12): trioctyl phosphate: the volume ratio of thinner (as cyclohexane or normal heptane etc.) is that the ratio of 1:5～10:5～10:15～20 is got the raw materials ready, add secondary octyl phenylium (CA-12) and trioctyl phosphate earlier and mix back adding thinner and HCl, stir with agitator again, its stirring velocity is 200～300r/min, last standing demix 15～20min, abandon lower floor's water, keep upper strata liquid and be extraction agent solution.
Its extraction mechanisms is: secondary octyl phenylium (being CA-12) by dividing the phenyl hydrophobic region in the molecule, can form hydrophobic the combination with the radish lsothiocyanates that contains phenyl, thereby be extracted from the smart extracting solution of radish red pigment; Because the octyl group of trioctyl phosphate partly has close ester, also can form hydrophobic the combination with the ester group of radish lsothiocyanates, thereby cutting out partial radish lsothiocyanates from the radish red pigment seminal fluid again; Under acidic conditions, the metal ion in the smart extracting solution of radish red pigment is solution state, and metal ions such as calcium wherein, magnesium can form coordinate bond with the phosphoric acid oxygen of trioctyl phosphate, and the sulphur of radish lsothiocyanates also can form coordinate bond with above-mentioned ion.Promptly under acidic conditions, form trioctyl phosphate-metal ion-radish lsothiocyanates coordination thing, thereby the radish lsothiocyanates is extracted out from the smart extracting solution of radish red pigment by this extraction agent; On the other hand, removed part mineral ion in the smart extracting solution of radish red pigment again.
(3) extraction and the separation of radish lsothiocyanates in the smart extracting solution of radish red pigment
1. extraction
Go on foot in the smart extracting solution of the radish red pigment of preparing (1), add (2) while stirring and go on foot the extraction agent of preparing, and continue to stir 5～10min, its stirring velocity is 200～300r/min, so that extract the radish lsothiocyanates from the smart extracting solution of radish red pigment.The volume ratio of smart extracting solution of radish red pigment and extraction agent is 1:1～1.5.
2. separate
Radish red pigment and radish lsothiocyanates extraction mixed solution that (3)-1. step was prepared are transferred in the liquid distributing device, behind standing demix 35～45min, extract upper strata radish lsothiocyanates extraction liquid and lower floor radish red pigment extraction liquid for the first time respectively, radish red pigment for the first time in the extraction liquid radish red pigment content be 0.3～0.65%, the radish lsothiocyanates for≤0.001%, ash content is 1.5～2.5%.
3. extraction again
Through (3)-1. with 2. step extraction, separates in the lower floor's radish red pigment extraction liquid first time of back extraction, add (2) once more while stirring and go on foot the extraction agent of preparing, and 5～10min is stirred in continuation, its stirring velocity is 200～300r/min, so that further extract the radish lsothiocyanates from the radish red pigment extraction liquid.The volume ratio of radish red pigment extraction liquid and extraction agent still is 1:1～1.5.
4. separate again
The radish red pigment extraction liquid second time and radish lsothiocyanates extraction mixed solution that (3)-3. step was prepared are transferred in the liquid distributing device, behind static layering 35～45min, extract upper strata radish lsothiocyanates extraction liquid and lower floor radish red pigment extraction liquid for the second time respectively, radish red pigment content is 0.03～0.68% to radish red pigment in the extraction liquid for the second time, the radish lsothiocyanates is 0, ash content is≤0.1%.
(4) preparation of radish red pigment powder
Go on foot after twice extraction, separating (3), the lower floor's radish red pigment that extracts is extraction liquid for the second time, by the aperture is that the filter membrane of 0.22～0.45 μ m carries out secondary filter, after removing impurity such as microorganism, carry out vacuum concentration to 520 nanometer optical density(OD) again more than or equal to 2.5, under-50～-55 ℃, carry out lyophilize at last, prepare outstanding valency 〉=65, radish isothiocyanate content and be 0, ash content is＜1% radish red pigment lyophilized powder, being heated to boiling 10min does not have the radish smell yet.
