CN111943955A - Preparation process for preparing sodium copper chlorophyllin from microalgae and product thereof - Google Patents
Preparation process for preparing sodium copper chlorophyllin from microalgae and product thereof Download PDFInfo
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- CN111943955A CN111943955A CN202010942577.XA CN202010942577A CN111943955A CN 111943955 A CN111943955 A CN 111943955A CN 202010942577 A CN202010942577 A CN 202010942577A CN 111943955 A CN111943955 A CN 111943955A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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Abstract
The invention provides a preparation process for preparing sodium copper chlorophyllin from microalgae and a product thereof. The invention not only has the characteristics of rich chlorophyll in raw materials, rapid growth, easy culture, no limitation of places and seasons and adjustable production scale, but also can extract the chlorophyll to be immediately mixed with Cu2+The conversion reaction is carried out, so that the extracted chlorophyll is protected from damage of light and heat to influence the subsequent yield, the obtained extract has higher stability, higher heat resistance and light resistance, and the yield and the product quality are improved.
Description
Technical Field
The invention relates to the technical field of pigment extraction, in particular to a preparation process for preparing sodium copper chlorophyllin from microalgae and a product thereof.
Background
Along with the improvement of living standard of people and the enhancement of health consciousness, people tend to advocate natural health products, natural pigments are widely applied to food, cosmetics and medicine industries in developed countries and regions such as the daily America and European Union, synthetic pigments are forbidden in children food, beverage food and roast marinated food, and the use ratio of the natural pigments accounts for more than 80 percent of the proportion of the whole colorant. In China, people pay more and more attention to food safety due to major food safety accidents such as 'Sudan red' event, 'poisonous milk powder' event and the like. In the field of food coloring, the use of synthetic pigments is gradually restricted, for example, the use of synthetic pigments has been restricted in children's food in China.
Chlorophyll and sodium copper chlorophyllin are common natural pigments, but the stability of sodium copper chlorophyllin is much higher than that of chlorophyll, so the application range is wider. The following are confirmed according to related literature reports: the amount of solar energy available in water is much less than that available on land, and to achieve the same energy conversion, the chlorophyll content of the plants in water involved in photosynthesis must be higher than that of the plants on land. The chlorophyll content of terrestrial plants in nature is about 0.3% -0.5%, and the chlorophyll content of microalgae is about 0.5% -2%. The microalgae contains rich chlorophyll, and has the characteristics of rapid growth, easy culture, no limitation of places and seasons, and adjustable production scale, thereby being beneficial to saving the cost and ensuring the resource supply. Therefore, the comprehensive utilization of microalgae can convert low-cost resources into products with high economic added values, and can be widely applied to the industries of food, medicine, health care products and the like.
The traditional extraction process of sodium copper chlorophyllin generally comprises the steps of extracting chlorophyll, then saponifying, replacing copper or replacing copper and saponifying, and when the extraction method is used, the chlorophyll is influenced by heating and illumination for a long time, so that decomposition reaction is easy to occur, and the yield of sodium copper chlorophyllin is reduced.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide a preparation process for preparing sodium copper chlorophyllin from microalgae and a product thereof. In order to achieve the purpose, the invention adopts the following technical scheme:
(II) technical scheme
A preparation process for preparing sodium copper chlorophyllin from microalgae and a product thereof comprise the following steps:
step one, preparing raw materials: selecting microalgae with a certain mass;
