CN110903677A - Method for simultaneously preparing gardenia yellow pigment and blue pigment - Google Patents
Method for simultaneously preparing gardenia yellow pigment and blue pigment Download PDFInfo
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- CN110903677A CN110903677A CN201911279426.4A CN201911279426A CN110903677A CN 110903677 A CN110903677 A CN 110903677A CN 201911279426 A CN201911279426 A CN 201911279426A CN 110903677 A CN110903677 A CN 110903677A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0096—Purification; Precipitation; Filtration
Abstract
The invention discloses a method for simultaneously preparing gardenia yellow pigment and blue pigment. The method comprises the steps of firstly preparing gardenia yellow pigment by using gardenia powder, then recovering gardenoside from collected waste liquid, and further performing biotransformation to obtain gardenia blue pigment, wherein the obtained two pigments meet respective quality standards. Compared with the prior art, the method has the advantages that the gardenia raw material powder is firstly degreased to obtain the gardenia oil, and the remaining degreased gardenia raw materials of the same batch can be simultaneously prepared to obtain two products of high-purity gardenia yellow pigment and gardenia blue pigment, so that the comprehensive utilization of the effective components of the gardenia raw materials is realized, and the economic benefit of enterprises is greatly improved.
Description
Technical Field
The invention belongs to the technical field of plant pigment extraction, and particularly relates to a preparation method for extracting and preparing yellow pigment from gardenia, simultaneously utilizing all waste liquid generated in the process of preparing the yellow pigment in real time, recovering geniposide from the waste liquid, and preparing the high-purity blue pigment from the geniposide.
Technical Field
The Gardenia jasminoides Ellis is prepared from Gardenia jasminoides Ellis of Rubiaceae by selecting Gardenia jasminoides Ellis, Gardenia jasminoides Ellis leaf, Gardenia jasminoides flower and Gardenia jasminoides root, wherein Gardenia jasminoides is common Chinese medicinal material. Gardenia is produced mainly in Jiangxi, Hunan, Fujian provinces and the like, and is the first medical and edible dual-purpose resource issued by the national Wei-Jian Commission. Gardenia has the effects of diminishing inflammation, relieving fever, stopping bleeding, relieving pain, protecting liver, benefiting gallbladder, reducing blood fat and the like.
The production of gardenia fruits in the current market is seriously more than the demand due to excessive planting, the deep processing of gardenia is carried out to improve the added value of gardenia, and the problem of profit of planting farmers is imminent.
The gardenia yellow pigment is the main effective component in gardenia fruits, and the content can reach more than 15 percent. The gardenia yellow pigment can well imitate the color tone of natural lemon yellow, is bright and natural in coloring, has strong coloring capability and stable property, has the advantages of nutrition, health and the like, and has no toxic or side effect. Is widely applied to coloring foods such as cakes, beverages, ice cream, wine and the like, and the demand is increasing greatly in domestic and international markets.
The gardenia blue pigment is prepared by using gardenoside contained in gardenia as a raw material, and hydrolyzing the gardenoside by using glucosidase, cellulase and the like to remove glucose to obtain genipin. And polymerizing genipin and amino acid, and performing rearrangement reaction to obtain the gardenia blue pigment. The gardenia blue pigment has good stability and strong coloring capability, and is widely used in various beverages, pickling, sauce pickling, candies, puffing, convenience foods and the like. The sale price of the gardenia yellow pigment is 2.5 to 5 times of that of gardenia yellow pigment, and the gardenia yellow pigment is a high-end natural food additive and has huge market demand.
Gardenia yellow pigment as a natural food colorant has numerous advantages. However, when the gardenia yellow pigment is added into food, the natural coexisting impurity components such as gardenoside can make the food green and dark, and the additional value and commercial value of the food are obviously reduced. Only the purity of the gardenia yellow pigment is continuously improved, the content of the geniposide which is a main impurity is reduced, and the OD value ratio (OD) of the geniposide to the yellow pigment is ensured238/OD440) To below 0.4 to effectively solve this problem. In order to effectively reduce the OD value to below 0.4, as described in chinese patent (CN 108794551 a), a large amount of water-elution resin column is required to remove macromolecular water-soluble impurities (protein, polysaccharide) during the actual production of gardenia yellow pigment, and a considerable portion of gardenoside is eluted together during the water-elution. After removing water-soluble impurities, the resin column needs to be eluted by using low-concentration ethanol (5% -25%) to remove specific impurities such as geniposide and chlorogenic acid. And finally eluting the resin column by using high-concentration ethanol to prepare the gardenia yellow pigment products with different purities and color values meeting the requirements. In addition, according to the laboratory measurement, in the process of loading the macroporous adsorption resin before extracting the gardenia yellow pigment, the loading overflow liquid also contains a large amount of gardenoside which is discarded as waste liquid.
