CN100404538C - Production method of chlorophyll cupric acid and its sodium salt - Google Patents
Production method of chlorophyll cupric acid and its sodium salt Download PDFInfo
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- CN100404538C CN100404538C CNB011289422A CN01128942A CN100404538C CN 100404538 C CN100404538 C CN 100404538C CN B011289422 A CNB011289422 A CN B011289422A CN 01128942 A CN01128942 A CN 01128942A CN 100404538 C CN100404538 C CN 100404538C
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- chlorophyll
- acid
- copper
- silkworm excrement
- filter residue
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Abstract
The present invention discloses a method for producing acid copper chlorophyllin and sodium thereof by silkworm droppings, which comprises the following steps: directly saponifying the silkworm droppings to be centrifugally separated; adding copper to prepare a crude product of the acid copper chlorophyllin; washing by acetone and alcohol to continuously remove impurities step by step; drying to obtain a superfine product of the acid copper chlorophyllin; treating by sodium to prepare sodium copper chlorophyllin. As the method uses NaOH to directly saponify the silkworm droppings, the copper is added under an alkaline condition and the acetone and the alcohol are used for continuously removing the impurities, a technological process is effectively shortened. Compared with the background art, equipment investment can be reduced by 40%, power consumption is saved about 30% and production cycle is shortened by 70 to 80%; the present invention has the characteristics of few organic solvent, low operation cost, high productivity and product quality, etc. The present invention overcomes the disadvantages of the background art of long technological process, complicated operation, large solvent use level, much equipment configuration, large volume, high power consumption, poor product quality, etc.
Description
Technical field
The invention belongs in the field of fine chemical with the silkworm excrement is the method for raw material production chlorophyll cupric acid and sodium salt thereof (that is: chlorophyll copper sodium).
Background technology
Chlorophyll cupric acid and sodium salt thereof have purposes widely in industries such as pharmacy, food and household chemicals, its price is also expensive.Up to the present, traditional production technique is: silkworm excrement is added water softening → organic solvent extraction of dewatering → add → isolate extraction liquid → vacuum distillation recovered solvent concentrate chlorophyll → add NaOH simultaneously and heat saponification → propose yellow to remove yellow substance such as carotenoid, triacontanol price quote, phytol etc. add copper sulphate powder to put copper and to make its abundant copperization → be settled out chlorophyll cupric acid → employing distilled water again to purify chlorophyll → adding ethanol and to regulate behind the alcohol concn in the saponification liquor, ethanol and gasoline multiple times of filtration are washed to such an extent that chlorophyll cupric acid → sodium processing → evaporation drying → crushing screening promptly gets aqueous fusion chlorophyll copper sodium powder.
Though above-mentioned production technique has characteristics such as technical maturity, all exist technical process long, the production cycle reaches 40-45 hour, and complicated operation is put copper bar spare harshness; Consumption of organic solvent is big, and required recovery and bunkerage are many and device volume is big, reclaim the energy consumption height accordingly; Purifying difficult and be difficult to remove in calcium sulfate, influence the defectives such as purity of product.
Technology contents
The objective of the invention is at the existing Study of Defects a kind of more simple and practical production chlorophyll cupric acid of design of background technology and the processing method of sodium salt thereof, to reach shortened process and production cycle, minimizing equipment consumption and investment thereof, reduce consumption of organic solvent, energy consumption and running cost are boosted productivity and purpose such as quality product.
Solution of the present invention is just directly to add the saponification of NaOH solution after the raw material silkworm excrement is cleaned removal of impurities, adopts simultaneously at alkaline condition underlying copper, and acetone, the removal of impurities continuously of ethanol substep, thus reach its purpose.Therefore, the inventive method comprises:
A, saponification: with stand-by after the metering of raw material silkworm excrement, the cleaning removal of impurities; In enamel or ceramic soap pan, add heavy 4-6 times clear water of clean silkworm excrement and NaOH or the liquid caustic soda of silkworm excrement weight 15-20%, after the potential of hydrogen of solution transferred to pH=14, add stand-by silkworm excrement when being heated to 75 °～85 ℃, under 60 °～70 ℃ temperature condition, stir saponification 50-70 minute;
B, centrifugation: the mixed solution centrifuging after the saponification is separated, and stoste and washings after the filter residue after the separation also will filter for 2 times with the clear water washing continuously merge;
C, put copper: above-mentioned filtrate is moved in pottery or the copper reactor, and the concentration that adds equivalent by the volume of filtrate is the ethanol more than 95%, be heated with stirring to 60 °-70 ℃ in confined conditions after, slowly add copper sulphate powder; Finish, under heat-retaining condition, continue to stir 5-10 minute; The consumption of copper sulfate is the 0.8-1.5% of clean silkworm excrement weight.
