CN114716841A - Preparation method of high-color-value gardenia yellow pigment - Google Patents
Preparation method of high-color-value gardenia yellow pigment Download PDFInfo
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- CN114716841A CN114716841A CN202210478463.3A CN202210478463A CN114716841A CN 114716841 A CN114716841 A CN 114716841A CN 202210478463 A CN202210478463 A CN 202210478463A CN 114716841 A CN114716841 A CN 114716841A
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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
- 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
- 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
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Abstract
The invention discloses a preparation method of high-color-value gardenia yellow pigment, which comprises the steps of selecting fresh and mature gardenia fruits, crushing the fruits to obtain the gardenia yellow pigment with the granularity of about 0-2mm, adding cold water with the mass of 10-15 times, leaching for 1-2 days at room temperature, repeating for 2-3 times, filtering impurities in leaching liquor at room temperature by silica gel, and separating byproducts such as colorless gardenoside, chlorogenic acid and the like by adopting a macroporous resin refining method to obtain the high-color-value gardenia yellow pigment. The macroporous resin preferably has high adsorption rate and high resolution rate, such as LSA-10 type macroporous resin, then the pigment solution purified by the macroporous resin is subjected to rotary evaporation by a vacuum rotary evaporator to obtain a concentrated solution, and finally the concentrated solution is subjected to vacuum freeze drying to obtain the gardenia yellow pigment product with high color value. The method has the advantages of low cost, simple and convenient operation and high safety, and the obtained gardenia yellow pigment has less impurities, high color value, lower content of gardenoside and chlorogenic acid, difficult moisture absorption and agglomeration and wider application range.
Description
Technical Field
The invention relates to a refining method of plant pigment, in particular to a refining method of high-color-value gardenia yellow pigment.
Background
The gardenia yellow pigment is a natural water-soluble pigment obtained by extracting, refining and drying mature fruits of gardenia jasminoides ellis of rubiaceae, and the main components of the pigment are crocin and crocin, the pigment has the advantages of strong tinting strength, good safety, high nutritional value and the like, is safe and nontoxic, and meets the national standard GB 2760 plus 2011 national standard for food safety additives. The method is widely applied to industries such as food, medicine, industry and the like, and is widely concerned by people. Internationally, the color value and the OD value are usually used as indexes for measuring the quality of the gardenia yellow pigment, wherein the color value is the absorbance of 1g/100mL gardenia yellow solution at 440nm, and the content of crocin is reacted; OD value is the ratio A of the maximum absorbance (absorption peak at 238 nm) of geniposide in the gardenia yellow pigment to the maximum absorbance (absorption peak at 440 nm) of crocin238/A440Reflecting the content of geniposide, the occurrence of green change can be avoided as long as the OD value is less than 0.4. The gardenia yellow pigment sold by the company at present generally has the defects of low color value, more impurities such as chlorogenic acid, geniposide and the like, easy occurrence of green change and the like. Although there are also gardenia yellow pigments with high color value on the market, the purification process is complicated, and repeated purification is always needed, so that the cost of the pigment product is greatly increased. The macroporous resin, also called full-porous resin, is a cross-linked polymer containing various ion exchange groups, has stable properties and is not easily influenced by the external environment. When the adsorption resin works, the adsorption resin is adsorbed by the huge specific surface of the adsorption resin by virtue of Van der Waals force between the adsorption resin and adsorbed molecules, and then specific adsorbed molecules are eluted by a certain elution solvent according to the adsorption force and the molecular weight of the adsorbed molecules so as to achieve the purposes of separation and purification. The macroporous resin has the advantages of high physical and chemical stability, large specific surface area, large adsorption capacity, good selectivity, high adsorption speed, soft analysis condition, convenient and quick regeneration treatment, long service cycle, suitability for forming closed cycle, great cost saving and the