阅读说明：本技术 一种新型黑胡萝卜色素精制方法 (Novel black carrot pigment refining method ) 是由 刘素华 文雁君 李林正 金子恒 潘天义 于 2020-06-22 设计创作，主要内容包括：本发明公开了一种新型黑胡萝卜色素精制方法,将黑胡萝卜粉碎后,压榨,过滤,然后向黑胡萝卜残渣中添加无机盐溶液和亲水性低分子有机物,搅拌均匀,静置分相,花青素被萃取分到上相,将静置液上相进行减压浓缩,得到黑胡萝卜提取液。将所得的黑胡萝卜提取液用大孔吸附树脂进行吸附,然后进行减压浓缩,得到黑胡萝卜浓缩液进行喷雾干燥,得到黑胡萝卜色素粉末,其色价在130～150之间。本发明方法所需的有机溶剂较少,分离较快,无需加热,采用双水相萃取结合大孔吸附树脂技术,能在一定程度上缩短时间,提高产品的纯度,同时大孔吸附树脂的再生技术适合于大生产,能够很大程度上降低成本,提高有效成分的含量。(The invention discloses a novel black carrot pigment refining method, which comprises the steps of crushing black carrots, squeezing, filtering, adding an inorganic salt solution and a hydrophilic low-molecular organic matter into black carrot residues, uniformly stirring, standing for phase splitting, extracting anthocyanin to obtain an upper phase, and concentrating the upper phase of the standing liquid under reduced pressure to obtain a black carrot extracting solution. And adsorbing the obtained black carrot extract by using macroporous adsorption resin, then carrying out reduced pressure concentration to obtain a black carrot concentrated solution, and carrying out spray drying to obtain black carrot pigment powder, wherein the color value of the black carrot pigment powder is 130-150. The method of the invention needs less organic solvent, has quick separation, does not need heating, adopts the technology of combining aqueous two-phase extraction with macroporous adsorption resin, can shorten the time to a certain extent and improve the purity of the product, and simultaneously, the regeneration technology of the macroporous adsorption resin is suitable for large-scale production, can reduce the cost to a great extent and improve the content of effective components.)

1. A novel method for refining black carrot pigment is characterized by comprising the following steps:

crushing black carrots, squeezing, filtering, adding an inorganic salt solution and a hydrophilic low-molecular organic substance into black carrot residues, extracting, and concentrating a standing liquid phase under reduced pressure to obtain a black carrot extracting solution; adsorbing the obtained black carrot extract by using macroporous adsorption resin to obtain a black carrot refined solution; concentrating the refined black carrot solution to obtain a concentrated black carrot solution; and drying the black carrot concentrated solution to obtain black carrot pigment powder.

2. The method for refining black carrot pigment according to claim 1, comprising the following steps:

(1) pre-treatment: and cleaning fresh black carrots for later use.

(2) Crushing black carrots, squeezing, filtering, adding an inorganic salt solution and a hydrophilic low-molecular organic substance into black carrot residues, wherein the material-liquid ratio is 1: 5-1: 10, the extraction temperature is 20-30 ℃, the mass percent of the inorganic salt is 15-25%, the mass fraction of the added hydrophilic low-molecular organic substance in the whole double-aqueous-phase system is 25-35%, uniformly stirring, standing for 3-5 h for phase separation, extracting and separating anthocyanin into an upper phase, and separating the rest into a lower phase or a phase between the two phases;

(3) concentrating the standing liquid phase under reduced pressure, and recovering ethanol to obtain black carrot extract;

(4) diluting the obtained black carrot extract, adsorbing by using macroporous adsorption resin, washing a column by using water, and desorbing the black carotene by using ethanol with a certain concentration to obtain a black carrot refined solution;

(5) finely filtering the refined black carrot solution, concentrating the refined black carrot solution by using a nanofiltration membrane, and then concentrating the refined black carrot solution under reduced pressure to obtain a concentrated black carrot solution;

(6) and (3) carrying out spray drying on the black carrot concentrated solution to obtain black carrot pigment powder.

