CN103012415B - Method for preparing copper chlorophyll and sodium salt thereof from silkworm excrement - Google Patents
Method for preparing copper chlorophyll and sodium salt thereof from silkworm excrement Download PDFInfo
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- CN103012415B CN103012415B CN201210570056.1A CN201210570056A CN103012415B CN 103012415 B CN103012415 B CN 103012415B CN 201210570056 A CN201210570056 A CN 201210570056A CN 103012415 B CN103012415 B CN 103012415B
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Abstract
The invention discloses a method for preparing copper chlorophyll and a sodium salt thereof from silkworm excrement. The method comprises the following steps of (1) washing the silkworm excrement with water; (2) extracting the silkworm excrement by using acidic ethanol containing CuSO4, standing an extracting solution in cold and filtering; (3) taking a macroporous resin, loading the extracting solution obtained from the step (2), eluting firstly with water and low concentration ethanol and then with an alkaline ethanol solution and collecting the alkaline ethanol eluant; (4) concentrating the alkaline ethanol eluant obtained from the step (3) to a low ethanol concentration, filtering insoluble substances, adjusting a pH value to an acidic state, filtering precipitated precipitate, washing with water until the pH value is in a neutral state, so that the copper chlorophyll is obtained; and (5) adjusting a pH value of the copper chlorophyll obtained from the step (4) to 10-11 by using a NaOH solution, stirring, filtering, and drying the filtrate by concentrating under a reduced pressure or spray drying to obtain the sodium copper chlorophyll. A finished product prepared by the method has high purity, and the method is simple in process and low in cost.
Description
Technical field
It take silkworm excrement as the method that raw material prepares Chlorophyll Cu and sodium salt thereof that the present invention is specifically related to a kind of.
Background technology
Containing a large amount of chlorophyll (chlorophyll) in silkworm excrement.Chlorophyll belongs to magnesium porphyrin cyclic complexes, is generally fat-soluble, not soluble in water, and the magnesium ion in chlorophyll molecule is easily replaced by copper, iron, cobalt plasma and becomes phyllins (chlorophyll derivatives, CPD).Chlorophyll itself is to chemical factors extremely unstable such as light, heat, acid, alkali, enzymes, and its derivative is then relatively stable, so chlorophyll is generally made into derivative.Chlorophyll ketonic acid and sodium salt thereof use the widest a kind of phyllins, and it has a very wide range of application in chemical industry, medicine, food, health care etc.
Prepare sodium copper chlorophyllin both at home and abroad and mainly contain several typical process: one is lixiviate, saponification, copper generation, another kind is lixiviate, copper generation, saponification.Because the chlorophyll of underivatized is unstable to light and heat, so easily cause the destruction of leaching process Determination of Chlorophyll and affect finished product content.And the dedoping step after saponification often uses the inflammable toxic organic solvents such as benzene, gasoline, sherwood oil to extract, and easily produces environmental pollution, and have high requirements to production plant explosion-proof in production process.
Summary of the invention
The object of the invention is to overcome the defect in existing technique, design a kind of more simple and practical, production Chlorophyll Cu of safety and environmental protection and the processing method of sodium salt thereof.
In order to achieve the above object, the invention provides a kind of method preparing Chlorophyll Cu and sodium salt thereof from silkworm excrement, the method comprises the following steps:
(1) silkworm excrement use water is rinsed, remove silt;
(2) with containing CuSO
4acidic ethanol be solvent extraction silkworm excrement, extracting solution refrigeration leave standstill, filter; Described ethanol is with inorganic acid for adjusting pH to 1-4, and consumption is 4-10 times of silkworm excrement medicinal material amount, the CuSO added
4be 1: 100-3: 100 with the ratio of medicinal material weight;
(3) get nonpolar or low-pole macroporous resin, by the extracting solution loading obtained in step (2), with water and low alcoholic degree ethanol elution, discard elutriant; Use 60-80% alkaline ethanol solution wash-out again, collect elutriant; Described nonpolar or low-pole macroporous resin comprises D101, HPD-100, AB-8, X-5, NKA; The pH scope of described 60-80% alkaline ethanol is 10-12.
(4) the alkaline ethanol elutriant that step (3) obtains is concentrated into determining alcohol 10-30%, filters insolubles.Filtrate adds acid for adjusting pH to 2-3, the precipitation separated out is filtered, and be washed with water to pH in neutral, cryodrying, obtains chlorophyll ketone.
(5) the chlorophyll ketone of step (4) gained 5-10%NaOH solution is regulated PH10-11, stir, make it fully react.Filter, filtrate is dry with concentrating under reduced pressure, or spraying dry, obtains chlorophyll copper sodium.