step two, leaching and primary acidification copper substitution: 70-95% ethanol which is 3-6 times of the weight of the microalgae is adopted, and 20% C which is 1-10% of the weight of the microalgae is addedUSO4Adjusting pH to 2-3 with dilute sulfuric acid, leaching the raw materials in continuous countercurrent extraction equipment for 4-6 hours at room temperature to obtain leaching liquor;
step three, filtering and separating: filtering the leaching solution, and separating solid impurities to obtain filtrate;
step four, concentration: concentrating the filtrate under reduced pressure to obtain paste;
step five, saponification: dissolving the paste with equal amount of ethanol, adjusting pH to 11-12 with liquid alkali, and heating at 40-60 deg.C for 30-60min to obtain saponified solution;
step six, secondary copper acidification: adjusting the pH value of the saponification solution to 2-3 by using dilute sulfuric acid, and adding 20% of copper sulfate solution accounting for 1% -10% of the weight of the microalgae; heating at 40-60 deg.C for 30-60min to obtain acidified copper substitute solution;
seventhly, removing impurities for the first time: concentrating the acidified copper substitute solution under reduced pressure to obtain a paste, washing with petroleum ether, filtering to obtain dark green granular copper chlorophyllin with loose metal color, washing with purified water until the filtrate is colorless, and drying at 50 deg.C to remove water;
step eight, saponificationSalt: dissolving the above copper chlorophyllin with 3 times of acetone, and adding 1mol/L KOH-C2H5Adjusting the pH value of the OH solution to 11-12, and filtering to obtain sodium copper chlorophyllin powder;
step nine, drying: drying the sodium copper chlorophyllin powder to obtain black powder with impurities;
step ten, secondary impurity removal: adding 3-5 times of ethanol into the black color band impurity powder, repeatedly washing until the filtrate is light green to obtain black powder, and drying at 50 ℃ to remove ethanol;
step eleven, sterilization: sterilizing the black powder;
step twelve, sieving to remove iron: passing the black powder through a 60-120 mesh sieve and a 8000- & ltSUB & gt 12000 & lt/SUB & gt GS iron remover;
step thirteen, mixing: placing the powder after sieving and removing the iron in a powder mixer for fully mixing to obtain a sodium copper chlorophyllin product;
step fourteen, packaging: and (3) carrying out vacuum packaging on the sodium copper chlorophyllin product to obtain a finished product of sodium copper chlorophyllin.
Further, the filtration mode is plate-frame filtration, diatomite filtration, bag filtration, chamber filter pressing, vacuum filtration or tubular filtration.
Further, the separation equipment is a plate-and-frame or tube centrifuge.
Further, the microalgae is at least one of cyanophyta, chlorophyta, chrysophyta, phaeophyta, xanthophyta, dinophyta, stonechia, diatom, cryptophyta, and euglenophyta.
Further, the sterilization mode is ultrahigh temperature instant sterilization, the sterilization temperature is 121-.
(III) advantageous effects
Compared with the prior art, the invention has obvious advantages and beneficial effects, and particularly has the following two beneficial effects:
firstly, the method comprises the following steps: the microalgae contains rich chlorophyll, and has the characteristics of rapid growth, easy culture, no limitation of site and season, and no regulation and control of production scale, thereby not only being beneficial to saving cost, but also ensuring resource supply and improving economic benefit;
secondly, the method comprises the following steps: the chlorophyll extraction and the copper acidification substitution are carried out simultaneously, so that the extracted chlorophyll is immediately mixed with Cu2+The conversion reaction is carried out, so that the extracted chlorophyll is protected from being damaged by light and heat to influence the subsequent yield, the obtained extract has higher stability, higher heat resistance and light resistance, and simultaneously, the yield and the product quality are improved, the raw materials are comprehensively utilized, the cost is reduced, and the basis is laid for industrial application.
Detailed Description
The present invention will be further illustrated with reference to the following examples.