3. The novel refining method of black carrot pigment according to claim 2, characterized in that in the step (2), black carrot is crushed, squeezed and then filtered by a plate and frame filter; the inorganic salt used in the aqueous two-phase system is ammonium sulfate, and the hydrophilic low-molecular organic matter used is absolute ethyl alcohol.

4. The novel refining method of black carrot pigment according to claim 2, characterized in that in the step (4), the macroporous adsorption resin used is LS-300B Shaanxi blue Special resin Co., Ltd, and the adsorption is dynamic adsorption.

5. The method for refining black carrot pigment according to claim 2, wherein in the step (4), 80% ethanol is used for elution.

6. The method for refining black carrot pigment according to claim 2, wherein in the step (5), the black carrot pigment is concentrated to a solid content of 30-40%.

7. The method for refining black carrot pigment according to claim 2, wherein in the step (6), the spray drying temperature is 185-200 ℃ at the inlet and 85-100 ℃ at the outlet.

8. The method for refining black carrot pigment according to any one of claims 1-7, wherein the prepared black carrot pigment powder has a color value of 130-150 and an anthocyanin content of 25-30%.

9. The novel refining method of black carrot pigment according to claim 2, characterized in that in the step (2), black carrot is crushed, squeezed and then filtered by a plate and frame filter; the inorganic salt used in the aqueous two-phase system is ammonium sulfate, and the hydrophilic low-molecular organic matter used is absolute ethyl alcohol; in the step (4), the used macroporous adsorption resin is LS-300B Shaanxi blue deep special resin Co., Ltd, the adsorption is dynamic adsorption, and the elution is carried out by using 80% ethanol for desorption; in the step (5), the mixture is concentrated until the solid content is 30-40%; in the step (6), the inlet temperature of spray drying is 195 ℃ and the outlet temperature is 100 ℃;

the prepared black carrot pigment powder has a color value of 130-150 and an anthocyanin content of 25-30%.

10. The method for refining black carrot pigment according to claim 1 or 2, comprising the steps of:

(1) cleaning fresh black carrots for later use;

(2) crushing clean black carrots, squeezing and filtering to obtain two parts, wherein one part is black carrot extract and the other part is black carrot residue; adding 30% of absolute ethyl alcohol and 20% of ammonium sulfate into the black carrot residue, extracting at 25 ℃, uniformly stirring the black carrot residue and the aqueous two-phase extract in a material-liquid ratio of 1:5, and standing for 3 hours;

(3) concentrating the standing liquid phase under reduced pressure, and recovering ethanol to obtain black carrot extract;

(4) diluting the obtained black carrot extract, refining with LS-300B macroporous adsorbent resin, washing the column with water, and desorbing black carotene with 80% ethanol to obtain black carrot refined solution;

(5) finely filtering the refined black carrot liquid, concentrating the refined black carrot liquid by using a nanofiltration membrane until the content of solid matters is 30-40%, and then carrying out reduced pressure concentration to obtain a concentrated black carrot liquid;

(6) spray drying the collected black carrot concentrated solution at inlet temperature of 195 deg.C and outlet temperature of 100 deg.C to obtain black carrot pigment powder;

or:

(1) cleaning fresh black carrots for later use;

(2) pulverizing clean black carrot, squeezing, and filtering to obtain two parts, one part is black carrot extract, and the other part is black carrot residue. Adding 25% of absolute ethyl alcohol and 20% of ammonium sulfate into the black carrot residue, extracting at the temperature of 30 ℃, enabling the material-liquid ratio of the black carrot residue to the aqueous two-phase extraction liquid to be 1:5, uniformly stirring, and standing for 3 hours;

(3) concentrating the standing liquid phase under reduced pressure, and recovering ethanol to obtain black carrot extract;