(5) regeneration of extraction agent
1. strip and separate
In the upper strata radish lsothiocyanates extraction liquid that after (3) goes on foot through twice extracting and separating, extracts, adding pH value is 8.5～10.5 dilute alkaline aqueous solution, be warming up to 35～55 ℃ then, the volume ratio of radish lsothiocyanates extraction liquid and dilute alkaline aqueous solution is 1:1～1.5, stir again, its stirring velocity is 200～300r/min, and churning time is 20～30min, strips fully.So that the hydroxide radical in the solution is under alkaline condition, with the trioctyl phosphate-metal ion-radish lsothiocyanates coordination thing reaction in the radish lsothiocyanates extraction liquid, thereby form water-insoluble precipitate metal hydroxides, trioctyl phosphate-metal ion-radish lsothiocyanates coordination thing is destroyed, and the radish lsothiocyanates is taken out in back extraction; Under this external alkaline condition, the radish lsothiocyanates is electronegative, and solvability increases, and weakens with the bonding force of extraction agent, thereby is stripped and enter in the aqueous solution.Then this mixed solution is transferred in the liquid distributing device, carry out static layering after, extract extraction agent and lower floor's radish lsothiocyanates anti-stripping agent after stripping in the upper strata respectively.
2. regeneration
In the extraction agent after stripping in the upper strata of (5)-1. step extraction, HCl10～the 20mL of adding 1.0%, speed with 200～300r/min stirs, extraction agent volume ratio after 1%HCL that adds and the extraction is 1: 20～25, standing demix then, abandon lower floor's water, extract the upper strata regenerating extracting agent, can be used for once more from radish red pigment liquid extraction radish lsothiocyanates.
(6) preparation of radish lsothiocyanates
In lower floor's radish lsothiocyanates anti-stripping agent of (5)-1. step extraction, add strongly basic anion ion exchange resin (as D201, D245, D393 etc.), the anionite-exchange resin that adds and the volume ratio of radish lsothiocyanates anti-stripping agent are 1: 20～25, speed with 200～300r/min stirs, and churning time is 20～30min, so that carry out sufficient permutoid reaction.Use the NaOH wash-out of 0.1～0.5mol/L then, collect elutriant.With 0.1～0.2Mpa steam distillation, 30～40min, the collection distillate is used CaCl to the elutriant collected
2The dehydration back is a radish lsothiocyanates product.And extract the anionite-exchange resin that wash-out goes out the radish lsothiocyanates and carry out manipulation of regeneration.
(7) anionite-exchange resin regeneration
The wash-out of (6) step extraction is gone out the anionite-exchange resin of radish lsothiocyanates, 4～8% NaOH regenerated from washing with 5～10 times 4～8% dilute hydrochloric acid and 5～10 times, after removing other impurity, just make the anion regenerant exchange resin, can reuse.
After the present invention adopts technique scheme, can fully utilize the radish resource, reduce the discharging of waste and waste water, help environment protection, save resources and energy.This production technique is simple, and equipment is simple, helps characteristics such as safety in production.The radish red pigment that adopts the present invention to produce is a natural plant pigment, can be widely used in the painted of food such as beverage, cake, candy, jelly; The radish lsothiocyanates of producing is a kind of functional food additives of very strong antitumous effect, the effect that has antibiotic, deinsectization effect and coordinate plant growth again, can be widely used in anti-breast cancer, skin carcinoma etc., can be used for killing insect of cress and the growth metabolism of adjusting plant etc. again.
Five. embodiment
Below in conjunction with embodiment, further specify the present invention
Embodiment 1
The preparation method's of a kind of radish red pigment and radish lsothiocyanates step is as follows:
(1) preparation of radish red pigment solution
1. the preparation of crude extract
100g " red flesh " radish is added 1000mL distilled water, is heated to 50 ℃ after crushed, and keep 60min, then with 8 layers of gauzes squeezing till do not have a juice discharge.Remove the radish slag, filtrate is heated to boiling and keeps 10min, then filtrate is carried out diatomite filtration, at last filtrate is cooled to room temperature, just make the radish red pigment crude extract;
2. the preparation of smart extracting solution
With the 1. radish red pigment crude extract prepared of step, by the molecular weight that dams is after the ultra-filtration membrane of 6000Da carries out ultrafiltration, and the filtrate of reservation is for the radish isothiocyanate content is 0.035%, radish red pigment content is 0.65%, ash content is 0.34% the smart extracting solution of radish red pigment;
(2) preparation of extraction agent