Example 1:
step one, preparing raw materials: selecting 1000kg of spirulina in cyanophyta;
step two, leaching and primary acidification copper substitution: adopting 80% ethanol 4 times of the weight of Spirulina, and adding 20% C3% of the weight of SpirulinaUSO4Adjusting the pH of the solution to 2.3 by using dilute sulfuric acid, and leaching the raw materials in continuous countercurrent extraction equipment for 4.5 hours at room temperature to obtain a leaching solution;
step three, filtering and separating: filtering the leaching solution, and filtering to separate solid impurities in the leaching solution to obtain filtrate;
step four, concentration: concentrating the filtrate under reduced pressure to obtain paste;
step five, saponification: dissolving the paste with 80% ethanol, adjusting pH to 11.3 with liquid alkali, and heating at 45 deg.C for 35min to obtain saponified solution;
step six, secondary copper acidification: adjusting pH of the saponified solution to 2.3 with dilute sulfuric acid, and adding 20% copper sulfate solution 3% of spirulina weight; heating at 45 deg.C for 35min to obtain acidified copper substitute solution;
seventhly, removing impurities for the first time: concentrating the acidified copper substitute solution under reduced pressure to obtain a paste, washing with petroleum ether, filtering to obtain dark green granular copper chlorophyllin with loose metal color, washing with purified water until the filtrate is colorless, and drying at 50 deg.C to remove water;
step eight, saponification and salt formation: dissolving the above copper chlorophyllin with 3 times of acetone, and adding 1mol/L KOH-C2H5Adjusting the pH value of the OH solution to 11.3, and filtering to obtain sodium copper chlorophyllin powder;
step nine, drying: drying the sodium copper chlorophyllin powder to obtain black powder with impurities;
step ten, secondary impurity removal: adding 3.5 times of ethanol into the impurity powder of the black color band, repeatedly washing until the filtrate is light green to obtain black powder, and drying at 50 ℃ to remove the ethanol;
step eleven, sterilization: performing high-temperature instantaneous sterilization treatment on the black powder, wherein the sterilization temperature is 125 ℃, and the sterilization time is 5 s;
step twelve, sieving to remove iron: passing the black powder through an 80-mesh sieve and a 9000GS iron remover;
step thirteen, mixing: putting the powder after sieving and removing the iron into a powder mixer for fully mixing to obtain 19.43kg of sodium copper chlorophyllin products;
step fourteen, packaging: and (3) carrying out vacuum packaging on the sodium copper chlorophyllin product to obtain a finished product of sodium copper chlorophyllin.
Example 2:
step one, preparing raw materials: selecting 1100kg of Chlorella in Chlorophyta;
step two, leaching and primary acidification copper substitution: adopting 80% ethanol 4.5 times of Chlorella, and adding 20% C5% of ChlorellaUSO4Adjusting the pH of the solution to 2.5 by using dilute sulfuric acid, and leaching the raw materials in continuous countercurrent extraction equipment for 5 hours at room temperature to obtain a leaching solution;
step three, filtering and separating: filtering the leaching solution, and filtering to separate solid impurities in the leaching solution to obtain filtrate;
step four, concentration: concentrating the filtrate under reduced pressure to obtain paste;
step five, saponification: dissolving the paste with equal amount of ethanol, adjusting pH to 11.5 with liquid alkali, and heating at 45 deg.C for 40min to obtain saponified solution;
step six, secondary copper acidification: adjusting pH of the saponified solution to 2.5 with dilute sulphuric acid, and adding 20% copper sulfate solution 5% of Chlorella; heating at 45 deg.C for 35min to obtain acidified copper substitute solution;
seventhly, removing impurities for the first time: concentrating the acidified copper substitute solution under reduced pressure to obtain a paste, washing with petroleum ether, filtering to obtain dark green granular copper chlorophyllin with loose metal color, washing with purified water until the filtrate is colorless, and drying at 50 deg.C to remove water;
step eight, saponification and salt formation: dissolving the above copper chlorophyllin with 3 times of acetone, and adding 1mol/L KOH-C2H5Adjusting the pH value of the OH solution to 11.5, and filtering to obtain sodium copper chlorophyllin powder;
step nine, drying: drying the sodium copper chlorophyllin powder to obtain black powder with impurities;
step ten, secondary impurity removal: adding 4 times of ethanol into the impurity powder of the black color band, repeatedly washing until the filtrate is light green to obtain black powder, and drying at 50 ℃ to remove the ethanol;
step eleven, sterilization: performing high-temperature instantaneous sterilization treatment on the black powder, wherein the sterilization temperature is 130 ℃, and the sterilization time is 6 s;
step twelve, sieving to remove iron: passing the black powder through an 80-mesh sieve and a 9000GS iron remover;
step thirteen, mixing: putting the powder after sieving and removing the iron into a powder mixer for fully mixing to obtain 19.98kg of sodium copper chlorophyllin products;
step fourteen, packaging: and (3) carrying out vacuum packaging on the sodium copper chlorophyllin product to obtain a finished product of sodium copper chlorophyllin.