(4) diluting the obtained black carrot extract, refining with LS-300B macroporous adsorbent resin, washing the column with water, and desorbing black carotene with 80% ethanol to obtain black carrot refined solution;

(5) finely filtering the refined black carrot liquid, concentrating the refined black carrot liquid by using a nanofiltration membrane, and then concentrating the refined black carrot liquid under reduced pressure until the content of solid matters is 30-40% to obtain a concentrated black carrot liquid;

(6) spray drying the collected black carrot concentrated solution at inlet temperature of 195 ℃ and outlet temperature of 85 ℃ to obtain black carrot pigment powder;

or:

(1) cleaning fresh black carrots for later use;

(2) crushing clean black carrots, squeezing and filtering to obtain two parts, wherein one part is black carrot extract and the other part is black carrot residue; adding 30% of absolute ethyl alcohol and 25% of ammonium sulfate into the black carrot residue, extracting at 25 ℃, uniformly stirring the black carrot residue and the aqueous two-phase extract in a material-liquid ratio of 1:5, and standing for 3 hours;

(3) concentrating the standing liquid phase under reduced pressure, and recovering ethanol to obtain black carrot extract;

(4) diluting the obtained black carrot extract, refining with LS-300B macroporous adsorbent resin, washing the column with water, and desorbing black carotene with 80% ethanol to obtain black carrot refined solution;

(5) finely filtering the refined black carrot liquid, concentrating the refined black carrot liquid by using a nanofiltration membrane, and then concentrating the refined black carrot liquid under reduced pressure until the content of solid matters is 30-40% to obtain a concentrated black carrot liquid;

(6) and (3) carrying out spray drying on the collected black carrot concentrated solution, wherein the inlet temperature is 200 ℃, and the outlet temperature is 95 ℃, so as to obtain black carrot pigment powder.

Technical Field

The invention belongs to the field of natural organic chemistry, relates to a novel black carrot pigment refining method, and particularly relates to a method for purifying black carrot pigment by using aqueous two-phase extraction and macroporous adsorption resin.

Background

Black carrot (Daucus carota ssp. Sativus var. atrorubens Alef.) is originated from Turkey, Afghanistan, Egyptian, India and far east countries, has been planted for more than 3000 years, and begins to be planted in China in recent years, but the planting area is small, the yield is not high, and the application of the black carrot is limited. The black carrot belongs to a plant with semi-cold resistance, preference for cold climate and long sunshine, is suitable for growing at a proper temperature of 15-25 ℃, has good development of fleshy roots at a temperature of 18-20 ℃, and is suitable for cold season cultivation in spring and autumn. Sowing autumn carrots in 7-8 months generally, and harvesting in 11-12 months; the spring carrots are generally sown in 2-3 months and harvested in 5-7 months, and the sowing can be carried out in advance to 1 month in the protected field cultivation; the cultivation can be carried out in summer in northern areas or in high mountains with low temperature.

The black carrot is rich in carotene, the black carrot root contains alpha, beta (most of the carotenoid is hidden in the outer skin), gamma, -carotene, tomato hydrocarbon, hexahydrotomato hydrocarbon and other carotenoids, and the carotene treats night blindness, protects respiratory tract and promotes the growth of children. Black carrot contains a large amount of anthocyanins, which is measured to be 28 times more than other carrots, and it also contains more vitamins (e.g. B1, B2, B3, B5, etc.) and minerals such as calcium, phosphorus and iron. The saccharide may be starch, cellulose, etc.

At present, black carrot has extremely high research value and application prospect as a precious anthocyanin extract which is not developed completely. However, there are few reports on black carrots in foreign and domestic literature. The extraction process of black carrots is researched in China mostly, and most of the extraction methods adopting water or organic solvents have the defects of relatively low extraction rate, long extraction time and the like, so that the method for purifying the black carrots by adopting the two-aqueous-phase extraction macroporous adsorption resin is provided.

