CN113214081A - Method for flocculating, decoloring and purifying rosmarinic acid by membrane separation - Google Patents
Method for flocculating, decoloring and purifying rosmarinic acid by membrane separation Download PDFInfo
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- CN113214081A CN113214081A CN202110301238.8A CN202110301238A CN113214081A CN 113214081 A CN113214081 A CN 113214081A CN 202110301238 A CN202110301238 A CN 202110301238A CN 113214081 A CN113214081 A CN 113214081A
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- DOUMFZQKYFQNTF-WUTVXBCWSA-N (R)-rosmarinic acid Chemical compound C([C@H](C(=O)O)OC(=O)\C=C\C=1C=C(O)C(O)=CC=1)C1=CC=C(O)C(O)=C1 DOUMFZQKYFQNTF-WUTVXBCWSA-N 0.000 title claims abstract description 146
- ZZAFFYPNLYCDEP-HNNXBMFYSA-N Rosmarinsaeure Natural products OC(=O)[C@H](Cc1cccc(O)c1O)OC(=O)C=Cc2ccc(O)c(O)c2 ZZAFFYPNLYCDEP-HNNXBMFYSA-N 0.000 title claims abstract description 73
- DOUMFZQKYFQNTF-MRXNPFEDSA-N rosemarinic acid Natural products C([C@H](C(=O)O)OC(=O)C=CC=1C=C(O)C(O)=CC=1)C1=CC=C(O)C(O)=C1 DOUMFZQKYFQNTF-MRXNPFEDSA-N 0.000 title claims abstract description 73
- TVHVQJFBWRLYOD-UHFFFAOYSA-N rosmarinic acid Natural products OC(=O)C(Cc1ccc(O)c(O)c1)OC(=Cc2ccc(O)c(O)c2)C=O TVHVQJFBWRLYOD-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000012528 membrane Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 29
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- 230000016615 flocculation Effects 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 16
- 238000004042 decolorization Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 23
- 239000012535 impurity Substances 0.000 claims description 18
- 239000012466 permeate Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000341 volatile oil Substances 0.000 claims description 14
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000012488 sample solution Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000000523 sample Substances 0.000 claims description 7
- 239000000284 extract Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
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- 238000010992 reflux Methods 0.000 claims description 5
- 238000009736 wetting Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
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- 102000004169 proteins and genes Human genes 0.000 description 7
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- IWLBIFVMPLUHLK-UHFFFAOYSA-N azane;formaldehyde Chemical compound N.O=C IWLBIFVMPLUHLK-UHFFFAOYSA-N 0.000 description 5
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- ZIVWELAEVLWTBK-UHFFFAOYSA-N 2-cyanoguanidine;formaldehyde Chemical compound O=C.NC(N)=NC#N ZIVWELAEVLWTBK-UHFFFAOYSA-N 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 102000019197 Superoxide Dismutase Human genes 0.000 description 2
- 108010012715 Superoxide dismutase Proteins 0.000 description 2
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- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
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- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of purifying rosmarinic acid, and particularly relates to a method for purifying rosmarinic acid by using flocculation decoloration and membrane separation technologies. The method takes rosmarinic acid with the content of 5% extracted from rosemary branches and leaves as a raw material, and decolors and purifies the rosmarinic acid by a chemical flocculation method and a membrane separation technology, so that the content of the rosmarinic acid is increased from 5.47% to 11-13%. The invention combines flocculation and membrane separation for purification and decolorization of rosmarinic acid, and can provide reference for enterprises to prepare rosmarinic acid products higher than the food additive (GB 1886.172-2016 national food safety standard). The method has the advantages of simple process and remarkable decolorizing effect, and is favorable for expanding the production scale and market application of the rosmarinic acid product.
Description
Technical Field
The invention relates to the field of preparation and purification of effective components of Chinese herbal medicines, in particular to a method for purifying effective components of rosmarinic acid by flocculation and decoloration and membrane separation.