Example 3:
step one, preparing raw materials: selecting 1200kg of the Cyclotella Hupehensis in the Diatom;
step two, leaching and primary acidification copper substitution: adopting 85% ethanol 5 times of the weight of the small cyclocarya Hupehensis, and simultaneously adding 20% C7% of the weight of the small cyclocarya HupehensisUSO4The solution is adjusted to pH 2.2 with dilute sulfuric acid and kept at room temperatureLeaching the raw materials for 5 hours in continuous countercurrent extraction equipment to obtain a leaching solution;
step three, filtering and separating: filtering the leaching solution, and filtering to separate solid impurities in the leaching solution to obtain filtrate;
step four, concentration: concentrating the filtrate under reduced pressure to obtain paste;
step five, saponification: dissolving the paste with equal amount of ethanol, adjusting pH to 11.7 with liquid alkali, and heating at 55 deg.C for 45min to obtain saponified solution;
step six, secondary copper acidification: adjusting the pH value of the saponification solution to 2.3 by using dilute sulfuric acid, and adding 20% copper sulfate solution which accounts for 7% of the weight of the Cyclotella subcontracting lake; heating at 55 deg.C for 40min to obtain acidified copper substitute solution;
seventhly, removing impurities for the first time: concentrating the acidified copper substitute solution under reduced pressure to obtain a paste, washing with petroleum ether, filtering to obtain dark green granular copper chlorophyllin with loose metal color, washing with purified water until the filtrate is colorless, and drying at 50 deg.C to remove water;
step eight, saponification and salt formation: dissolving the above copper chlorophyllin with 3 times of acetone, and adding 1mol/L KOH-C2H5Adjusting the pH value of the OH solution to 11.6, and filtering to obtain sodium copper chlorophyllin powder;
step nine, drying: drying the sodium copper chlorophyllin powder to obtain black powder with impurities;
step ten, secondary impurity removal: adding 4 times of ethanol into the impurity powder of the black color band, repeatedly washing until the filtrate is light green to obtain black powder, and drying at 50 ℃ to remove the ethanol;
step eleven, sterilization: performing high-temperature instantaneous sterilization treatment on the black powder, wherein the sterilization temperature is 125 ℃, and the sterilization time is 6 s;
step twelve, sieving to remove iron: passing the black powder through an 80-mesh sieve and a 9000GS iron remover;
step thirteen, mixing: putting the sieved and deironized powder into a powder mixer for fully mixing to obtain 21.67kg of sodium copper chlorophyllin product;
step fourteen, packaging: and (3) carrying out vacuum packaging on the sodium copper chlorophyllin product to obtain a finished product of sodium copper chlorophyllin.
The physical and chemical indexes of the sodium copper chlorophyllin prepared in the three examples are determined as shown in the following table
| Item | Finger watch (GB264406-2011) | Example 1 | Example 2 | Example 3 |
| pH | 9.5～11.0 | 10.18 | 10.16 | 9.89 |
| Absorbance [ E1% (405nm + -3 nm)]≥ | 568 | 585 | 576 | 574 |
| Absorbance ratio | 3.2～4.0 | 3.74 | 3.71 | 3.82 |
| Total copper (Cu), w/% < or less | 8 | 6.74 | 6.81 | 6.78 |
| Free copper (Cu), w/% < w ≦ | 0.025 | 0.0159 | 0.0161 | 0.0162 |
| Drying and reducing weight, w/% > is less than or equal to | 5 | 3.45 | 3.49 | 3.46 |
| Total arsenic (calculated by As)/(mg/kg) is less than or equal to | 2 | ＜2 | ＜2 | ＜2 |
| Lead (Pb)/(mg/kg) is less than or equal to | 5 | ＜5 | ＜5 | ＜5 |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (5)
1. A preparation process for preparing sodium copper chlorophyllin from microalgae and a product thereof are characterized in that: the method comprises the following steps:
step one, preparing raw materials: selecting microalgae with a certain mass;
step two, leaching and primary acidification copper substitution: 70-95% ethanol which is 3-6 times of the weight of the microalgae is adopted, and 20% C which is 1-10% of the weight of the microalgae is addedUSO4Adjusting pH to 2-3 with dilute sulfuric acid, leaching the raw materials in continuous countercurrent extraction equipment for 4-6 hours at room temperature to obtain leaching liquor;