Be 1% HCl according to concentration: secondary octyl phenylium (being CA-12): trioctyl phosphate: the volume ratio of normal heptane thinner is that the ratio of 1:5:5:15 is got the raw materials ready, add secondary octyl phenylium (CA-12) and trioctyl phosphate earlier and mix back adding normal heptane thinner and HCl, stir with agitator again, its stirring velocity is 200r/min, last standing demix 15min, abandon lower floor's water, keep upper strata extraction agent solution;
(3) extraction and the separation of radish lsothiocyanates in the smart extracting solution of radish red pigment
1. extraction
Go on foot in the smart extracting solution of the radish red pigment of preparing (1), add (2) while stirring and go on foot the extraction agent of preparing, and continue to stir 5min, its stirring velocity is 200r/min, and the volume ratio of radish red pigment essence extracting solution and extraction agent is 1:1;
2. separate
Radish red pigment and radish lsothiocyanates extraction mixed solution that (3)-1. step was prepared are transferred in the liquid distributing device, behind the standing demix 35min, extract upper strata radish lsothiocyanates extraction liquid and lower floor radish red pigment extraction liquid for the first time respectively, radish red pigment for the first time in the extraction liquid radish red pigment content be 0.78%, the radish lsothiocyanates for≤0.00063%, ash content is 0.15%;
3. extraction again
Through (3)-1. with 2. step extraction, separates in the lower floor's radish red pigment extraction liquid first time of back extraction, add (2) once more while stirring and go on foot the extraction agent of preparing, and 5min is stirred in continuation, its stirring velocity is 200r/min, and the volume ratio of radish red pigment extraction liquid and extraction agent still is 1:1;
4. separate again
The radish red pigment extraction liquid second time and radish lsothiocyanates extraction mixed solution that (3)-3. step was prepared are transferred in the liquid distributing device, behind the standing demix 35min, extract upper strata radish lsothiocyanates extraction liquid and lower floor radish red pigment extraction liquid for the second time respectively, radish red pigment content is 0.48% to radish red pigment in the extraction liquid for the second time, the radish lsothiocyanates is 0, ash content is≤0.082%;
(4) preparation of radish red pigment powder
Go on foot after twice extracting and separating (3), the lower floor's radish red pigment that extracts is extraction liquid for the second time, by the aperture is that the filter membrane of 0.22 μ m carries out secondary filter, carry out vacuum concentration to 520 nanometer optical density(OD) 〉=2.5 again, at last under-50 ℃, carry out lyophilize, prepare outstanding valency and be 65, the radish isothiocyanate content is 0, ash content is 0.54% radish red pigment lyophilized powder, being heated to boiling 10min does not have the radish smell yet;
(5) regeneration of extraction agent
1. strip and separate
In the upper strata radish lsothiocyanates extraction liquid that after (3) goes on foot through twice extracting and separating, extracts, adding pH value is rare NaOH aqueous solution of 8.5, be warming up to 35 ℃ then, the volume ratio of its radish lsothiocyanates extraction liquid and this solution is 1:1, stirs again, and its stirring velocity is 200r/min, churning time is 20min, then this mixed solution is transferred in the liquid distributing device, carries out standing demix, extract extraction agent and lower floor's radish lsothiocyanates anti-stripping agent after stripping in the upper strata respectively;
2. regeneration
In the extraction agent after stripping in the upper strata of (5)-1. step extraction, the HCl 10mL of adding 1.0%, speed with 200r/min stirs, extraction agent volume ratio after 1%HCl that adds and the extraction is 1: 20, standing demix then, abandon lower floor's water, extract the upper strata regenerating extracting agent, can be used for once more from radish red pigment liquid extraction radish lsothiocyanates;
(6) preparation of radish lsothiocyanates
In lower floor's radish lsothiocyanates anti-stripping agent of (5)-1. step extraction, add D201 strongly basic anion ion exchange resin, the volume ratio that adds anionite-exchange resin and radish lsothiocyanates anti-stripping agent is 1: 20, speed with 200r/min stirs, with the NaOH wash-out of 0.1mol/L, collect elutriant behind the stirring 20min.To the elutriant of collecting 0.1Mpa steam distillation 40min, collect distillate, use CaCl
2Dehydration back be a radish lsothiocyanates product, and the anionite-exchange resin that the extraction wash-out goes out the radish lsothiocyanates carries out manipulation of regeneration;
(7) anionite-exchange resin regeneration
The wash-out that (6) step was extracted goes out the anionite-exchange resin of radish lsothiocyanates, with 8% NaOH regenerated from washing of 5 times 8% dilute hydrochloric acid and 5 times, remove other impurity after, just make the anion regenerant exchange resin, can reuse.