Background
Natural Rosmarinic acid (Rosmarinic acid) is a secondary metabolite of plant cells, has a molecular formula of C18H16O8 (molecular weight: 360), contains 4 phenolic hydroxyl groups, belongs to natural phenolic acid in classification, has good oxidation resistance which is higher than that of VE, and is a third-generation natural food antioxidant. Although the content of rosmarinic acid as an additive is more than 5 percent specified in the standard of food additives (GB 1886.172-2016 national food safety standard), when the purity of a rosmarinic acid crude extract is about 5 percent, the rosmarinic acid crude extract contains more impurities such as polysaccharide, pigment, macromolecular protein and the like, so that the product is dark in color and easy to be wetted, and the content of rosmarinic acid is reduced along with the standing time, so that the application range of rosmarinic acid is greatly limited. The purification method of rosmarinic acid includes solvent extraction, macroporous resin adsorption, membrane treatment, and crystallization. For example, the invention patent "preparation process of rosmarinic acid by separation and purification with macroporous adsorbent resin" (application publication No. CN101139291) applied by tianjin science and technology university in 2006 uses macroporous adsorbent resin to purify rosmarinic acid. The invention patent of northwest industrial university in 2018, namely a method for separating and purifying superoxide dismutase by using a crystallization method (application publication CN 108486074A), discloses a method for purifying plant extract superoxide dismutase by using a crystallization method. The invention patent of 'an antioxidant rosmarinic acid purification method for cigarettes' (application publication No. CN 102952018A) applied by 2013 of tobacco industry Limited liability company in Hubei is that an extracting solution containing rosmarinic acid firstly passes through an inorganic membrane with the thickness of 30nm, then passes through an organic roll-type membrane with the molecular weight cutoff of 3000, filtrate is concentrated through a reverse osmosis membrane, and a concentrated sample is subjected to purification means such as column chromatography, recrystallization and the like to obtain the rosmarinic acid with higher purity. Chemical flocculation is a solid-liquid separation technique for separating and purifying the effective components of Chinese herbal medicines. The chemical flocculation can remove protein, pectin, pigment, saccharide, etc. from the rosmarinic acid extract to a certain extent. At present, no report related to the purification of rosmarinic acid by chemical flocculation exists in China, but Wang Guo 'application research of technology combining flocculation and membrane separation in impurity removal and purification of traditional Chinese medicines' (D) research proves that the chemical flocculation is feasible in the aspect of separation and purification of natural substances. The method combines chemical flocculation and membrane separation to be applied to purification and decoloration of the rosmarinic acid, lays a foundation for the research work of separation and purification of the rosmarinic acid, and provides reference for enterprises to facilitate expansion of the production scale and market application of rosmarinic acid products.
Disclosure of Invention
The invention aims to provide a method for flocculating, decoloring and purifying rosmarinic acid by membrane separation. The invention has simple process, is designed aiming at the problems that when the crude extract of the rosmarinic acid has the purity of about 5 percent, the rosmarinic acid contains more impurities such as polysaccharide, pigment, macromolecular protein and the like, so that the product has dark color and is easy to be affected with damp, the content can be reduced along with the standing time and the like, can efficiently remove the impurities such as macromolecular polysaccharide, protein, pigment and the like from the crude extract of the rosmarinic acid, extracts the crude product of the rosmarinic acid with high purity, reduces the chroma and is favorable for expanding the market application of the rosmarinic acid.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for flocculating, decoloring and purifying rosmarinic acid by membrane separation is characterized by comprising the following steps:
1) pretreatment of raw materials: cutting stem and leaf of herba Rosmarini officinalis into segments of about 1cm, wetting, adding into an extraction tank, distilling with water vapor for 30min to remove essential oil and hydrolat, wherein the extraction tank is used for removing essential oil and hydrolat;
2) preparing a rosmarinic acid crude product solution: extracting essential oil and pure dew sample by water distillation, refluxing with 45% alcohol at a ratio of material to liquid (mass/volume) of 1:8-10, stirring for 1 hr, separating solid and liquid, mixing filtrates, filtering or centrifuging to remove particulate insoluble substances, and distilling to recover alcohol to obtain rosmarinic acid water solution;
3) the flocculation, decoloration and impurity removal step: distilling to recover alcohol to obtain a rosmarinic acid aqueous solution sample solution, adding 1% dicyandiamide-dicyandiamide formaldehyde flocculant, stirring for flocculation and decolorization, standing for half an hour, centrifuging or filtering, and removing precipitate to obtain a flocculation decolorized impurity-removed sample solution;
4) the membrane treatment step: passing the obtained sample liquid after flocculation, decoloration and impurity removal through a 800nm tubular membrane to remove granular substances, adding a proper amount of water into the concentrated solution for continuous concentration when the permeate passes through 2/3, combining the permeate, filtering the permeate through a roll-type membrane with the molecular weight cutoff of 1000, further removing impurities from the material, removing polysaccharides, small molecular proteins and macromolecular pigment substances, and filtering the permeate through a roll-type membrane with the molecular weight cutoff of 300 to obtain a concentrated solution for later use;
5) the spray drying step comprises: the concentrated solution obtained by membrane treatment is sprayed and dried to obtain the product with the content of 11-13 percent.