In patent CN 10374013B, enzymolysis fructus Gardeniae powder is used as raw material, macroporous resin is used for adsorption and refining, and the refined solution is concentrated and recrystallized to obtain high-purity fructus Gardeniae yellow pigment product. The patent does not utilize the waste liquid containing the geniposide in the process of preparing the yellow pigment by the macroporous resin, the yellow pigment product obtained by the recrystallization method has too low yield and high cost, and all gardenia fruits can only prepare one product of the yellow pigment, so the product cost is very high.
Chinese patent (CN 108794551A) prepares high-purity geniposide from waste liquid of preparing gardenia yellow pigment. According to the technical scheme, gardenia yellow pigment waste liquid is concentrated into extract, the extract is adsorbed by a resin column, then the crude extract is decolorized by adopting activated carbon to obtain a gardenoside crude extract, and a gardenoside crystal is obtained by adding ethyl acetate for crystallization. In the technical scheme, a large amount of energy is consumed for concentrating the gardenia yellow pigment waste liquid; a large amount of dead adsorption can be generated in the decoloring process of the active carbon, so that the recovery rate of the geniposide is reduced; in the crystallization process using ethyl acetate, the crystallization yield and effect are also influenced by a plurality of factors such as the purity of the geniposide in the crude extract of the geniposide.
Chinese patent (CN 104152508B) directly extracts genipin from waste liquid produced in gardenia yellow pigment production, three membranes with different specifications are sequentially used for pretreatment in the technical scheme, so that the problems of very high treatment cost, easy membrane blockage, large consumption of organic solvent and the like are caused.
CN 103614431B adopts gardenia fruit powder to prepare gardenia blue pigment through phase transfer, although the conversion rate of gardenia glycoside and the generation rate of blue pigment product are improved by utilizing the phase transition process, the concentration and purity of the gardenia glycoside are very low because the gardenia glycoside is not purified, and only one kind of blue pigment product can be prepared from all gardenia fruits, so that the product cost is very high.
The prior technical proposal is to prepare either gardenia yellow pigment (such as CN 105482494B) or blue pigment (CN 105624198B), and the preparation of the yellow pigment and the blue pigment is disjointed in the process and has no linkage and correlation, so that only one product of either the yellow pigment or the blue pigment can be obtained in the production process. On one hand, a large amount of waste liquid generated in the process of preparing the yellow pigment increases the treatment cost and the risk of environmental pollution, on the other hand, the intermediate geniposide required for preparing the blue pigment is obtained only by high-cost purchase or preparation, so that the problems of large increase of the preparation cost of the yellow pigment and the blue pigment, waste of gardenia raw material resources and the like are caused, the systematic and large-scale development and utilization of the gardenia raw material and the increase of the added value are seriously restricted, and the healthy development of the gardenia industry is limited.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for simultaneously preparing gardenia yellow pigment and gardenia blue pigment, mainly solves the problems that a large amount of waste liquid generated in the production process of the gardenia yellow pigment is simultaneously reused and the gardenia blue pigment with higher added value is generated, and provides powerful support for reducing the cost, reducing the resource consumption, reducing the environmental pollution and increasing the enterprise benefit in industrial production. The invention is realized by adopting the following technical scheme.
