CN103232456B - A kind of method of preparing chlorophyll cupric acid taking silkworm excrement as raw material - Google Patents
A kind of method of preparing chlorophyll cupric acid taking silkworm excrement as raw material Download PDFInfo
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Abstract
A kind of method of preparing chlorophyll cupric acid taking silkworm excrement as raw material of the present invention, relates to the preparing technical field of chlorophyll cupric acid. The method is in ethanol-NaOH double-aqueous phase system, directly the chlorophyll in silkworm excrement is carried out to saponification, the saponification chlorophyll of generation is extracted to phase on double-aqueous phase system simultaneously, then separate phase on double-aqueous phase system, copper is put in acidifying, make copper chlorophyll acid crude, then after distilled water, benzinum, 40 ~ 50% ethanol washings, make the acid of refining chlorophyll copper. Compared with traditional handicraft, shorten technological process, reduce consumption of organic solvent, reduce material consumption and energy consumption. Overcome conventional process flow long, consumption of organic solvent is large, the defect that material consumption and energy consumption are high.
Description
Technical field
The present invention relates to the preparing technical field of chlorophyll cupric acid, particularly a kind of method of preparing chlorophyll cupric acid taking silkworm excrement as raw material.
Background technology
Sodium copper chlorophyllin is a kind of natural food colour that FAO (Food and Agriculture Organization of the United Nation), the World Health Organization and the approval of food additives standard committee of China are used, compared with chlorophyll, sodium copper chlorophyllin stable in properties, resistance to processing, be widely used in food and medicine industry. Chlorophyll cupric acid is to prepare the important intermediate of sodium copper chlorophyllin. The method that tradition is prepared chlorophyll cupric acid mainly comprises following process: 1. organic solvent extraction is prepared chlorophyll paste; 2. chlorophyll paste saponification is prepared chlorophyllin sodium; 3. acidifying is put copper reaction and is prepared copper chlorophyll acid crude; 4. the acid of refining chlorophyll copper is prepared in the removal of impurities of copper chlorophyll acid crude. This technological process is long, and consumption of organic solvent is large, and material consumption and energy consumption are high.
Double-aqueous phase system (AqueousTwo-PhaseSystem, ATPS) is that one or more materials mix with finite concentration in water, the immiscible two-phase water solution system forming under certain condition. Aqueous two-phase extraction (AqueousTwo-PhaseExtraction, ATPE) is a kind of new separation technology that has future occurring in recent years. Aqueous two-phase extraction principle is similar to traditional organic solvent extractionprocess, is all in two alternate selective distribution according to material. Traditional solvent extraction is the mass transport process from water to organic phase normally, and in extracting at diversified separation of products, high purity material of task, has many categories that polar organic matter separates that belong to, and this has limited solvent-extracted extensive use to a great extent. There is the biologically active separating-purifying of valuable material again for some, use traditional solvent extraction technology can cause sex change and the inactivation of bioactivator, in order to prevent the destruction of organic solvent to bioactivator, on solvent-extracted basis, develop a kind of novel liquid-liquid extraction and separation technology-aqueous two-phase extraction from a water mass transfer to another water. This method operating condition gentleness, safety non-toxic or low toxicity, technique is simple, can utilize the mixing, the centrifugal and separation equipment that in original organic solvent extraction production, use, in addition, can use existing extraction principle scale-up parameter in proportion, be highly suitable for industrial production, realize computer-controlled serialization abroad and produced.
Chlorophyll is mainly present in the organelle such as plastid, vacuole and cell membrane. Therefore clasmatosis is the committed step of extracting phytochrome, directly has influence on quality, output and the production cost of product. Conventional cell wall breaking method comprises Physical (as high-pressure homogenization method, freeze-thaw method, ultramicro grinding method, sonioation method etc.), chemical method (as surfactant method, organic solvent method, salt broken wall method etc.) and bioanalysis (combined-enzyme method). Wherein organic solvent method can change the permeability of cell membrane or film, thereby thing in born of the same parents is infiltrated selectively, and therefore chlorophyll paste can adopt solvent extraction method to extract. Salt method broken wall is the permeability that utilizes the salt of high concentration to produce high osmotic pressure to change cell membrane, makes cell dehydration, and plasmolysis, discharges thing in born of the same parents thereby make under external force cell self break. While adopting ethanol-NaOH double-aqueous phase system to extract phytochrome, system self has the double action of organic solvent method and salt method broken wall concurrently, by regulating salt and solvent composition and consumption, can greatly increase the permeability of cell membrane or film, thing in born of the same parents is infiltrated selectively.
Summary of the invention
The object of the invention is to overcome the defect that the current chlorophyll cupric acid technological process of production is long, the preparation method of the more simple chlorophyll cupric acid of a kind of technological process is provided.