Embodiment 2
The preparation method's of a kind of radish red pigment and radish lsothiocyanates step is as follows:
(1) preparation of radish red pigment solution
1. the preparation of crude extract
100g " red flesh " radish is added 1200mL distilled water, is heated to 60 ℃ after crushed, and keep 80min, then with 8 layers of gauzes squeezing till do not have a juice discharge.Remove the radish slag, filtrate is heated to boiling and keeps 15min, then filtrate is carried out diatomite filtration, at last filtrate is cooled to room temperature, just make the radish red pigment crude extract;
2. the preparation of smart extracting solution
With the 1. radish red pigment crude extract prepared of step, by the molecular weight that dams is after the ultra-filtration membrane of 6000Da carries out ultrafiltration, and the filtrate of reservation is for the radish isothiocyanate content is 0.03%, radish red pigment content is 0.45%, ash content is 0.26% the smart extracting solution of radish red pigment;
(2) preparation of extraction agent
Be 1% HCl according to concentration: secondary octyl phenylium (being CA-12): trioctyl phosphate: the volume ratio of hexanaphthene thinner is that the ratio of 1:5:5:15 is got the raw materials ready, add secondary octyl phenylium (CA-12) and trioctyl phosphate earlier and mix back adding hexanaphthene thinner and HCl, stir with agitator again, its stirring velocity is 300r/min, last standing demix 20min, abandon lower floor's water, keep upper strata extraction agent solution;
(3) extraction and the separation of radish lsothiocyanates in the smart extracting solution of radish red pigment
1. extraction
Go on foot in the smart extracting solution of the radish red pigment of preparing (1), add (2) while stirring and go on foot the extraction agent of preparing, and continue to stir 10min, its stirring velocity is 300r/min, and the volume ratio of radish red pigment essence extracting solution and extraction agent is 1:1;
2. separate
Radish red pigment and radish lsothiocyanates extraction mixed solution that (3)-1. step was prepared are transferred in the liquid distributing device, behind the standing demix 45min, extract upper strata radish lsothiocyanates extraction liquid and lower floor radish red pigment extraction liquid for the first time respectively, radish red pigment for the first time in the extraction liquid radish red pigment content be 0.55%, the radish lsothiocyanates for≤0.00033%, ash content is 1.5%;
3. extraction again
Through (3)-1. with 2. step extraction, separates in the lower floor's radish red pigment extraction liquid first time of back extraction, add (2) once more while stirring and go on foot the extraction agent of preparing, and 10min is stirred in continuation, its stirring velocity is 300r/min, and the volume ratio of radish red pigment extraction liquid and extraction agent still is 1:1;
4. separate again
The radish red pigment extraction liquid second time and radish lsothiocyanates extraction mixed solution that (3)-3. step was prepared are transferred in the liquid distributing device, behind the standing demix 45min, extract upper strata radish lsothiocyanates extraction liquid and lower floor radish red pigment extraction liquid for the second time respectively, radish red pigment content is 0.68% to radish red pigment in the extraction liquid for the second time, the radish lsothiocyanates is 0, ash content is≤0.053%;
(4) preparation of radish red pigment powder
Go on foot after twice extracting and separating (3), the lower floor's radish red pigment that extracts is extraction liquid for the second time, by the aperture is that the filter membrane of 0.22 μ m carries out secondary filter, carrying out vacuum concentration to 520 nanometer optical density(OD) again is 2.5, under-50 ℃, carries out lyophilize at last, preparing outstanding valency is 65, the radish isothiocyanate content is 0, and ash content is 0.34% radish red pigment lyophilized powder, and being heated to boiling 10min does not have the radish smell yet;
(5) regeneration of extraction agent
1. strip and separate
In the upper strata radish lsothiocyanates extraction liquid that after (3) goes on foot through twice extracting and separating, extracts, adding pH value is rare NaOH aqueous solution of 10.5, be warming up to 55 ℃ then, the volume ratio of its radish lsothiocyanates extraction liquid and this solution is 1:1, stirs again, and its stirring velocity is 300r/min, churning time is 20min, then this mixed solution is transferred in the liquid distributing device, carries out standing demix, extract extraction agent and lower floor's radish lsothiocyanates anti-stripping agent after stripping in the upper strata respectively;
2. regeneration
In the extraction agent after stripping in the upper strata of (5)-1. step extraction, the HCl 20mL of adding 1.0%, speed with 200r/min stirs, extraction agent volume ratio after 1%HCl that adds and the extraction is 1: 20, standing demix then, abandon lower floor's water, extract the upper strata regenerating extracting agent, can be used for once more from radish red pigment liquid extraction radish lsothiocyanates;