A method for simultaneously preparing gardenia yellow pigment and blue pigment comprises the following steps:
(1) weighing gardenia powder, adding an organic solvent to extract gardenia oil, and drying the gardenia powder after the oil is extracted for later use;
(2) adding the gardenia powder obtained in the step (1) into an ethanol solution, extracting at constant temperature, centrifuging the extracting solution for 3 times, and then mixing; concentrating the filtrate under reduced pressure to recover B, adding deionized water to obtain gardenia yellow pigment solutions with different mass concentrations, and storing at 4 ℃ for later use;
(3) soaking the macroporous adsorbent with 95% ethanol for 24 hr, filtering, washing with ethanol until the eluate is not turbid, and washing with water; soaking in 1.5-3BV hydrochloric acid with the mass fraction of 5% for 0.5-3h, washing with water to be nearly neutral, soaking in 1.5-3BV sodium oxide solution with the mass fraction of 2% for 0.5-3h, washing with water to be nearly neutral, and filtering for later use; respectively feeding the gardenia yellow pigment solution obtained in the step (2) to a macroporous resin column at the flow rate of 1-2BV/h, and collecting overflow liquid as waste liquid 1; stopping the sample loading when the effluent reaches saturation, namely 1/10 with the effluent mass concentration being the sample loading liquid; washing with 3-10BV deionized water to remove impurities, and collecting all water washing liquid as waste liquid 2; washing off a large amount of geniposide and chlorogenic acid by using an ethanol solution with the volume fraction of 10-20% of 3-7BV, and collecting a low-alcohol eluent which is marked as a waste liquid 3; finally, eluting with 50-80% ethanol with 3-7BV volume fraction to obtain gardenia yellow pigment eluent, concentrating and drying to obtain a gardenia yellow pigment product with the color value of more than 250; if the yellow pigment is dissolved, the yellow pigment is applied to a silica gel chromatographic column, and ethyl acetate: methanol: performing gradient elution with water to prepare an ultra-high purity yellow pigment product with the color value of more than 600;
(4) combining the waste liquid 1, the waste liquid 2 and the waste liquid 3 obtained in the step (3), uniformly mixing the mixture, and putting the mixture on macroporous adsorption resin columns with the same column bed and different types in the step (3); or the waste liquid 1, the waste liquid 2 and the waste liquid 3 in the step (3) are immediately put on the macroporous adsorption resin columns with the same column bed and different models as those in the step (3) after being generated. No matter the waste liquid is combined and loaded or sequentially loaded, the adsorption can be ensured not to be saturated, after the loading adsorption is finished, 3-10BV water is used for washing, then 3-7BV ethanol solution with the volume fraction of 10% -20% is used for washing impurities, finally 3-7BV ethanol solution is used for eluting to obtain high-content geniposide solution, and the geniposide powder with the purity of more than 90% is obtained through combination, concentration and drying;
(5) taking the geniposide obtained in the step (4) as a raw material, hydrolyzing the genipin into genipin through enzymolysis, and adding amino acid to synthesize the gardenia blue pigment.
Preferably, the gardenia powder in the step (1) is sieved by a 30-80-mesh sieve, the adopted organic solvent is a solvent suitable for vegetable oil extraction, the extraction material-liquid ratio is 1:5-1:40(g/ml), and the drying method is vacuum drying or normal-pressure hot air drying.
Preferably, the gardenia powder in the step (1) is sieved by a 60-mesh sieve, the adopted organic solvent is a solvent (such as n-hexane or petroleum ether) suitable for vegetable oil extraction, and the extraction material-liquid ratio is 1:20 (g/ml).
Preferably, the alcohol concentration adopted in the step (2) is 30-100%, the material-liquid ratio is 1:5-1:40(g/ml), the extraction temperature is 50-80 ℃, and the stirring time is 1-3 h.
Preferably, the alcohol concentration adopted in the step (2) is 60%, the material-liquid ratio is 1:20(g/ml), the extraction temperature is 80 ℃, and the stirring time is 1.5 h.
Preferably, the model of the macroporous adsorption resin adopted in the step (3) is NKA, LX-21 or LS-300; collecting the waste liquid 1 in the step (3), and directly sampling the waste liquid 2 and the waste liquid 3 without concentration; the concentration of the elution ethanol is 40-100%.
Preferably, the model of the macroporous adsorption resin adopted in the step (4) is HPD200A, and the concentration of the eluting ethanol is 40-100%; and mixing the waste liquid 1, the waste liquid 2 and the waste liquid 3, adding macroporous adsorption resin HPD-200A at the flow rate of 2BV/h, and washing with 6BV of deionized water after saturation.