like, and is a popular purification method. But because the different types of macroporous resin have different adsorption capacities on the pigment, the achieved refining effects are different,therefore, the method initially screens out the gardenia yellow pigment with high adsorption rate, high resolution and low A by a static adsorption experiment238/A440And low A328/A440The most preferred macroporous resin. And then dynamically adsorbing the gardenia yellow pigment through an amplification experiment, and obtaining the high-color-value pigment only through one-time purification. In addition, the gardenia yellow pigment extracting solution is often accompanied by jelly-like impurities, which bring serious interference to the refining of the following macroporous resin, not only can prevent the macroporous resin from adsorbing the pigment, but also can cause the blockage of the column. Therefore, pretreatment of the gardenia yellow pigment extract is necessary. In the prior art, filter paper filtration is a common filtration method. Although filter paper filtration is inexpensive and simple to operate, the rate of pigment solution penetration through the filter paper layer is slow and clogging occurs in a short time, requiring filter paper replacement. The membrane separation method is to use a selective permeation membrane as a separation medium and to realize the separation, purification and concentration by utilizing the difference of the permeability of the membrane to each component of the mixture. Common membrane separation methods are microfiltration, ultrafiltration, nanofiltration, reverse osmosis and electrodialysis. The membrane separation method does not need heating, and can retain the bioactivity of natural products. However, the membrane has high cost and small pore size, which is both an advantage and a disadvantage, and is easy to block due to untimely cleaning, and is not easy to clean due to small pore size. The invention adopts a silica gel adsorption method to remove impurities in the gardenia yellow crude body fluid. The method has simple operation and low cost, and can rapidly remove flocculent impurities in the gardenia yellow pigment extracting solution.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the preparation method of the gardenia yellow pigment with high extraction rate, high color value, low energy consumption and low cost.
The invention provides a production method of gardenia yellow pigment with high color value, which comprises the following steps: a) crushing: crushing fresh gardenia fruits to enable the granularity of the fresh gardenia fruits to be 0-2mm, and obtaining gardenia fruit pulp; b) extraction: putting fresh gardenia fruit pulp into an extraction tank, adding cold water with the mass of about 10-15 times of that of the fresh gardenia fruit pulp, leaching for 1-2 days at room temperature, repeating for 2-3 times, and combining extracting solutions; c) pretreatment of an extracting solution: removing flocculent impurities such as pectin by adopting a silica gel adsorption technology at room temperature, and preventing the macroporous resin from being blocked when the macroporous resin is refined at the later stage; d) refining: refining the pigment solution obtained in the step c) by using macroporous resin; e) concentration: concentrating by using a rotary evaporator; f) and (3) drying: and drying the concentrated solution by adopting a vacuum freeze-drying method to obtain a high-color-value water gardenia yellow pigment product.
Wherein, the specific step of pretreating the extracting solution by the silica gel adsorption technology in the step c) is as follows: 10-15g of 200-mesh 300-mesh silica gel powder is put into a Buchner funnel paved with filter paper, and filtration is carried out by adopting a reduced pressure filtration mode.
Wherein, the conditions of reduced pressure filtration are as follows: the pressure is 0.01-0.05 Mpa, the room temperature and the flow rate is 2.5-8.5 m/s.
Wherein, in the step d), 10-20% by volume of ethanol solution with pH of 5-6 and 80-90% by volume of ethanol solution are respectively used as eluent for elution.
Wherein, the ethanol solution with the volume percentage of 10-20% and the pH value of 5-6 is used as the eluent, and the purpose is to elute a part of impurities such as geniposide, chlorogenic acid and the like.
Wherein, ethanol solution with the volume percentage of 80 percent to 90 percent is selected as eluent for resolving and adsorbing the gardenia yellow pigment.
Wherein, the flow rate of the adsorption and desorption in the step d) is controlled to be 2-3 drops per second, and 2-3 column volumes are washed.
Wherein the conditions of the concentration in step e): the rotating speed is 70 r/min, the temperature is 55-65 ℃, and the pressure is-0.1 Mpa.