6) The preparation method of the dicyandiamide-dicyandiamide formaldehyde flocculating agent comprises the following steps: adding 100mL of 37 percent formaldehyde into a 500mL three-necked bottle provided with a stirrer, a thermometer and a condenser, adding 50-52g of dicyandiamide under stirring, and naturally raising the temperature to about 38 ℃; adding 10g of aluminum chloride (catalyst) at 40 ℃, and reacting for about 30min until the solution becomes clear; controlling the temperature to be about 40 ℃ (the temperature is raised in the reaction process), stirring until the solution is transparent (about 1h), adding 100mL of water, raising the temperature to 65-70 ℃, reacting for 2-2.5h, and observing the viscosity; before cooling, 100mL of water was added and stirred for 30 min.
The method is characterized in that the rosmarinic acid is purified by flocculation decolorization and membrane separation for the first time, relevant process parameters need to be creatively tested and selected according to the physicochemical characteristics of the rosmarinic acid, and the test results are as follows:
1. selection of inorganic and organic flocculant species
Preparing 2mg/mL crude rosmarinic acid extract, selecting 8 different flocculants to treat the crude rosmarinic acid extract, measuring the light absorption value (diluted by 20 times) at 352nm, calculating the decoloring rate of the different flocculants, centrifuging the decoloring solution, rotating and evaporating to dryness, weighing, adding water to dissolve the decoloring solution into 1mg/mL sample solution, and measuring the content, wherein the results are shown in Table 1:
TABLE 1 table of decolorization rates and contents of inorganic and organic flocculants
It can be seen from table 1 that the highest decolorization rate is activated carbon, dicyandiamide formaldehyde-dicyandiamide formaldehyde and dicyandiamide formaldehyde ammonium salt, calcium hypochlorite and activated clay, and the content of activated clay, dicyandiamide formaldehyde-dicyandiamide formaldehyde and dicyandiamide formaldehyde ammonium salt is high.
2. Flocculant addition selection
The addition amounts of activated clay, dicyandiamide formaldehyde-dicyandiamide formaldehyde and dicyandiamide formaldehyde ammonium salt were optimized, and the results are shown in the following table:
TABLE 2 influence of flocculant addition on color and content
The addition of the flocculant influences the decoloring rate and the content, and the dicyandiamide formaldehyde ammonium salt flocculant and the dicyandiamide-dicyandiamide formaldehyde flocculant are preferably added in an amount of 0.25mL (1%) and activated clay in an amount of 4%.
3. Optimized decoloring process for orthogonal test
Design L9(34) Three-factor three-level orthogonal table of (A) flocculant types1Dicyandiamide formaldehyde flocculant, A2Dicyandiamide formaldehyde ammonium salt flocculant and A3Activated clay and B1＝0.5％，B2＝1％，B11.5%,) and C flocculation stirring speed (C)1＝80rpm，C2＝100rpm，C3120rpm) on rosmarinic acid decolorization rate and content, the results are given in the following table:
TABLE 3 Quadrature experimental results and analysis of flocculant decolorization
Note: integrated index (%) × decolorization ratio (%) × 0.3+ content (%) × 0.7.