D, system Chlorophyll Cu acid crude: add concentrated hydrochloric acid and transfer above-mentioned potential of hydrogen of putting copper liquid, and after stirring 30-60 minute under 60 ° of-70 ℃ of temperature, staticly settled 3.0～4.0 hours to PH=1-3; Through centrifuging, filtrate uses it for anything else then, and filter residue promptly gets the Chlorophyll Cu acid crude after drying;
E, acetone removal of impurities (fine purifiation for the first time): it is in the acetone solvent more than 95% that gained Chlorophyll Cu acid crude is dissolved in concentration, solvent load is by every gram (g) 4-6ml solvent, treat fully to dissolve after-filtration, filter residue again with the acetone of same amount repeat to wash molten, filter once after; Filter residue (calcium ions is at insolubless such as interior inorganic salt, folic acid, tartaric acid) removes, and filtrate (being chlorophyll cupric acid and acetone mixed solution) promptly gets the chlorophyll cupric acid dry product behind the fine purifiation one time after then placing and distilling recovery acetone under 60 ° of-70 ℃ of temperature;
F, pure eccysis assorted (fine purifiation for the second time): it is in the ethanol more than 95% that above-mentioned gained chlorophyll cupric acid dry product is dissolved in concentration again, solvent load is every gram dry product 50-70ml ethanol, treat fully to dissolve after-filtration, filter residue removes, filtrate slowly adds in the distilled water of 10 times of total amount of alcohol, the limit edged stirs, finish to staticly settle and get the Chlorophyll Cu Acid precipitation after 4 hours, filter rear filtrate and be used to reclaim ethanol, filter residue again through distilled water wash with after removing chlorion, under 70 °～80 ℃ temperature, be drying to obtain the chlorophyll cupric acid elaboration.
The isolating filter residue of mixed solution after the above-mentioned saponification is continuously with clear water washing 2 times, and each used clear water amount is the heavy 2-3 of clean silkworm excrement times.Described putting slowly adds copper sulphate powder in the copper process, after its adding method also can be dissolved in NaOH solution or ammonia solution with it, slowly add again.
Above-mentioned gained chlorophyll cupric acid is fat-soluble chlorophyll, can directly enter commercial use.Make raw material with it and handle through pure melt into salt again, that is:
Above-mentioned gained chlorophyll cupric acid elaboration is dissolved in the dehydrated alcohol that 5-10 doubly measures again, slowly adds concentration then and be the ethanolic soln of 5% NaOH, solution is transferred to PH=11-12, chlorophyll copper sodium ethanol and solid mixture; At last this mixture is placed distiller, distill being no more than under 80 ℃ the condition, the solid that ethanol reclaims the blackish green colour band metalluster of gained is chlorophyll copper sodium.
The present invention directly adds NaOH solution saponification silkworm excrement owing to adopting, saved to add water softening, and solvent dehydration, organic solvent extraction, vacuum distillation recovered solvent, concentrated chlorophyll, gasoline are put forward operations such as Huang and recovery gasoline; At alkaline condition underlying copper and adopt third bronze medal, the removal of impurities of ethanol continuous process, thereby shortened technical process effectively, reduced facility investment and energy consumption, compared with background technology and can save investment 40%, energy-conservation about 30%, shorten production cycle 70-80%; Therefore, it is simple and direct, practical that the present invention has technical process, low equipment investment, and energy consumption is low, with short production cycle, consumption of organic solvent is few, and running cost low and productivity and quality product are than characteristics such as height.