(6) preparation of radish lsothiocyanates
In lower floor's radish lsothiocyanates anti-stripping agent of (5)-1. step extraction, add D201 strongly basic anion ion exchange resin, the volume ratio that adds anionite-exchange resin and radish lsothiocyanates anti-stripping agent is 1: 25, speed with 300r/min stirs, with the NaOH wash-out of 0.1mol/L, collect elutriant behind the stirring 20min.To the elutriant of collecting 0.2Mpa steam distillation 30min, collect distillate, use CaCl
2The dehydration back is a radish lsothiocyanates product, and the anionite-exchange resin that wash-out is gone out the radish lsothiocyanates carries out manipulation of regeneration;
(7) anionite-exchange resin regeneration
(6) step wash-out is gone out the anionite-exchange resin of radish lsothiocyanates, with 4% NaOH regenerated from washing of 10 times 4% dilute hydrochloric acid and 10 times, remove other impurity after, just make the anion regenerant exchange resin, can reuse
Claims (3)
1. the preparation method of radish red pigment and radish lsothiocyanates is characterized in that the concrete grammar step is as follows:
(1) preparation of radish red pigment solution
1. the preparation of crude extract
" red flesh " radish is cleaned, after being cut into small pieces, add distilled water, the weightmeasurement ratio of its radish and distilled water is 1:10～12, is heated to 50～65 ℃ after crushed, and keeps 60～90min, then with the squeezing of 4～10 layers of gauze till do not have juice and discharge, filtrate is heated to boiling and keeps 10～15min, then filtrate is carried out diatomite filtration, at last filtrate is cooled to room temperature;
2. the preparation of smart extracting solution
With the 1. radish red pigment crude extract prepared of step, by the molecular weight that dams is that the ultra-filtration membrane of 6000Da～10000Da carries out ultrafiltration, and its filtrate is for the radish isothiocyanate content is 0.03～0.06%, radish red pigment content is 0.25～0.60%, ash content is 0.2～0.3% the smart extracting solution of radish red pigment;
(2) preparation of extraction agent
Be 1% HCl according to concentration: secondary octyl phenylium: trioctyl phosphate: the volume ratio of hexanaphthene or normal heptane thinner is that the ratio of 1:5～10:5～10:15～20 is got the raw materials ready, after adding the mixing of secondary octyl phenylium and trioctyl phosphate earlier, add thinner and HCl, stir with agitator again, its stirring velocity is 200～300r/min, last static layering 15～20min abandons lower floor's water, keeps upper strata extraction agent solution;
(3) extraction and the separation of radish lsothiocyanates in the smart extracting solution of radish red pigment
1. extraction
Go on foot in the smart extracting solution of the radish red pigment of preparing (1), add (2) while stirring and go on foot the extraction agent of preparing, and continue to stir 5～10min, its stirring velocity is 200～300r/min, the volume ratio of smart extracting solution of radish red pigment and extraction agent is 1:1～1.5;
2. separate
Radish red pigment and radish lsothiocyanates extraction mixed solution that (3)-1. step was prepared are transferred in the liquid distributing device, behind standing demix 35～45min, extract upper strata radish lsothiocyanates extraction liquid and lower floor radish red pigment extraction liquid for the first time respectively, radish red pigment for the first time in the extraction liquid radish red pigment content be 0.3～0.65%, the radish lsothiocyanates for≤0.001%, ash content is 1.5～2.5%;
3. extraction again
Through (3)-1. with 2. step extraction, separates in the lower floor's radish red pigment extraction liquid first time of back extraction, add (2) once more while stirring and go on foot the extraction agent of preparing, and 5～10min is stirred in continuation, its stirring velocity is 200～300r/min, and the volume ratio of radish red pigment extraction liquid and extraction agent still is 1:1～1.5;
4. separate again
The radish red pigment extraction liquid second time and radish lsothiocyanates extraction mixed solution that (3)-3. step was prepared are transferred in the liquid distributing device, behind standing demix 35～45min, extract upper strata radish lsothiocyanates extraction liquid and lower floor radish red pigment extraction liquid for the second time respectively, radish red pigment content is 0.03～0.68% to radish red pigment in the extraction liquid for the second time, the radish lsothiocyanates is 0, ash content is≤0.1%;
(4) preparation of radish red pigment powder