Technical scheme of the present invention is summarized as follows: a kind of method of preparing chlorophyll cupric acid taking silkworm excrement as raw material, and the method comprises the following steps:
(1) be 0.36 ~ 0.70gmL by concentration-1Sodium hydrate aqueous solution and ethanol mix by 3:7 ~ 7:3 by volume, prepare ethanol-NaOH double-aqueous phase system.
(2) silkworm excrement is added in the described ethanol-NaOH of step (1) double-aqueous phase system, in every milliliter of ethanol-NaOH double-aqueous phase system, add silkworm excrement 0.01 ~ 0.1g, vibration mixes, and leaves standstill phase-splitting under 50 ~ 70 DEG C of conditions after stirring reaction 1 ~ 3h, separates mutually upper.
(3) regulating upper phase pH value with hydrochloric acid is 2～3, and then adding mass concentration is 10 ~ 20%CuSO4Solution, upper and 10 ~ 20%CuSO4The volume ratio of solution is 50～250:1, under 50 ~ 70 DEG C of conditions, reacts 1 ~ 2h, and suction filtration is dried filter residue to make copper chlorophyll acid crude.
(4) be 40 ~ 50% ethanol washings by distilled water, benzinum, mass concentration respectively by copper chlorophyll acid crude, filter, then under 50 ~ 70 DEG C of conditions, be dried and make the acid of refining chlorophyll copper. Cleaning solvent distilled water, benzinum and 40 ~ 50% ethanol consumptions are by every gram of copper chlorophyll acid crude 10 ~ 20mL, and washing times is 1～3 time.
The present invention compared with prior art, has the following advantages and beneficial effect:
1. the method is in ethanol-NaOH double-aqueous phase system, directly the chlorophyll in silkworm excrement is carried out to saponification, the saponification chlorophyll of generation is extracted to phase on double-aqueous phase system simultaneously, then separates phase acidifying on double-aqueous phase system and put copper, then will after washing of precipitate, make the acid of refining chlorophyll copper. Compared with traditional handicraft, shorten technological process, reduce consumption of organic solvent, reduce material consumption and energy consumption.
2. in ethanol-NaOH double-aqueous phase system, in the process of stirring reaction, the upper form with droplet that is rich in ethanol is scattered in the water that is rich in NaOH, in the water that is rich in NaOH, there is saponification in the chlorophyll in silkworm excrement and NaOH, chlorophyllin sodium is transferred to once generating the upper phase that is rich in ethanol, this process is conducive to the carrying out of saponification, improves productive rate. Silkworm excrement Determination of Chlorophyll and NaOH saponification generate the process of chlorophyllin sodium and the process of aqueous two-phase extraction chlorophyllin sodium completes in ethanol-NaOH double-aqueous phase system simultaneously.
3. ethanol-NaOH double-aqueous phase system system self has the double action of organic solvent method and salt method broken wall concurrently, by regulating salt and solvent composition and consumption, can greatly increase the permeability of cell membrane or film, and born of the same parents' inner chlorophyll is more easily infiltrated.
Detailed description of the invention
Embodiment is below in order to make those skilled in the art understand the present invention, but limits the present invention never in any form.
Below in conjunction with instantiation, the present invention is further illustrated.
Embodiment 1
Prepare a method for chlorophyll cupric acid, taking silkworm excrement as raw material, comprise the following steps:
(1) be 0.40gmL by concentration-1Sodium hydrate aqueous solution and ethanol mix by 6:4 by volume, prepare ethanol-NaOH double-aqueous phase system, cumulative volume is 1L.
(2) 10g silkworm excrement is added in the described ethanol-NaOH of step (1) double-aqueous phase system, vibration mixes, and leaves standstill phase-splitting under 60 DEG C of conditions after stirring reaction 2h, separates mutually upper.
(3) regulating upper phase pH value with hydrochloric acid is 2, then adds 20%CuSO4Solution 4mL reacts 2h under 60 DEG C of conditions, and suction filtration is dried filter residue to make copper chlorophyll acid crude.
(4) copper chlorophyll acid crude is washed respectively 1 time with 10mL distilled water, 10mL benzinum, 10mL40% ethanol respectively, filter, then the dry refining chlorophyll copper acid 0.053g that makes under 60 DEG C of conditions.
Embodiment 2
Prepare a method for chlorophyll cupric acid, taking silkworm excrement as raw material, comprise the following steps:
(1) be 0.40gmL by concentration-1Sodium hydrate aqueous solution and ethanol mix by 3:7 by volume, prepare ethanol-NaOH double-aqueous phase system, cumulative volume is 1L.
(2) 10g silkworm excrement is added in the described ethanol-NaOH of step (1) double-aqueous phase system, vibration mixes, and leaves standstill phase-splitting under 60 DEG C of conditions after stirring reaction 2h, separates mutually upper.