step three, filtering and separating: filtering the leaching solution, and separating solid impurities to obtain filtrate;
step four, concentration: concentrating the filtrate under reduced pressure to obtain paste;
step five, saponification: dissolving the paste with equal amount of ethanol, adjusting pH to 11-12 with liquid alkali, and heating at 40-60 deg.C for 30-60min to obtain saponified solution;
step six, secondary copper acidification: adjusting the pH value of the saponification solution to 2-3 by using dilute sulfuric acid, and adding 20% of copper sulfate solution accounting for 1% -10% of the weight of the microalgae; heating at 40-60 deg.C for 30-60min to obtain acidified copper substitute solution;
seventhly, removing impurities for the first time: concentrating the acidified copper substitute solution under reduced pressure to obtain a paste, washing with petroleum ether, filtering to obtain dark green granular copper chlorophyllin with loose metal color, washing with purified water until the filtrate is colorless, and drying at 50 deg.C to remove water;
step eight, saponification and salt formation: dissolving the above copper chlorophyllin with 3 times of acetone, and adding 1mol/L KOH-C2H5Adjusting the pH value of the OH solution to 11-12, and filtering to obtain sodium copper chlorophyllin powder;
step nine, drying: drying the sodium copper chlorophyllin powder to obtain black powder with impurities;
step ten, secondary impurity removal: adding 3-5 times of ethanol into the black color band impurity powder, repeatedly washing until the filtrate is light green to obtain black powder, and drying at 50 ℃ to remove ethanol;
step eleven, sterilization: sterilizing the black powder;
step twelve, sieving to remove iron: passing the black powder through a 60-120 mesh sieve and a 8000- & ltSUB & gt 12000 & lt/SUB & gt GS iron remover;
step thirteen, mixing: placing the powder after sieving and removing the iron in a powder mixer for fully mixing to obtain a sodium copper chlorophyllin product;
step fourteen, packaging: and (3) carrying out vacuum packaging on the sodium copper chlorophyllin product to obtain a finished product of sodium copper chlorophyllin.
2. The process for preparing sodium copper chlorophyllin from microalgae and the product thereof according to claim 1 are characterized in that: the filtration mode is plate-frame filtration, diatomite filtration, bag filtration, van-type filter pressing, vacuum filtration or tubular filtration.
3. The process for preparing sodium copper chlorophyllin from microalgae and the product thereof according to claim 1 are characterized in that: the separation device is one of a plate-and-frame or tube centrifuge.
4. The process for preparing sodium copper chlorophyllin from microalgae and the product thereof according to claim 1 are characterized in that: the microalgae is at least one of cyanophyta, chlorophyta, chrysophyta, phaeophyta, xanthophyta, dinophyta, stonewort, diatom, cryptophyta, and euglena.
5. The process for preparing sodium copper chlorophyllin from microalgae and the product thereof according to claim 1 are characterized in that: the sterilization mode is ultrahigh temperature instant sterilization, the sterilization temperature is 121-137 ℃, and the sterilization time is 4-10 s.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113754671A (en) * | 2021-10-14 | 2021-12-07 | 云南博瑞生物科技有限公司 | Preparation method of sodium copper chlorophyllin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102199153A (en) * | 2011-03-29 | 2011-09-28 | 晨光生物科技集团天津有限公司 | Method for preparing sodium copper chlorophyllin by using silkworm excrement as raw material |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199153A (en) * | 2011-03-29 | 2011-09-28 | 晨光生物科技集团天津有限公司 | Method for preparing sodium copper chlorophyllin by using silkworm excrement as raw material |
Non-Patent Citations (2)
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| 蔡成翔等: "草坪草制取叶绿素铜钠盐工艺研究", 《广西右江民族师专学报》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113754671A (en) * | 2021-10-14 | 2021-12-07 | 云南博瑞生物科技有限公司 | Preparation method of sodium copper chlorophyllin |
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