Go on foot after twice extraction, separating (3), the lower floor's radish red pigment that extracts is extraction liquid for the second time, by the aperture is that the filter membrane of 0.22～0.45 μ m carries out secondary filter, carry out vacuum concentration to 520 nanometer optical density(OD) again more than or equal to 2.5, at last under-50～-55 ℃, carry out lyophilize, prepare outstanding valency 〉=65, radish isothiocyanate content and be 0, ash content is＜1% radish red pigment lyophilized powder;
(5) regeneration of extraction agent
1. strip and separate
In the upper strata radish lsothiocyanates extraction liquid that after (3) goes on foot through twice extracting and separating, extracts, adding pH value is 8.5～10.5 dilute alkaline aqueous solution, be warming up to 35～55 ℃ then, the volume ratio of radish lsothiocyanates extraction liquid and dilute alkaline aqueous solution is 1:1～1.5, stir again, its stirring velocity is 200～300r/min, churning time is 20～30min, then this mixed solution is transferred in the liquid distributing device, after carrying out standing demix, extract extraction agent and lower floor's radish lsothiocyanates anti-stripping agent after stripping in the upper strata respectively;
2. regeneration
In the extraction agent after stripping in the upper strata of (5)-1. step extraction, HCl 10～the 20mL of adding 1.0%, speed with 200～300r/min stirs, extraction agent volume ratio after 1% HCL that adds and the extraction is 1: 20～25, standing demix then, abandon lower floor's water, extract the upper strata regenerating extracting agent;
(6) preparation of radish lsothiocyanates
In lower floor's radish lsothiocyanates anti-stripping agent of (5)-1. step extraction, add strongly basic anion ion exchange resin, the anionite-exchange resin that adds and the volume ratio of radish lsothiocyanates anti-stripping agent are 1: 20～25, speed with 200～300r/min stirs, and churning time is 20～30min, uses the NaOH wash-out of 0.1～0.5mol/L then, collect elutriant, with 0.1～0.2Mpa steam distillation, 30～40min, the collection distillate is used CaCl to the elutriant collected
2Dehydration, and extract the anionite-exchange resin that wash-out goes out the radish lsothiocyanates;
(7) anionite-exchange resin regeneration
The wash-out that (6) step was extracted goes out the anionite-exchange resin of radish lsothiocyanates, with 4～8% NaOH regenerated from washing of 5～10 times 4～8% dilute hydrochloric acid and 5～10 times.
2. the preparation method of radish red pigment and radish lsothiocyanates is characterized in that concrete method steps is as follows:
(1) preparation of radish red pigment solution
1. the preparation of crude extract
100g " red flesh " radish is added 1000mL distilled water, be heated to 50 ℃ after crushed, and keep 60min, then with the squeezing of 8 layers of gauze till do not have juice and discharge, filtrate is heated to boiling and keeps 10min, then filtrate is carried out diatomite filtration, at last filtrate is cooled to room temperature;
2. the preparation of smart extracting solution
With the 1. radish red pigment crude extract prepared of step, by the molecular weight that dams is after the ultra-filtration membrane of 6000Da carries out ultrafiltration, and the filtrate of reservation is for the radish isothiocyanate content is 0.035%, radish red pigment content is 0.65%, ash content is 0.34% the smart extracting solution of radish red pigment;
(2) preparation of extraction agent
Be 1% HCl according to concentration: secondary octyl phenylium: trioctyl phosphate: the volume ratio of normal heptane thinner is that the ratio of 1:5:5:15 is got the raw materials ready, add secondary octyl phenylium and trioctyl phosphate earlier and mix back adding normal heptane thinner and HCl, stir with agitator again, its stirring velocity is 200r/min, last standing demix 15min, abandon lower floor's water, keep upper strata extraction agent solution;
(3) extraction and the separation of radish lsothiocyanates in the smart extracting solution of radish red pigment
1. extraction
Go on foot in the smart extracting solution of the radish red pigment of preparing (1), add (2) while stirring and go on foot the extraction agent of preparing, and continue to stir 5min, its stirring velocity is 200r/min, and the volume ratio of radish red pigment essence extracting solution and extraction agent is 1:1;
2. separate
Radish red pigment and radish lsothiocyanates extraction mixed solution that (3)-1. step was prepared are transferred in the liquid distributing device, behind the standing demix 35min, extract upper strata radish lsothiocyanates extraction liquid and lower floor radish red pigment extraction liquid for the first time respectively, radish red pigment for the first time in the extraction liquid radish red pigment content be 0.78%, the radish lsothiocyanates for≤0.00063%, ash content is 0.15%;
3. extraction again
Through (3)-1. with 2. step extraction, separates in the lower floor's radish red pigment extraction liquid first time of back extraction, add (2) once more while stirring and go on foot the extraction agent of preparing, and 5min is stirred in continuation, its stirring velocity is 200r/min, and the volume ratio of radish red pigment extraction liquid and extraction agent still is 1:1;