(3) regulating upper phase pH value with hydrochloric acid is 2, then adds 20%CuSO4Solution 4mL reacts 2h under 60 DEG C of conditions, and suction filtration is dried filter residue to make copper chlorophyll acid crude.
(4) copper chlorophyll acid crude is washed respectively 1 time with 10mL distilled water, 10mL benzinum, 10mL40% ethanol respectively, filter, then the dry refining chlorophyll copper acid 0.12g that makes under 60 DEG C of conditions.
Embodiment 3
Prepare a method for chlorophyll cupric acid, taking silkworm excrement as raw material, comprise the following steps:
(1) be 0.40gmL by concentration-1Sodium hydrate aqueous solution and ethanol mix by 3:7 by volume, prepare ethanol-NaOH double-aqueous phase system, cumulative volume is 1L.
(2) 20g silkworm excrement is added in the described ethanol-NaOH of step (1) double-aqueous phase system, vibration mixes, and leaves standstill phase-splitting under 60 DEG C of conditions after stirring reaction 2h, separates mutually upper.
(3) regulating upper phase pH value with hydrochloric acid is 2, then adds 20%CuSO4Solution 4mL reacts 2h under 60 DEG C of conditions, and suction filtration is dried filter residue to make copper chlorophyll acid crude.
(4) copper chlorophyll acid crude is washed respectively 1 time with 10mL distilled water, 10mL benzinum, 10mL40% ethanol respectively, filter, then the dry refining chlorophyll copper acid 0.23g that makes under 60 DEG C of conditions.
Embodiment 4
Prepare a method for chlorophyll cupric acid, taking silkworm excrement as raw material, comprise the following steps:
(1) be 0.70gmL by concentration-1Sodium hydrate aqueous solution and ethanol mix by 3:7 by volume, prepare ethanol-NaOH double-aqueous phase system, cumulative volume is 1L.
(2) 20g silkworm excrement is added in the described ethanol-NaOH of step (1) double-aqueous phase system, vibration mixes, and leaves standstill phase-splitting under 60 DEG C of conditions after stirring reaction 2h, separates mutually upper.
(3) regulating upper phase pH value with hydrochloric acid is 2, then adds 20%CuSO4Solution 4mL reacts 2h under 60 DEG C of conditions, and suction filtration is dried filter residue to make copper chlorophyll acid crude.
(4) copper chlorophyll acid crude is washed respectively 1 time with 10mL distilled water, 10mL benzinum, 10mL40% ethanol respectively, filter, then the dry refining chlorophyll copper acid 0.13g that makes under 60 DEG C of conditions.
Embodiment 5
Prepare a method for chlorophyll cupric acid, taking silkworm excrement as raw material, comprise the following steps:
(1) be 0.70gmL by concentration-1Sodium hydrate aqueous solution and ethanol mix by 3:7 by volume, prepare ethanol-NaOH double-aqueous phase system, cumulative volume is 1L.
(2) 10g silkworm excrement is added in the described ethanol-NaOH of step (1) double-aqueous phase system, vibration mixes, and leaves standstill phase-splitting under 60 DEG C of conditions after stirring reaction 2h, separates mutually upper.
(3) regulating upper phase pH value with hydrochloric acid is 2, then adds 20%CuSO4Solution 4mL reacts 2h under 70 DEG C of conditions, and suction filtration is dried filter residue to make copper chlorophyll acid crude.
(4) copper chlorophyll acid crude is washed respectively 1 time with 10mL distilled water, 10mL benzinum, 10mL40% ethanol respectively, filter, then the dry refining chlorophyll copper acid 0.069g that makes under 60 DEG C of conditions.
Claims (5)
1. prepare a method for chlorophyll cupric acid taking silkworm excrement as raw material, it is characterized in that carrying out according to following step:
(1) be 0.40gmL by concentration-1Sodium hydrate aqueous solution and ethanol mix by 6:4 by volume, prepare ethanol-NaOH double-aqueous phase system, cumulative volume is 1L;
(2) 10g silkworm excrement is added in the described ethanol-NaOH of step (1) double-aqueous phase system, vibration mixes, and leaves standstill phase-splitting under 60 DEG C of conditions after stirring reaction 2h, separates mutually upper;
(3) regulating upper phase pH value with hydrochloric acid is 2, then adds 20%CuSO4Solution 4mL reacts 2h under 60 DEG C of conditions, and suction filtration is dried filter residue to make copper chlorophyll acid crude;
(4) copper chlorophyll acid crude is washed respectively 1 time with 10mL distilled water, 10mL benzinum, 10mL40% ethanol respectively, filter, then the dry refining chlorophyll copper acid 0.053g that makes under 60 DEG C of conditions.