The results of the cross-over test were analyzed for variance, and the results were as follows:
TABLE 4 orthogonal ANOVA Table
The factor of flocculant A with a remarkable level for the decolorization rate is known by variance analysis. The factor of addition B was significant in the effect of the content. The comprehensive index A factor and the comprehensive index B factor reach obvious levels and are controlled to be at the optimal level, and the comprehensive index C factor is not obvious and can be at any level. The optimum level combination selected is A1B2C1Namely: the flocculating agent is dicyandiamide-dicyandiamide formaldehyde, the adding amount is 1 percent, and the stirring speed is 80 rpm.
4. Experiment of Membrane separation treatment
And (3) selecting roll-type membranes with three molecular weights of 10000Da, 1000Da and 300Da to filter the supernatant obtained by pretreatment (flocculation), wherein the 10000Da intercepts large-particle substances, and the 1000Da permeate passes through the 300Da membrane to be mainly dehydrated and removed with low-molecular-weight substances. The rosmarinic acid content was 11.24%, thus determining the optimal molecular weight of 1000Da for roll-film purified rosmarinic acid.
The method comprises the following steps of selecting dicyandiamide-formaldehyde flocculant to treat a batch of stock solution of extracting solution, dividing the stock solution into five parts, treating the five parts by a roll-type membrane, concentrating the treated solution to obtain a product containing 10% of solid matters, performing spray drying to obtain a rosmarinic acid product, and performing liquid chromatography detection on a certain sample, wherein the results are as follows:
TABLE 5 results after crude flocculation Membrane treatment
The data in Table 5 show that the content of the membrane is improved from 5.47% to 11-13% after the treatment of dicyandiamide formaldehyde flocculant and two types of spiral membranes with 10000 molecular weight and 1000 molecular weight.
Compared with the prior art, the invention has the following advantages:
1) the process is simple, the decolorizing effect is obvious, rosmarinic acid products higher than the food additive (GB 1886.172-2016 national food safety standard) standard can be efficiently prepared from rosemary stems and leaves, and the production scale and market application of rosmarinic acid can be expanded.
2) Aiming at the fact that when the purity of a rosmarinic acid crude extract is about 5%, the rosmarinic acid crude extract contains more impurities such as polysaccharide, pigment, macromolecular protein and the like, so that the product is dark in color and easy to wet, and the content of the rosmarinic acid crude extract is reduced along with the standing time, so that the application range of the rosmarinic acid is greatly limited. Flocculation is a solid-liquid separation technique for separating and purifying the effective components of Chinese herbal medicines. The chemical flocculation can remove protein, pectin, pigment, saccharide, etc. from the rosmarinic acid extract to a certain extent. At present, no report related to the purification of rosmarinic acid by chemical flocculation exists in China, and the chemical flocculation and membrane separation are combined and applied to the purification and decoloration of rosmarinic acid to obtain higher content of rosmarinic acid.
Drawings
FIG. 1 is a schematic view of the process of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
1. Removing soil from 1000 g of naturally dried rosemary stems and leaves, cutting into 1-2cm small segments, mixing, wetting, placing into a 20L extraction tank, introducing steam for distillation, starting an essential oil hydrosol condenser, distilling for 30min, evaporating essential oil and hydrosol, and collecting the sample from the extraction tank;
2) adding 8000ml of 45% alcohol into the extraction tank (removing essential oil and pure dew) at a ratio of 1:8 (mass/volume), opening a steam generator, refluxing, stirring, extracting for 1 hr, and filtering with 4 layers of gauze. Obtaining 5000ml of filtrate, adding 5000ml of 45% alcohol into the materials, extracting once, mixing the filtrates, 8000ml of filtrate, filtering or centrifuging to remove granular insoluble substances, and recovering alcohol by flash evaporation to obtain 5000ml of rosmarinic acid aqueous solution.