4. separate again
The radish red pigment extraction liquid second time and radish lsothiocyanates extraction mixed solution that (3)-3. step was prepared are transferred in the liquid distributing device, behind the standing demix 35min, extract upper strata radish lsothiocyanates extraction liquid and lower floor radish red pigment extraction liquid for the second time respectively, radish red pigment content is 0.48% to radish red pigment in the extraction liquid for the second time, the radish lsothiocyanates is 0, ash content is≤0.082%;
(4) preparation of radish red pigment powder
Go on foot after twice extracting and separating (3), the lower floor's radish red pigment that extracts is extraction liquid for the second time, by the aperture is that the filter membrane of 0.22 μ m carries out secondary filter, carry out vacuum concentration to 520 nanometer optical density(OD) 〉=2.5 again, at last under-50 ℃, carry out lyophilize, prepare outstanding valency and be 65, the radish isothiocyanate content is 0, ash content is 0.54% radish red pigment lyophilized powder;
(5) regeneration of extraction agent
1. strip and separate
In the upper strata radish lsothiocyanates extraction liquid that after (3) goes on foot through twice extracting and separating, extracts, adding pH value is rare NaOH aqueous solution of 8.5, be warming up to 35 ℃ then, the volume ratio of its radish lsothiocyanates extraction liquid and this solution is 1:1, stirs again, and its stirring velocity is 200r/min, churning time is 20min, then this mixed solution is transferred in the liquid distributing device, carries out standing demix, extract extraction agent and lower floor's radish lsothiocyanates anti-stripping agent after stripping in the upper strata respectively;
2. regeneration
In the extraction agent after stripping in the upper strata of extracting in (5)-1. step, add 1.0% HCl 10mL, stir with the speed of 200r/min, extraction agent volume ratio after 1% HCl that adds and the extraction is 1: 20, standing demix is abandoned lower floor's water then, extracts the upper strata regenerating extracting agent;
(6) preparation of radish lsothiocyanates
In lower floor's radish lsothiocyanates anti-stripping agent of (5)-1. step extraction, add D201 strongly basic anion ion exchange resin, the volume ratio that adds anionite-exchange resin and radish lsothiocyanates anti-stripping agent is 1: 20, speed with 200r/min stirs, with the NaOH wash-out of 0.1mol/L, collect elutriant behind the stirring 20min, to the elutriant of collecting 0.1Mpa steam distillation 40min, collect distillate, use CaCl
2Dehydration, and extract the anionite-exchange resin that wash-out goes out radish radish lsothiocyanates;
(7) anionite-exchange resin regeneration
The wash-out that (6) step was extracted goes out the anionite-exchange resin of radish radish lsothiocyanates, with 8% NaOH regenerated from washing of 5 times 8% dilute hydrochloric acid and 5 times.
3. according to the preparation method of described radish red pigment of claim 1 and radish lsothiocyanates, it is characterized in that concrete method steps is as follows:
(1) preparation of radish red pigment solution
1. the preparation of crude extract
100g " red flesh " radish is added 1200mL distilled water, be heated to 60 ℃ after crushed, and keep 80min, then with the squeezing of 8 layers of gauze till do not have juice and discharge, filtrate is heated to boiling and keeps 15min, then filtrate is carried out diatomite filtration, at last filtrate is cooled to room temperature;
2. the preparation of smart extracting solution
With the 1. radish red pigment crude extract prepared of step, by the molecular weight that dams is after the ultra-filtration membrane of 6000Da carries out ultrafiltration, and the filtrate of reservation is for the radish isothiocyanate content is 0.03%, radish red pigment content is 0.45%, ash content is 0.26% the smart extracting solution of radish red pigment;
(2) preparation of extraction agent
Be 1% HCl according to concentration: secondary octyl phenylium: trioctyl phosphate: the volume ratio of hexanaphthene thinner is that the ratio of 1:5:5:15 is got the raw materials ready, add secondary octyl phenylium and trioctyl phosphate earlier and mix back adding hexanaphthene thinner and HCl, stir with agitator again, its stirring velocity is 300r/min, last static layering 20min, abandon lower floor's water, keep upper strata extraction agent solution;
(3) extraction and the separation of radish lsothiocyanates in the smart extracting solution of radish red pigment
1. extraction
Go on foot in the smart extracting solution of the radish red pigment of preparing (1), add (2) while stirring and go on foot the extraction agent of preparing, and continue to stir 10min, its stirring velocity is 300r/min, and the volume ratio of radish red pigment essence extracting solution and extraction agent is 1:1;