Disclosure of Invention

In order to achieve the purpose, the technical scheme adopted by the invention is as follows: crushing black carrots, squeezing, filtering, adding an inorganic salt solution and a hydrophilic low-molecular organic substance into black carrot residues, extracting, and concentrating a standing liquid phase under reduced pressure to obtain a black carrot extracting solution; adsorbing the obtained black carrot extract by using macroporous adsorption resin to obtain a black carrot refined solution; concentrating the refined black carrot solution to obtain a concentrated black carrot solution; and drying the black carrot concentrated solution to obtain black carrot pigment powder.

The invention provides a novel method for refining black carrot pigment, which preferably comprises the following steps:

(1) pre-treatment: and cleaning fresh black carrots for later use.

(2) Crushing black carrots, squeezing, filtering, adding an inorganic salt solution and a hydrophilic low-molecular organic substance into black carrot residues, wherein the material-liquid ratio is 1: 5-1: 10, the extraction temperature is 20-30 ℃, the mass percent of the inorganic salt is 15-25%, the mass fraction of the added hydrophilic low-molecular organic substance in the whole double-aqueous-phase system is 25-35%, uniformly stirring, standing for 3-5 h for phase separation, extracting and separating anthocyanin into an upper phase, and separating the rest into a lower phase or a phase between the two phases;

(3) concentrating the standing liquid phase under reduced pressure, and recovering ethanol to obtain black carrot extract;

(4) diluting the obtained black carrot extract, adsorbing by using macroporous adsorption resin, washing a column by using water, and desorbing the black carotene by using ethanol with a certain concentration to obtain a black carrot refined solution;

(5) finely filtering the refined black carrot solution, concentrating the refined black carrot solution by using a nanofiltration membrane, and then concentrating the refined black carrot solution under reduced pressure to obtain a concentrated black carrot solution;

(6) and (3) carrying out spray drying on the black carrot concentrated solution to obtain black carrot pigment powder.

More preferably, in the step (2), the black carrots are crushed, squeezed and filtered by a plate and frame filter; the inorganic salt used in the aqueous two-phase system is ammonium sulfate, and the hydrophilic low-molecular organic matter used is absolute ethyl alcohol.

In the step (4), the used macroporous adsorption resin is LS-300B Shaanxi blue deep special resin company, and the adsorption is dynamic adsorption; elution was performed with 80% ethanol.

In the step (5), the mixture is concentrated until the solid content is 30-40%.

In the step (6), the inlet temperature of spray drying is 185-200 ℃, and the outlet temperature is 85-100 ℃.

More preferably, in the step (2), the black carrots are crushed, squeezed and filtered by a plate and frame filter; the inorganic salt used in the aqueous two-phase system is ammonium sulfate, and the hydrophilic low-molecular organic matter used is absolute ethyl alcohol; in the step (4), the used macroporous adsorption resin is LS-300B Shaanxi blue deep special resin Co., Ltd, the adsorption is dynamic adsorption, and the elution is carried out by using 80% ethanol for desorption; in the step (5), the mixture is concentrated until the solid content is 30-40%; in the step (6), the inlet temperature of spray drying is 195 ℃ and the outlet temperature is 100 ℃.

The black carrot pigment powder prepared by the novel black carrot pigment refining method has the color value of 130-150, and the content of the effective component anthocyanin can reach 25-30%.

Compared with the prior art, the invention has the following remarkable progress: the color value of the black carrot pigment prepared by the method can reach 100-130, and the content of the effective component anthocyanin can reach 25-30%. The preparation method of the invention needs less organic solvent, has quick separation, does not need heating, can be carried out at ambient temperature, and the obtained extract has small volume and high concentration, and is beneficial to the purification of the subsequent part. The invention adopts the technology of combining aqueous two-phase extraction with macroporous adsorption resin, can shorten the time to a certain extent and improve the purity of the product, and simultaneously, the regeneration technology of the macroporous adsorption resin is suitable for large-scale production, can reduce the cost to a great extent and improve the content of effective components.

Detailed Description