Wherein, in step f), the drying conditions are: drying at-50 deg.C and vacuum degree of 0.06mbar or less for 24 hr
Drawings
FIG. 1 shows the adsorption and desorption rates (a) of different macroporous resins and the A238/A440 and A328/A440 values (b) of different macroporous resins
FIG. 2 is a diagram of the refined gardenia yellow pigment with high color value
Detailed Description
The invention provides a preparation method of high-color-value gardenia yellow pigment, which comprises the following steps:
a) crushing: crushing fresh gardenia fruits to enable the granularity of the fresh gardenia fruits to be 0-2mm, and obtaining gardenia fruit pulp; b) extraction: putting fresh gardenia fruit pulp into an extraction tank, adding cold water with the mass about 10-15 times that of the fresh gardenia fruit pulp, leaching for 1-2 days at room temperature, repeating for 2-3 times, and combining extracting solutions; c) pretreatment of an extracting solution: removing flocculent impurities such as pectin by adopting a silica gel adsorption technology at room temperature, and preventing the macroporous resin from being blocked when the macroporous resin is refined at the later stage; d) refining: refining the pigment solution obtained in the step c) by using macroporous resin; e) and (3) concentrating: concentrating by using a rotary evaporator, keeping the temperature at 55-65 ℃, and rotating at 70 r/min; f) and (3) drying: and drying the concentrated solution by adopting a vacuum freeze-drying method to obtain a high-color-value gardenia yellow pigment product.
The present invention will be described in detail below by way of examples.
Macroporous resin screening
In order to screen out the optimal resin, 11 kinds of macroporous resin are selected, including LX-60, LX-68M, LX-10G, LSA-10, LX-12, XDA-7, HPD-700, HPD-200A, XDA-6, X-5 and LX-68G type macroporous resin. 1g of each of 11 kinds of dried macroporous resin materials was taken and mixed with 50mL of a water gardenia yellow pigment dilution in a 250mL conical flask with a cap, and the absorbance was measured. Then placing into a shaking table, continuously shaking for 24h at 28 deg.C (120rpm), measuring absorbance of the supernatant pigment, and calculating adsorption rate Ar (%) ═ A0-A1)/A0100% of the total weight. Wherein A is0Absorbance of yellow pigment before adsorption, A1The absorbance of the adsorbed yellow pigment was used. After adsorption equilibrium of LSA-10 type macroporous resin (1g), the pigment remaining on the resin surface was washed with distilled water, mixed with 50ml of ethanol aqueous solution (10%, 30%, 70%, 80%, 90%, 100%) at different concentrations, added to a 250ml Erlenmeyer flask, and the resulting mixture was shaken for 24 hours at 28 ℃ (120rpm) in a shaker to measure the UV spectrophotometric value, and the resolution Dr (%) ═ A was calculated2/(A0-A1) 100% of the total weight. Wherein A is0Absorbance of yellow pigment before adsorption, A1Absorbance of adsorbed yellow pigment, A2To solveAbsorbance of yellow pigment after adsorption. Measuring absorbance of the obtained solution at 238nm (maximum absorption wavelength of geniposide) and 328nm (maximum absorption wavelength of chlorogenic acid), respectively, and calculating A238/A440And A328/A440The value of (c). By comparing the adsorption rate, the resolution and A238/A440And A328/A440The value of (a) is to screen out macroporous resin with better effect.
The results are shown in fig. 1, the LSA-10 type macroporous resin has better refining effect on the gardenia yellow pigment, and can obviously improve the purity of the gardenia yellow pigment. Adsorption rate, resolution ratio, A after shaking table static adsorption238/A440And A328/A44093.77%, 89.66%, 1.15 and 0.87, respectively.