2. separate
Radish red pigment and radish lsothiocyanates extraction mixed solution that (3)-1. step was prepared are transferred in the liquid distributing device, behind the static layering 45min, extract upper strata radish lsothiocyanates extraction liquid and lower floor radish red pigment extraction liquid for the first time respectively, radish red pigment for the first time in the extraction liquid radish red pigment content be 0.55%, the radish lsothiocyanates for≤0.00033%, ash content is 1.5%;
3. extraction again
Through (3)-1. with 2. step extraction, separates in the lower floor's radish red pigment extraction liquid first time of back extraction, add (2) once more while stirring and go on foot the extraction agent of preparing, and 10min is stirred in continuation, its stirring velocity is 300r/min, and the volume ratio of radish red pigment extraction liquid and extraction agent still is 1:1;
4. separate again
The radish red pigment extraction liquid second time and radish lsothiocyanates extraction mixed solution that (3)-3. step was prepared are transferred in the liquid distributing device, behind the static layering 45min, extract upper strata radish lsothiocyanates extraction liquid and lower floor radish red pigment extraction liquid for the second time respectively, radish red pigment content is 0.68% to radish red pigment in the extraction liquid for the second time, the radish lsothiocyanates is 0, ash content is≤0.053%;
(4) preparation of radish red pigment powder
Go on foot after twice extracting and separating (3), the lower floor's radish red pigment that extracts is extraction liquid for the second time, by the aperture is that the filter membrane of 0.22 μ m carries out secondary filter, carrying out vacuum concentration to 520 nanometer optical density(OD) again is 2.5, at last under-50 ℃, carry out lyophilize, prepare outstanding valency and be 65, the radish isothiocyanate content is 0, ash content is 0.34% radish red pigment lyophilized powder;
(5) regeneration of extraction agent
1. strip and separate
In the upper strata radish lsothiocyanates extraction liquid that after (3) goes on foot through twice extracting and separating, extracts, adding pH value is rare NaOH aqueous solution of 10.5, be warming up to 55 ℃ then, the volume ratio of its radish lsothiocyanates extraction liquid and this solution is 1:1, stirs again, and its stirring velocity is 300r/min, churning time is 20min, then this mixed solution is transferred in the liquid distributing device, carries out standing demix, extract extraction agent and lower floor's radish lsothiocyanates anti-stripping agent after stripping in the upper strata respectively;
2. regeneration
In the extraction agent after stripping in the upper strata of extracting in (5)-1. step, add 1.0% HCl 20mL, stir with the speed of 200r/min, extraction agent volume ratio after 1% HCl that adds and the extraction is 1:20, standing demix is abandoned lower floor's water then, extracts the upper strata regenerating extracting agent;
(6) preparation of radish lsothiocyanates
In lower floor's radish lsothiocyanates anti-stripping agent of (5)-1. step extraction, add D201 strongly basic anion ion exchange resin, the volume ratio that adds anionite-exchange resin volume and radish lsothiocyanates anti-stripping agent is 1: 25, speed with 300r/min stirs, with the NaOH wash-out of 0.1mol/L, collect elutriant behind the stirring 20min, to the elutriant of collecting 0.2Mpa steam distillation 30min, collect distillate, use CaCl
2Dehydration, and extract the anionite-exchange resin that wash-out goes out the radish lsothiocyanates;
(7) anionite-exchange resin regeneration
The wash-out that (6) step was extracted goes out the anionite-exchange resin of radish lsothiocyanates, with 4% NaOH regenerated from washing of 10 times 4% dilute hydrochloric acid and 10 times.
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| CN101543284B (en) * | 2009-04-29 | 2012-06-20 | 石勇 | Preparation method of foodstuff toning sauce and foodstuff toning sauce |
| CN102190608A (en) * | 2010-03-12 | 2011-09-21 | 天津市食品研究所有限公司 | Method for extracting mustard oil from green radish peel |
| CN102134402B (en) * | 2011-01-04 | 2014-04-02 | 重庆海巨农业发展有限公司 | Method for preparing and purifying alkylated radish red pigment |
| CN102174617B (en) * | 2011-01-04 | 2013-10-30 | 重庆大学 | Method for synthesizing and purifying glycosylated red radish haematochrome |
| CN102093748B (en) * | 2011-01-17 | 2013-10-23 | 重庆海巨农业发展有限公司 | Method for preparing radish red pigment homopolymer and radish proanthocyanidin from red-core radishes |
| CN102070915B (en) * | 2011-01-18 | 2013-06-05 | 烟台大学 | Radish red deodorizing technology without odor return |
| CN104961667B (en) * | 2015-06-16 | 2017-03-29 | 赣州华汉生物科技有限公司 | A kind of purification process of sulforaphen |
| CN106982856A (en) * | 2016-01-21 | 2017-07-28 | 黄柏园 | Natural bactericidal agent and its preparation method |
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