Preferably, the enzyme adopted in the enzymolysis in the step (5) is β -glucosidase, the amino acid type is taurine, the mass ratio of taurine to geniposide is 5:1-1:5, and the enzymolysis conditions are that the enzymolysis temperature is 30-70 ℃, the pH value is 4-8, and the enzymolysis time is 10-50 h.
Preferably, the mass ratio of the taurine to the geniposide is 1: 1; the enzymolysis conditions are as follows: the enzymolysis temperature is 50 ℃, the pH value is 6, and the enzymolysis time is 20 h.
Compared with the prior art, the invention has the following advantages:
(1) the gardenia raw material powder is firstly degreased to obtain gardenia oil, and the remaining degreased gardenia raw materials of the same batch can be simultaneously prepared to obtain two products of high-purity gardenia yellow pigment and gardenia blue pigment, so that the comprehensive utilization of effective components in the gardenia raw materials is realized, and the economic benefit of enterprises is greatly improved.
(2) The specific macroporous resin obtained by screening is utilized to carry out real-time synchronous treatment on a large amount of waste liquid generated in the process of preparing the gardenia yellow pigment in the first procedure, so that the effective treatment on the waste liquid is realized, the high-added-value and high-purity gardenoside is prepared, and the high-added-value gardenia blue pigment product is prepared by utilizing the gardenoside, so that the waste water discharge and treatment cost is reduced, the waste is changed into valuable, the enterprise production cost is greatly reduced, and the market competitiveness of the product is greatly enhanced.
(3) The process for extracting the gardenia yellow pigment can prepare yellow pigment products with different color values of 250-756.63 and different purities by connecting the macroporous resin column and the silica gel column in series, meet the requirements of different users, simultaneously recycle waste liquid generated in the process of preparing the yellow pigment in real time to obtain the geniposide with the purity of more than 90 percent, and prepare the blue pigment with the color value of more than 160 by utilizing the geniposide.
Drawings
FIG. 1 shows the process flow chart of the simultaneous preparation of gardenia yellow pigment and gardenia blue pigment.
Detailed Description
The technical solution of the present invention is described in detail below, but the scope of the present invention is not limited to the embodiments.
Example 1
Weighing 60g of gardenia powder sieved by a 60-mesh sieve, adding 1200mL of normal hexane, extracting gardenia oil by an automatic Soxhlet extraction method, and drying the gardenia powder after the oil extraction in a vacuum drying oven for later use. Adding the gardenia powder into an ethanol solution with volume fraction of 60%, wherein the material-liquid ratio is 1:20(g/mL), stirring and extracting at constant temperature of 80 ℃ for 1.5h, combining extracting solutions after extracting for 3 times, centrifuging at 4500r/min for 10min, concentrating the filtrate under reduced pressure until no alcohol smell exists, adding deionized water to obtain gardenia yellow pigment solutions with different mass concentrations, and storing at 4 ℃ for later use.
Soaking NKA macroporous adsorbent with 95% ethanol for 24 hr, vacuum filtering, washing with ethanol until the eluate is not turbid, and washing with water until no alcohol smell is detected. Soaking with 2BV hydrochloric acid with the mass fraction of 5% for 2h, washing with water to be nearly neutral, soaking with 2BV sodium oxide solution with the mass fraction of 2% for 2h, washing with water to be nearly neutral, and filtering for later use.
And (3) respectively loading the crude gardenia yellow pigment extract on an NKA resin column at the flow rate of 2BV/h, and collecting effluent (waste liquid 1). Stopping sampling when the effluent is saturated (the mass concentration of the effluent is 1/10 of the sample injection liquid), washing with 5BV of deionized water to remove impurities, and collecting all water washing liquid (waste liquid 2); washing off a large amount of geniposide and chlorogenic acid (waste liquid 3) by using an ethanol solution with the volume fraction of 5BV being 15%, finally eluting by using an ethanol solution with the volume fraction of 3BV being 60% to obtain a gardenia yellow pigment eluent, concentrating and drying in vacuum to obtain a gardenia yellow pigment product with the color value of 252. If the yellow pigment is taken as ethyl acetate: methanol: water 10:1:0.5 and ethyl acetate: methanol: the ultra-high purity yellow pigment product with the color value of 756.63 can be obtained by gradient elution with water of 10:2: 1.