2. prepare a method for chlorophyll cupric acid taking silkworm excrement as raw material, it is characterized in that carrying out according to following step:
(1) be 0.40gmL by concentration-1Sodium hydrate aqueous solution and ethanol mix by 3:7 by volume, prepare ethanol-NaOH double-aqueous phase system, cumulative volume is 1L;
(2) 10g silkworm excrement is added in the described ethanol-NaOH of step (1) double-aqueous phase system, vibration mixes, and leaves standstill phase-splitting under 60 DEG C of conditions after stirring reaction 2h, separates mutually upper;
(3) regulating upper phase pH value with hydrochloric acid is 2, then adds 20%CuSO4Solution 4mL reacts 2h under 60 DEG C of conditions, and suction filtration is dried filter residue to make copper chlorophyll acid crude;
(4) copper chlorophyll acid crude is washed respectively 1 time with 10mL distilled water, 10mL benzinum, 10mL40% ethanol respectively, filter, then the dry refining chlorophyll copper acid 0.12g that makes under 60 DEG C of conditions.
3. prepare a method for chlorophyll cupric acid taking silkworm excrement as raw material, it is characterized in that carrying out according to following step:
(1) be 0.40gmL by concentration-1Sodium hydrate aqueous solution and ethanol mix by 3:7 by volume, prepare ethanol-NaOH double-aqueous phase system, cumulative volume is 1L;
(2) 20g silkworm excrement is added in the described ethanol-NaOH of step (1) double-aqueous phase system, vibration mixes, and leaves standstill phase-splitting under 60 DEG C of conditions after stirring reaction 2h, separates mutually upper;
(3) regulating upper phase pH value with hydrochloric acid is 2, then adds 20%CuSO4Solution 4mL reacts 2h under 60 DEG C of conditions, and suction filtration is dried filter residue to make copper chlorophyll acid crude;
(4) copper chlorophyll acid crude is washed respectively 1 time with 10mL distilled water, 10mL benzinum, 10mL40% ethanol respectively, filter, then the dry refining chlorophyll copper acid 0.23g that makes under 60 DEG C of conditions.
4. prepare a method for chlorophyll cupric acid taking silkworm excrement as raw material, it is characterized in that carrying out according to following step:
(1) be 0.70gmL by concentration-1Sodium hydrate aqueous solution and ethanol mix by 3:7 by volume, prepare ethanol-NaOH double-aqueous phase system, cumulative volume is 1L;
(2) 20g silkworm excrement is added in the described ethanol-NaOH of step (1) double-aqueous phase system, vibration mixes, and leaves standstill phase-splitting under 60 DEG C of conditions after stirring reaction 2h, separates mutually upper;
(3) regulating upper phase pH value with hydrochloric acid is 2, then adds 20%CuSO4Solution 4mL reacts 2h under 60 DEG C of conditions, and suction filtration is dried filter residue to make copper chlorophyll acid crude;
(4) copper chlorophyll acid crude is washed respectively 1 time with 10mL distilled water, 10mL benzinum, 10mL40% ethanol respectively, filter, then the dry refining chlorophyll copper acid 0.13g that makes under 60 DEG C of conditions.
5. prepare a method for chlorophyll cupric acid taking silkworm excrement as raw material, it is characterized in that carrying out according to following step:
(1) be 0.70gmL by concentration-1Sodium hydrate aqueous solution and ethanol mix by 3:7 by volume, prepare ethanol-NaOH double-aqueous phase system, cumulative volume is 1L;
(2) 10g silkworm excrement is added in the described ethanol-NaOH of step (1) double-aqueous phase system, vibration mixes, and leaves standstill phase-splitting under 60 DEG C of conditions after stirring reaction 2h, separates mutually upper;
(3) regulating upper phase pH value with hydrochloric acid is 2, then adds 20%CuSO4Solution 4mL reacts 2h under 70 DEG C of conditions, and suction filtration is dried filter residue to make copper chlorophyll acid crude;
(4) copper chlorophyll acid crude is washed respectively 1 time with 10mL distilled water, 10mL benzinum, 10mL40% ethanol respectively, filter, then the dry refining chlorophyll copper acid 0.069g that makes under 60 DEG C of conditions.
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| JPH05279368A (en) * | 1992-03-30 | 1993-10-26 | Masaki Kamata | Production of chlorophyll a type compound and feed comprising the same product |
| CN100404538C (en) * | 2001-10-11 | 2008-07-23 | 自贡亚欧桥集团有限公司 | Production method of chlorophyll cupric acid and its sodium salt |
| 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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Inventor after: Wang Bin Inventor after: Han Juan Inventor after: Chen Tong Inventor after: Ni Liang Inventor after: Li Yuliang Inventor after: Tang Xu Inventor after: Zhang Wenli Inventor before: Wang Bin Inventor before: Han Juan Inventor before: Ma Jingjing Inventor before: Wu Yingchun Inventor before: Hu Yutao Inventor before: Ni Liang |
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