Test example
Selecting 10kg of mature and fresh fructus gardeniae fruits, and crushing the fresh fruits by using a wall breaking machine, wherein the granularity is about 0-2 mm. Adding cold water of 10 times of the pulp, leaching at room temperature for 1d, repeating for 2-3 times, and collecting supernatant. Removing flocculent impurities such as pectin in 100L of the extract by silica gel (200 meshes, 300 meshes, 100g) adsorption and reduced pressure filtration, wherein the reduced pressure filtration is performed under the conditions of pressure of 0.01-0.05 Mpa and flow rate of 2.5-8.5 m/s. And adding the obtained pretreated pigment liquid into 2kg of macroporous resin LSA-10 in batches, controlling the flow rate at 2-3 drops per second, and flushing 2-3 column volumes until the adsorbed pigment liquid cannot detect the absorbance at 440 nm. Eluting a part of geniposide, chlorogenic acid and other impurities by using 10 volume percent ethanol solution with pH of 6 as an eluent, controlling the flow rate at 2-3 drops per second, and washing for 2-3 column volumes until the absorbance of the adsorbed pigment liquid is not detected at 440 nm. Then ethanol solution with the volume percentage of 90 percent is used as eluent for resolving and attaching the gardenia yellow pigment. Concentrating the desorbed liquid to 1/10 of original volume by rotary evaporator, maintaining the temperature at 55-65 deg.C, rotation speed at 70 r/min, and pressure at-0.1 Mpa. Freezing the concentrated solution at-80 deg.C for 12 hr, and vacuum freeze drying at-50 deg.C under vacuum degree of 0.06mbar for 24 hr to obtain fructus Gardeniae pigment powder with high color value (figure 2).
Dissolving 0.1g of water gardenia yellow pigment before and after refining in a 100mL volumetric flask to constant volume, and obtaining the test solution. Measuring the absorbance of the sample at 440nm with a 1cm quartz cuvette by a spectrophotometer, and calculating the color value
Where A is the absorbance at 440nm, m is the mass (g) of the sample, and f is the dilution factor, the results are shown in Table 1.
TABLE 1
| Sample (I) | Color value | A238/A440 | A328/A440 |
| Before refining | 38.74 | 1.15 | 0.87 |
| After refining | 534.47 | 0.20 | 0.19 |
As shown in Table 1, the method for refining water gardenia yellow pigment disclosed by the invention can obviously improve the purity of the water gardenia yellow pigment, and the refined gardenia yellow pigment solution A238/A440Value of 0.20、A328/A440The value is 0.19, A before purification238/A440Value 1.15, A328/A440The value is 0.87, which is reduced by 82.61% and 78.16%, respectively, which indicates that most of the impurities such as geniposide and chlorogenic acid are effectively removed by refining. Meanwhile, the color value of the gardenia yellow pigment powder before and after the purification is measured, the color value after the purification is 534.47, which is 13.80 times higher than that before the purification, namely 38.74. The result shows that the preparation method of the high-color-value water gardenia yellow pigment provided by the invention can obviously improve the color value of the gardenia yellow pigment and achieve the refining effect.
Claims (10)
1. A preparation method of high-color-value gardenia yellow pigment comprises the following steps:
(1) crushing fresh and mature fructus Gardeniae by a wall breaking machine to make its granularity about 0-2 mm;
(2) putting the crushed gardenia fruit pulp into an extraction tank, adding cold water with the mass about 10-15 times that of gardenia fruits, and leaching at room temperature;
(3) pretreating the extracting solution to remove impurities in the extracting solution to obtain a first pigment solution;
(4) refining the first pigment solution through macroporous resin to obtain a second pigment solution, wherein the macroporous resin is LSA-10;
(5) concentrating the second pigment solution by a vacuum rotary evaporator, controlling the vacuum at-0.1 Mpa and the temperature at 55-65 ℃, and ensuring that the yellow pigment is not degraded;
(6) and drying the concentrated solution by adopting a vacuum freeze-drying method to obtain the gardenia yellow pigment product with high color value.
2. The method according to claim 1, wherein in the step (2), leaching is performed 2-3 times for 1-2d each time.
3. The method according to claim 1, wherein in the step (3), the extract is pretreated by silica gel adsorption technique for removing flocculent impurities such as pectin to prevent clogging of the column.