Combining the generated waste liquid 1, the waste liquid 2 and the waste liquid 3, adding macroporous adsorption resin HPD-200A at the flow rate of 2BV/h, washing with 6BV deionized water after saturation, washing with 6BV ethanol solution with the volume fraction of 15%, eluting with 3BV ethanol solution with the volume fraction of 70% to obtain high-content geniposide solution, combining, concentrating and drying to obtain the geniposide powder with the purity of 94.67%.
Weighing 0.2g of the prepared geniposide raw material, adding 1mL of β -glucosidase with 7.7U/mg of enzyme activity and 0.2g of taurine, reacting for 50h at the temperature of 50 ℃ and the pH value of 6.0, and synthesizing the gardenia blue pigment with the color value of 175.
Example 2
Weighing 30g of gardenia powder, sieving the gardenia powder with a 80-mesh sieve, adding 900mL of petroleum ether, extracting gardenia oil by a Soxhlet reflux method, and drying the gardenia powder subjected to oil extraction in vacuum for later use. Adding the degreased gardenia powder into an ethanol solution with the volume fraction of 50%, wherein the material-liquid ratio is 1:40(g/mL), stirring and extracting for 1.0h in a thermostatic water bath at 60 ℃, combining extracting solutions after extracting for 3 times, centrifuging for 10min at 4500r/min, concentrating the filtrate under reduced pressure until no alcohol smell exists, adding deionized water to obtain gardenia yellow pigment solutions with different mass concentrations, and storing at 4 ℃ for later use.
Soaking LX-21 macroporous adsorbent with 95% ethanol for 24 hr, vacuum filtering, washing with ethanol until the eluate is not turbid, and washing with water until no alcohol smell is detected. Soaking with 1.5BV hydrochloric acid with the mass fraction of 5% for 3h, washing with water to be nearly neutral, soaking with 1.5BV sodium oxide solution with the mass fraction of 2% for 3h, washing with water to be nearly neutral, and filtering for later use.
Respectively loading the crude extract of gardenia yellow pigment on an LX-21 resin column at the flow rate of 1.5BV/h, and collecting effluent (waste liquid 1). When the effluent is saturated (the mass concentration of the effluent is 1/10 of the sample injection liquid), stopping sampling, firstly washing with 7BV of deionized water to remove impurities, and collecting all water washing liquid (waste liquid 2); washing off a large amount of geniposide and chlorogenic acid (waste liquid 3) by using an ethanol solution with the volume fraction of 7.5BV of 20 percent, finally eluting by using an ethanol solution with the volume fraction of 5BV of 50 percent to obtain a gardenia yellow pigment eluent, concentrating and drying in vacuum to obtain a gardenia yellow pigment product with the color value of 232. If the yellow pigment is taken as ethyl acetate: methanol: water 10:1:0.5 and ethyl acetate: methanol: the ultra-high purity yellow pigment product with the color value up to 736 can be prepared by gradient elution with water of 10:2: 1.
Mixing the generated waste liquid 1, waste liquid 2 and waste liquid 3, putting the mixture on macroporous adsorption resin HPD-200A, washing the mixture after the mixture is saturated, washing the mixture with 6BV ethanol solution with volume fraction of 15%, finally eluting the mixture with 5BV ethanol solution with volume fraction of 70% to obtain high-content geniposide solution, mixing the obtained product, concentrating and drying the obtained product to obtain the geniposide powder with purity of more than 91.7%.
Taking 1.0g of geniposide as a raw material, adding 5mL of β -glucosidase with 7.7U/mg of enzyme activity and 1.0g of taurine, and reacting for 36h under the conditions of 60 ℃ of reaction temperature and 5.0 of pH value to synthesize the gardenia blue pigment with the color value of 171.
Example 3
Weighing 50g of gardenia powder, sieving the gardenia powder with a 30-mesh sieve, adding 250mL of petroleum ether, extracting gardenia oil by a Soxhlet reflux method, and drying the gardenia powder subjected to oil extraction in vacuum for later use. Adding the degreased gardenia powder into an ethanol solution with the volume fraction of 50%, wherein the material-liquid ratio is 1:5(g/mL), stirring and extracting for 3.0h in a thermostatic water bath at 50 ℃, combining extracting solutions after extracting for 3 times, centrifuging for 10min at 4500r/min, concentrating the filtrate under reduced pressure until no alcohol smell exists, adding deionized water to obtain gardenia yellow pigment solutions with different mass concentrations, and storing at 4 ℃ for later use.