Embodiment
Present embodiment produces chlorophyll cupric acid with the clean silkworm excrement of 1kg and chlorophyll copper sodium is an example:
1. at first take by weighing raw material silkworm excrement 1.1kg and clean in clear water 2 times, sand wherein, lime mud etc. sink under water, and the silkworm excrement of bubbling through the water column takes out, approximately clean silkworm excrement 1kg (in dry measure), stand-by; In ceramic soap pan, add 5kg clear water and 170g left and right sides NaOH simultaneously, treat after the fully dissolving that potential of hydrogen with solution transfers to PH=14 and heats to 80 ℃, drop into stand-by silkworm excrement, stir saponification 1 hour at 60 ° of-70 ℃ of temperature range internal heating, this moment, the mixed solution potential of hydrogen was about PH-12;
2. centrifugation: with above-mentioned mixed solution centrifuging, continuously with clear water washing 2 times, each water consumption 2.5kg merges stoste and washings to filter residue again;
3. put copper: above-mentioned filtrate (saponification liquor) is placed copper reactor, adding 10L (liter) concentration is 95% ethanol, after being heated with stirring to 65 ℃ under the airtight condition, slowly add sulfuric acid copper powder 10g (adding after also can dissolving in NaOH or ammonia solution), the limit edged stirs, and finishes insulated and stirred 5-10 minute again;
4. system Chlorophyll Cu acid crude: add concentrated hydrochloric acid to above-mentioned putting in the copper liquid, transfer PH=2 and after stirring 30-60 minute under 65 ℃ the temperature, staticly settled 3.5 hours; With its centrifuging, filtrate uses it for anything else then, and filter residue promptly gets the about 20g of Chlorophyll Cu acid crude through 80 ℃ of warm air dryings;
5. acetone removal of impurities (fine purifiation): it is in 95% the acetone that above-mentioned gained crude product is dissolved in 110ml concentration, stir, treat that fully filter dissolving back (about about 3 minutes), filter residue drops in the acetone of the above-mentioned concentration of 110ml re-treatment once again, to remove the inorganic salt that comprise calcium salt, folic acid, insolubless such as pectin; Twice filtrate then places distiller, and distillation is reclaimed acetone (about 1 hour) and got the granular dry product 12g of chlorophyll cupric acid under 60 ° of-70 ° of temperature;
6. pure eccysis is mixed (secondary fine purifiation): it is in 97% the ethanol that above-mentioned dry product is dissolved in 65ml concentration again, treats fully to dissolve after-filtration, while filtering filtrate is splashed in the 650ml distilled water, and stirs simultaneously; Filter is complete to staticly settle about 4 hours; Filter then, filter residue again through distilled water wash once to remove residual chlorion; After 80 ℃ of warm air dryings promptly get elaboration chlorophyll cupric acid solid 10g.This elaboration can directly be used as the raw material of pharmacy, food, household chemicals, more above-mentioned chlorophyll cupric acid sodium is handled, that is:
The green mutual copper acid of above-mentioned gained 10g leaf elaboration is dissolved in the 70ml dehydrated alcohol, drip concentration simultaneously and be 5% NaOH ethanolic soln, wherein alcohol concn is 95%, transfers PH=11-12, makes it become chlorophyll copper sodium ethanol liquid and solid mixed solution; At last mixed solution is placed distiller, distill being no more than under 80 ℃ the temperature, ethanol reclaims, and the solid of the blackish green colour band metalluster of gained is chlorophyll copper sodium.Below being milled to granularity 175 μ m (promptly below 80 orders) place to be sealed under 4 ℃ of temperature in the brown glass bottle and store, get final product.