3) Adding 1% dicyandiamide-dicyandiamide formaldehyde flocculant (50ml) into rosmarinic acid aqueous solution, stirring for flocculation and decolorization, standing for half an hour, centrifuging or filtering, and removing precipitate to obtain 4000ml of flocculation, decolorization and impurity removal sample solution; preparing the dicyandiamide-dicyandiamide formaldehyde flocculating agent: adding 100mL of 37% formaldehyde into a 500mL three-necked bottle provided with a stirrer, a thermometer and a condenser, adding 50-52g of dicyandiamide under stirring, and naturally raising the temperature to about 38 ℃; adding 10g of aluminum chloride catalyst at 40 ℃, and reacting for about 30min until the solution becomes clear; controlling the temperature to be about 40 ℃, heating up in the reaction process, stirring until the solution is transparent, adding 100mL of water for about 1h, heating up to 65-70 ℃, reacting for 2-2.5h, and observing the viscosity; before cooling, 100mL of water was added and stirred for 30 min.
4) Passing the sample solution after flocculation, decoloration and impurity removal through a 800nm tubular membrane (ceramic membrane), removing particulate matters, when a permeate passes through 2/3 (2700ml), adding a proper amount of water (800ml) into the concentrated solution for continuous concentration, combining the permeate and filtering through a roll-type membrane with the molecular weight cut-off of 1000, further removing impurities from the materials, and filtering 3000ml of the permeate through a roll-type membrane with the molecular weight cut-off of 300 to obtain 800 plus 1000ml of concentrated solution;
5) 1000ml of concentrated solution 800-.
Example 2
1. Taking 800 g of naturally dried rosemary stems and leaves, removing soil, cutting into 1-2cm small sections, mixing, wetting, putting into a 20L extraction tank, introducing steam for distillation, starting an essential oil hydrosol condenser, distilling for 30min, evaporating essential oil and hydrosol, and taking a sample from which the essential oil and the hydrosol are removed in the extraction tank;
2) adding 8000ml of 45-65% alcohol into an extraction tank (removing essential oil and pure dew samples) according to a material-liquid ratio (mass/volume ratio) of 1:10, opening a steam generator, refluxing, stirring and extracting for 1 hour, and filtering by 4 layers of gauze. Obtaining 5000ml of filtrate, adding 5000ml of 45-65% alcohol into the materials, performing extraction once, combining the filtrates, 8000ml of filtrate, filtering or centrifuging to remove granular insoluble substances, and performing flash evaporation to recover alcohol to obtain 4000ml of rosmarinic acid aqueous solution.
3) Adding 1% dicyandiamide-dicyandiamide formaldehyde flocculant (40ml) into rosmarinic acid aqueous solution, stirring for flocculation and decolorization, standing for half an hour, centrifuging or filtering, and removing precipitate to obtain 3000ml of flocculation, decolorization and impurity removal sample solution; preparing the dicyandiamide-dicyandiamide formaldehyde flocculating agent: adding 100mL of 37% formaldehyde into a 500mL three-necked bottle provided with a stirrer, a thermometer and a condenser, adding 50-52g of dicyandiamide under stirring, and naturally raising the temperature to about 38 ℃; adding 10g of aluminum chloride catalyst at 40 ℃, and reacting for about 30min until the solution becomes clear; controlling the temperature to be about 40 ℃, heating up in the reaction process, stirring until the solution is transparent, adding 100mL of water for about 1h, heating up to 65-70 ℃, reacting for 2-2.5h, and observing the viscosity; before cooling, 100mL of water was added and stirred for 30 min.
4) Passing the sample solution after flocculation, decoloration and impurity removal through a 800nm tubular membrane (ceramic membrane), removing particulate matters, adding a proper amount of water (500ml) into the concentrated solution to continue concentration when the permeate solution permeates 2/3 (2000ml), combining the permeate solution, filtering through a roll-type membrane with the molecular weight cut-off of 1000, further removing impurities from the materials, and filtering 2300ml of the permeate solution through a roll-type membrane with the molecular weight cut-off of 300 to obtain 400 ml of the concentrated solution;
5) 400 ml of concentrated solution is sprayed and dried to obtain 80 g of product with the content of 10 to 11 percent.