Soaking LS-300 macroporous adsorbent in 95% ethanol for 24 hr, filtering, washing with ethanol until the eluate is not turbid with water, and washing with water until no alcohol smell is produced. Soaking in 3BV hydrochloric acid with a mass fraction of 5% for 0.5h, washing with water to near neutrality, soaking in sodium oxide solution with a mass fraction of 2% for 0.5h, washing with water to near neutrality, and filtering.
The crude gardenia yellow pigment extract is respectively put on an LS-300 resin column at the flow rate of 1.5BV/h, and effluent liquid (waste liquid 1) is collected. Stopping sampling when the effluent is saturated (the mass concentration of the effluent is 1/10 of the sample injection liquid), washing with 3BV of deionized water to remove impurities, and collecting all water washing liquid (waste liquid 2); washing off a large amount of geniposide and chlorogenic acid (waste liquid 3) by using 1BV of ethanol solution with the volume fraction of 20 percent, finally eluting by using 1BV of ethanol solution with the volume fraction of 80 percent to obtain gardenia yellow pigment eluent, concentrating and drying in vacuum to obtain a gardenia yellow pigment product with the color value of 232. If the yellow pigment is taken as ethyl acetate: methanol: water 10:1:0.5 and ethyl acetate: methanol: the ultra-high purity yellow pigment product with the color value of over 600 can be prepared by gradient elution with water of 10:2: 1.
Combining the generated waste liquid 1, the waste liquid 2 and the waste liquid 3, adding macroporous adsorption resin HPD-200A at the flow rate of 1.5BV/h, washing with 5BV water after saturation, washing with 5BV ethanol solution with the volume fraction of 15%, eluting with 5BV ethanol solution with the volume fraction of 45% to obtain high-content geniposide solution, combining, concentrating and drying to obtain the geniposide powder with the purity of more than 92.8%.
Taking 1.0g of geniposide as a raw material, hydrolyzing the geniposide into genipin under the combined action of β -glucosidase and taurine, adding glycine to synthesize the gardenia blue pigment, and reacting for 10 hours at the reaction temperature of 60 ℃ and the pH value of 5.0 to synthesize the gardenia blue pigment with the color value of 161.
Claims (9)
1. A method for simultaneously preparing gardenia yellow pigment and blue pigment is characterized by comprising the following steps:
(1) weighing gardenia powder, adding an organic solvent to extract gardenia oil, and drying the gardenia powder after the oil is extracted for later use;
(2) adding the gardenia powder obtained in the step (1) into an ethanol solution for constant-temperature extraction, carrying out centrifugal separation on the extracting solution for 3 times, and then combining the extracting solutions; concentrating the filtrate under reduced pressure to recover ethanol, adding deionized water to obtain gardenia yellow pigment solutions with different mass concentrations, and storing at 4 ℃ for later use;
(3) soaking the macroporous adsorbent with 95% ethanol for 24 hr, filtering, washing with ethanol until the eluate is not turbid, and washing with water; soaking in 1.5-3BV hydrochloric acid with the mass fraction of 5% for 0.5-3h, washing with water to be nearly neutral, soaking in 1.5-3BV sodium oxide solution with the mass fraction of 2% for 0.5-3h, washing with water to be nearly neutral, and filtering for later use; respectively feeding the gardenia yellow pigment solution obtained in the step (2) to a macroporous resin column at the flow rate of 1-2BV/h, and collecting overflow liquid as waste liquid 1; stopping the sample loading when the effluent reaches saturation, namely 1/10 with the effluent mass concentration being the sample loading liquid; washing with 3-10BV deionized water to remove impurities, and collecting all water washing liquid as waste liquid 2; washing off a large amount of geniposide and chlorogenic acid by using an ethanol solution with the volume fraction of 10-20% of 3-7BV, and collecting a low-alcohol eluent which is marked as a waste liquid 3; finally, eluting with 50-80% ethanol with 3-7BV volume fraction to obtain gardenia yellow pigment eluent, concentrating and drying to obtain a gardenia yellow pigment product with the color value of more than 250; if the yellow pigment is dissolved, the yellow pigment is applied to a silica gel chromatographic column, and ethyl acetate: methanol: performing gradient elution by water to prepare an ultra-high purity yellow pigment product with the color value of more than 600;
(4) combining the waste liquid 1, the waste liquid 2 and the waste liquid 3 obtained in the step (3), uniformly mixing the mixture, and putting the mixture on macroporous adsorption resin columns with the same column bed and different types in the step (3); or immediately putting the waste liquid 1, the waste liquid 2 and the waste liquid 3 in the step (3) on macroporous adsorption resin columns with the same column bed and different models as those in the step (3) after the generation, washing with 3-10BV water after sample loading adsorption is finished, washing impurities with 10-20% ethanol solution with the volume fraction of 3-7BV, eluting with 3-7BV ethanol solution to obtain high-content geniposide solution, combining, concentrating and drying to obtain geniposide powder with the purity of more than 90%;
(5) taking the geniposide obtained in the step (4) as a raw material, hydrolyzing the genipin into genipin through enzymolysis, and adding amino acid to synthesize the gardenia blue pigment.