Claims (3)
1. the production method of a chlorophyll cupric acid comprises with the silkworm excrement being raw material; It is characterized in that this method comprises:
A, saponification: with stand-by after the metering of raw material silkworm excrement, the cleaning removal of impurities; In enamel or ceramic soap pan, add heavy 4-6 times clear water of clean silkworm excrement and NaOH or the liquid caustic soda of silkworm excrement weight 15-20%, after the potential of hydrogen of solution transferred to PH=14, add stand-by silkworm excrement when being heated to 75 °-85 ℃, under 60 ° of-70 ℃ of temperature condition, stir, saponification 50-70 minute;
B, centrifugation: the mixed solution centrifuging after the saponification is separated, and stoste and washings after the filter residue after the separation also will filter for 2 times with the clear water washing continuously merge;
C, put copper: above-mentioned filtrate is moved in pottery or the copper reactor, and the concentration that adds equivalent by the volume of filtrate is the ethanol more than 95%, be heated with stirring to 60 °-70 ℃ in confined conditions after, slowly add copper sulphate powder; Finish, continue to stir 5-10 minute under heat-retaining condition, the consumption of copper sulfate is the 0.8-1.5% of clean silkworm excrement weight;
D, system Chlorophyll Cu acid crude: add concentrated hydrochloric acid and transfer above-mentioned potential of hydrogen of putting copper liquid, staticly settled 3.0～4.0 hours to PH=1-3 and after stirring 30-60 minute under 60 ° of-70 ℃ of temperature; Through centrifuging, filtrate uses it for anything else then, and the filter residue drying promptly gets the Chlorophyll Cu acid crude after handling;
E, acetone removal of impurities: it is that solvent load treats fully to dissolve after-filtration by every gram 4-6ml solvent in the acetone solvent more than 95% that gained Chlorophyll Cu acid crude is dissolved in concentration, filter residue again with the acetone of same amount repeat to wash molten, filter once after, filter residue removes; Filtrate promptly gets the chlorophyll cupric acid dry product behind the fine purifiation one time after then placing and distilling recovery acetone under 60 ° of-70 ℃ of temperature;
F, pure eccysis are assorted: it is in the ethanol more than 95% that above-mentioned gained chlorophyll cupric acid dry product is dissolved in concentration again, solvent load is every gram dry product 50-70ml ethanol, treat fully to dissolve after-filtration, filter residue removes, filtrate slowly adds in the distilled water of 10 times of total amount of alcohol, the limit edged stirs, finish to staticly settle and get the green copper Acid precipitation of leaf after 4 hours, after the filtration, filtrate being used to reclaimed ethanol, filter residue again through distilled water wash with after removing chlorion, drying treatment promptly gets the chlorophyll cupric acid elaboration under 70 ° of-80 ℃ of conditions.
2. press the production method of the described chlorophyll cupric acid of claim 1; It is characterized in that the filter residue after described saponification liquor separates washs 2 times with clear water continuously, each used clear water amount is the heavy 2-3 of clean silkworm excrement times.
3. press the production method of the described chlorophyll cupric acid of claim 1; It is characterized in that described slow adding copper sulphate powder, after its adding mode also can be dissolved in NaOH solution or ammonia solution with it, slowly add again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011289422A CN100404538C (en) | 2001-10-11 | 2001-10-11 | Production method of chlorophyll cupric acid and its sodium salt |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011289422A CN100404538C (en) | 2001-10-11 | 2001-10-11 | Production method of chlorophyll cupric acid and its sodium salt |
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| CN1412191A CN1412191A (en) | 2003-04-23 |
| CN100404538C true CN100404538C (en) | 2008-07-23 |
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| CNB011289422A Expired - Fee Related CN100404538C (en) | 2001-10-11 | 2001-10-11 | Production method of chlorophyll cupric acid and its sodium salt |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100390176C (en) * | 2004-10-12 | 2008-05-28 | 大连理工大学 | Method for extracting chlorophyl from silkworm faeces by microwave pretreatment and preparing chlorophyllin copper and sodium salts |
| CN101077871B (en) * | 2006-05-23 | 2011-11-30 | 罗海章 | Method for preparing copper chlorphyllin from silkworm excrement by using tap water |
| CN102229612B (en) * | 2011-04-20 | 2013-01-02 | 晨光生物科技集团天津有限公司 | Method for extracting chlorophyll Cu from silkworm excrements |
| CN102311441B (en) * | 2011-10-21 | 2014-02-26 | 四川通世达生物科技有限公司 | Production method of sodium copper chlorophyllin |
| CN103012415B (en) * | 2012-12-26 | 2015-06-10 | 江苏省中国科学院植物研究所 | Method for preparing copper chlorophyll and sodium salt thereof from silkworm excrement |
| CN103232456B (en) * | 2013-04-22 | 2016-05-25 | 江苏大学 | A kind of method of preparing chlorophyll cupric acid taking silkworm excrement as raw material |
| RU2611409C1 (en) * | 2016-03-15 | 2017-02-21 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Чувашский государственный университет имени И.Н. Ульянова" | Method for producing copper complex of chlorophyll |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063704A (en) * | 1991-12-29 | 1992-08-19 | 江西省林业科学研究所 | The method of chlorophyll copper sodium extracting from the leaf of bamboo |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063704A (en) * | 1991-12-29 | 1992-08-19 | 江西省林业科学研究所 | The method of chlorophyll copper sodium extracting from the leaf of bamboo |
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