Claims (7)
1. The method for flocculating, decoloring and purifying rosmarinic acid by membrane separation is characterized by comprising the following steps:
1) pretreatment of raw materials: cutting stem and leaf of herba Rosmarini officinalis into segments of about 1cm, wetting, and distilling with water vapor to obtain essential oil and hydrolat;
2) preparing a crude rosmarinic acid extract: adding 45% alcohol into an extraction tank according to the material-liquid ratio of 1:8-10 in the step 1), performing reflux extraction for 1h, filtering, and distilling to recover alcohol to obtain a rosmarinic acid aqueous solution;
3) flocculation, decoloration and impurity removal: adding 1% dicyandiamide-dicyandiamide formaldehyde flocculant into the rosmarinic acid aqueous solution obtained in the step 2) for decoloring, flocculating and filtering, and removing precipitates to obtain a sample solution after flocculating, decoloring and impurity removal;
4) film treatment: filtering the sample liquid obtained in the step 3) through a 800nm tubular membrane, filtering the permeate through a roll-type membrane with the molecular weight cut-off of 1000, and filtering the permeate through a roll-type membrane with the molecular weight cut-off of 300 to obtain a concentrated solution for later use;
5) spray drying: and 4) spray-drying the concentrated solution obtained in the step 4) to obtain the product.
2. The method for flocculation decolorizing and membrane separation and purification of rosmarinic acid according to claim 1, wherein the raw material pretreatment step is as follows: cutting stem and leaf of herba Rosmarini officinalis into segments of about 1cm, wetting, adding into an extraction tank, distilling with water vapor for 30min to remove essential oil and hydrolat, wherein the extraction tank is used for removing essential oil and hydrolat.
3. The method for flocculation decoloring and membrane separation and purification of rosmarinic acid as claimed in claim 1, wherein the extraction tank is filled with 45% alcohol according to the material-liquid ratio of 1:8-10 to remove essential oil and pure dew, reflux extraction is carried out for 1h, particulate insoluble substances are removed by filtration or centrifugation, and alcohol is recovered by distillation to obtain the rosmarinic acid aqueous solution.
4. The method for flocculating, decolorizing and purifying rosmarinic acid by membrane separation according to claim 1, wherein the flocculating, decolorizing and decontaminating step comprises: adding 1% dicyandiamide-dicyandiamide formaldehyde flocculant into the obtained rosmarinic acid aqueous solution sample solution obtained by distilling and recovering alcohol, stirring for flocculation and decolorization, standing for half an hour, centrifuging or filtering, and removing precipitate to obtain a flocculation, decolorization and impurity removal sample solution.
5. The method for flocculation decoloring and membrane separation and purification of rosmarinic acid as claimed in claim 1, wherein the membrane treatment step comprises: and (3) passing the obtained sample liquid after flocculation, decoloration and impurity removal through a 800nm tubular membrane, adding a proper amount of water into the concentrated solution for continuous concentration when the permeate passes through 2/3, combining the permeate, filtering the permeate through a roll-type membrane with the molecular weight cutoff of 1000, and filtering the permeate through a roll-type membrane with the molecular weight cutoff of 300 to obtain a concentrated solution for later use.
6. The method for flocculating, decolorizing and purifying rosmarinic acid by membrane separation according to claim 1, wherein the spray drying step comprises spray drying the concentrated solution obtained by membrane treatment to obtain 11% -13% product.
7. The method for flocculating and decolorizing and for purifying rosmarinic acid by membrane separation according to claim 1, characterized in that said dicyandiamide-dicyandiamide formaldehyde flocculant is prepared by: adding 100mL of 37% formaldehyde into a 500mL three-necked bottle provided with a stirrer, a thermometer and a condenser, adding 50-52g of dicyandiamide under stirring, and naturally raising the temperature to about 38 ℃; adding 10g of aluminum chloride catalyst at 40 ℃, and reacting for about 30min until the solution becomes clear; controlling the temperature to be about 40 ℃, heating up in the reaction process, stirring until the solution is transparent, adding 100mL of water for about 1h, heating up to 65-70 ℃, reacting for 2-2.5h, and observing the viscosity; before cooling, 100mL of water was added and stirred for 30 min.
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