2. The method for simultaneously preparing gardenia yellow pigment and blue pigment according to claim 1, characterized in that the gardenia powder in the step (1) is sieved by a 30-80 mesh sieve, the adopted organic solvent is a solvent suitable for vegetable oil extraction, the extraction material-liquid ratio is 1:5-1:40(g/ml), and the drying method is vacuum drying or normal-pressure hot air drying.
3. The method for simultaneously preparing gardenia yellow pigment and blue pigment according to claim 2, characterized in that the gardenia powder in the step (1) is sieved by a 60-mesh sieve, the adopted organic solvent is n-hexane or petroleum ether, and the extraction material-liquid ratio is 1:20 (g/ml).
4. The method for simultaneously preparing gardenia yellow pigment and blue pigment according to claim 1, characterized in that the alcohol concentration adopted in the step (2) is 30-100%, the material-liquid ratio is 1:5-1:40(g/ml), the extraction temperature is 50-80 ℃, and the stirring time is 1-3 h.
5. The method for simultaneously preparing gardenia yellow pigment and blue pigment according to claim 4, characterized in that the alcohol concentration adopted in the step (2) is 60%, the material-liquid ratio is 1:20(g/ml), the extraction temperature is 80 ℃, and the stirring time is 1.5 h.
6. The method for simultaneously preparing gardenia yellow pigment and blue pigment according to claim 1, wherein the model of the macroporous adsorption resin adopted in the step (3) is NKA, LX-21 or LS-300; collecting the waste liquid 1 in the step (3), and directly sampling the waste liquid 2 and the waste liquid 3 without concentration; the concentration of the elution ethanol is 40-100%.
7. The method for simultaneously preparing gardenia yellow pigment and blue pigment according to claim 1, characterized in that the model of the macroporous adsorption resin adopted in the step (4) is HPD200A, and the concentration of the eluting ethanol is 40% -100%; and mixing the waste liquid 1, the waste liquid 2 and the waste liquid 3, adding macroporous adsorption resin HPD-200A at the flow rate of 2BV/h, and washing with 6BV of deionized water after saturation.
8. The method for simultaneously preparing the gardenia yellow pigment and the blue pigment according to claim 1, which is characterized in that the enzyme adopted in the enzymolysis in the step (5) is β -glucosidase, the adopted amino acid is taurine, the mass ratio of the taurine to the gardenoside is 5:1-1:5, and the enzymolysis conditions comprise the enzymolysis temperature of 30-70 ℃, the pH value of 4-8 and the enzymolysis time of 10-50 h.
9. The method for simultaneously preparing the gardenia yellow pigment and the blue pigment according to claim 8, wherein the mass ratio of the taurine to the geniposide is 1: 1; the enzymolysis conditions are as follows: the enzymolysis temperature is 50 ℃, the pH value is 6, and the enzymolysis time is 20 h.
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| CN113402460A (en) * | 2021-05-10 | 2021-09-17 | 南京中医药大学 | Gardenia blue pigment with mental disease resistance and preparation method and application thereof |
| CN113817357A (en) * | 2021-09-27 | 2021-12-21 | 武汉淡雅香生物科技有限公司 | Natural pigment water-based ink for cigarette tipping paper and preparation method thereof |
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