4. The method comprises the following specific steps of pretreating an extracting solution according to the silica gel adsorption technology of claim 3: 10-15g of 200-mesh 300-mesh silica gel powder is put into a Buchner funnel paved with filter paper, and filtration is carried out by adopting a reduced pressure filtration mode.
5. The conditions for reduced pressure filtration according to claim 4: the pressure is 0.01-0.05 Mpa, the room temperature and the flow rate is 2.5-8.5 m/s.
6. The method according to claim 1, wherein in step (4), the flow rate of the adsorption and desorption is controlled to be 2 to 3 drops per second, and 2 to 3 column volumes are washed.
7. The method according to claim 1, wherein in the step (4), 10-20% by volume of ethanol solution with pH of 5-6 and 80-90% by volume of ethanol solution are respectively selected as eluents for elution.
8. The method of claim 6, wherein the ethanol solution with a volume percentage of 10-20% and a pH of 5-6 is used as the eluent to elute a part of impurities such as geniposide and chlorogenic acid; ethanol solution with the volume percentage of 80-90 percent is selected as eluent to analyze and attach the gardenia yellow pigment.
9. The method according to claim 1, wherein in the step (5), the rotation speed of the rotary evaporator is adjusted to 70 rpm, and the temperature is 55-65 ℃.
10. The process according to claim 1, wherein in step (6), drying is carried out at-50 ℃ under a vacuum of 0.06mbar or less for 24 h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082856A (en) * | 2023-01-29 | 2023-05-09 | 北京服装学院 | Plant dye liquor, preparation method and dyeing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807441A (en) * | 2006-02-23 | 2006-07-26 | 江南大学 | Method for producing high purity jasminoidin and high color number gardenia yellow pigment |
| CN101029183A (en) * | 2007-04-03 | 2007-09-05 | 福州大学 | Method for separating and purifying high-tone jasmine flavine from jasmine |
| CN102585545A (en) * | 2011-12-29 | 2012-07-18 | 浙江惠松制药有限公司 | Preparation method for water gardenia flavochrome |
| CN103740130A (en) * | 2014-01-11 | 2014-04-23 | 云南瑞宝生物科技有限公司 | Preparation method of gardenia yellow pigment |
| CN104327133A (en) * | 2014-10-15 | 2015-02-04 | 浙江天露生物科技有限公司 | Gardenia jasminoides effective component comprehensive extraction technology |
| CN112159599A (en) * | 2020-09-22 | 2021-01-01 | 江西丹霞生物科技股份有限公司 | Preparation process of purple sweet potato pigment and product thereof |
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- 2022-05-05 CN CN202210478463.3A patent/CN114716841A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807441A (en) * | 2006-02-23 | 2006-07-26 | 江南大学 | Method for producing high purity jasminoidin and high color number gardenia yellow pigment |
| CN101029183A (en) * | 2007-04-03 | 2007-09-05 | 福州大学 | Method for separating and purifying high-tone jasmine flavine from jasmine |
| CN102585545A (en) * | 2011-12-29 | 2012-07-18 | 浙江惠松制药有限公司 | Preparation method for water gardenia flavochrome |
| CN103740130A (en) * | 2014-01-11 | 2014-04-23 | 云南瑞宝生物科技有限公司 | Preparation method of gardenia yellow pigment |
| CN104327133A (en) * | 2014-10-15 | 2015-02-04 | 浙江天露生物科技有限公司 | Gardenia jasminoides effective component comprehensive extraction technology |
| CN112159599A (en) * | 2020-09-22 | 2021-01-01 | 江西丹霞生物科技股份有限公司 | Preparation process of purple sweet potato pigment and product thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082856A (en) * | 2023-01-29 | 2023-05-09 | 北京服装学院 | Plant dye liquor, preparation method and dyeing method |
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Application publication date: 20220708 |