Wherein, in step (2), extracting method is: every 1 kilogram of silkworm excrement adds the ethanol that 4-10L concentration is 80-95%, adds hydrochloric acid or sulfuric acid adjustment pH1-4, gets 10-30gCuSO
4add extracting solution after adding a small amount of water dissolution, 60-80 DEG C of refluxing extraction 4-8 hour, united extraction liquid, extracting solution refrigeration leaves standstill, and filters.Optimum extracting method is: every kilogram of silkworm excrement adds the ethanol that 8L concentration is 90%, salt adding acid for adjusting pH 2,12g CuSO
4add in extracting solution with a small amount of water dissolution, 80 DEG C of refluxing extraction 6 hours, filter, obtain extracting solution, extracting solution refrigeration leaves standstill, and filters.
Step (3) gets nonpolar or low-pole macroporous resin, and the weight ratio of macroporous resin and silkworm excrement is 1: 1-1: 3; First adopt water and low alcoholic degree ethanol elution, be eluted to elutriant substantially colourless, depolarization impurity, then with macroporous resin weight 3-10 60-80% alkaline ethanol solution wash-out doubly, collect alkaline ethanol elutriant.
The present invention has the following advantages:
(1) because chlorophyll is unstable to photo-thermal, traditional technology generally adopts organic solvent normal temperature leach extraction method, and due to acetone, perviousness is stronger at normal temperatures, general employing acetone is solvent, but acetone price is more expensive, there is certain toxicity, and be inflammable and explosively not suitable for factorial praluction.Adopt thermal reflow to extract and can significantly improve chlorophyllous extraction yield, but chlorophyll can be caused after heating unstable, it is relevant that this and the easy de-magging of chlorophyll heat generate phoeophytin.The present invention is to add CuSO
4acidic ethanol be that solvent carries out chlorophyllous extraction, carry out putting copper in leaching process, make to be converted into heat stable Chlorophyll Cu to heat-labile chlorophyll magnesium, chlorophyllous extraction yield is increased by the method increasing Extracting temperature, and acidifying is put copper and chlorophyll and extract and complete simultaneously, simplify the operation technique, and the present invention take ethanol as solvent, can extraction cost be reduced, increase production security.
(2) chlorophyll can propose high polar impurity in some in organic solvent extraction process simultaneously, as: flavones, polyose, and low polar impurity, as: pohytol, xenthophylls, carotenoid etc.For the impurity of middle high polarity, traditional method generally adopts with water or the impurity elimination of low alcoholic degree washing with alcohol after copper, and the method owing to easily impurity inclusion being affected impurity-eliminating effect in the Chlorophyll Cu of separating out during copper, and then affects finished product content.For low polar impurity, traditional technology generally adopts uses organic solvent by after chlorophyll saponification, as the low polar solvent extracting process such as benzene, gasoline, sherwood oil carry out removal of impurities, the method need use a large amount of organic solvent, these organic solvents are all poisonous and inflammable and explosive, easily produce environmental pollution in production process, and production plant explosion-proof is had high requirements.Macroporous adsorbent resin has good macroreticular structure and larger specific surface area, can by physical adsorption adsorb organic compound selectively from solution.The present invention adopts macroporous resin to refine chlorophyll, adopts water and low-concentration ethanol, carries out wash-out removal of impurities to high polar impurity in extraction.Adopt alkaline ethanol to carry out wash-out to chlorophyll, low polar impurity, as pohytol, xenthophylls, carotenoid etc., due to can not saponification, to be still adsorbed on resin by wash-out not out, chlorophyll are refined.Adopt Amberlyst process to refine, eliminate the step of saponification and organic solvent extraction impurity elimination, avoid using poisonous inflammable and explosive organic solvent, improve security and the economy of production process; And elution program is simple, easy and simple to handle, technique is relatively simple and easy.
(3) have the technique report adopting macroporous resin to refine chlorophyll, but many employing ether or ethyl acetate are that solvent carries out wash-out, these two kinds of solvents all have certain toxicity, and inflammable and explosive.The present invention adopts alkaline ethanol to be eluting solvent pair, and elution efficiency is close with ethyl acetate, and Suitable commercial is produced, and safety and environmental protection.
Embodiment
Optimal process embodiment
1. different solvents compares
1.1 Chlorophyll Cu assays
Precision pipettes different extraction process chlorophyll extracting solution 0.2mL, to in 10mL measuring bottle, scale is diluted to respectively with Extraction solvent, and be blank with Extraction solvent, absorbancy is measured in 650nm and 413nm place, be multiplied by extension rate respectively, divided by sampling amount, with the dulling luminosity ratio comparatively different process content of every g medicinal material extract Chlorophyll Cu.
1.2 Different Extraction Method
Precision takes 5.0g silkworm excrement 3 parts, adds 95% ethanol 50mL successively, 3mL 2.5%CuSO
4, add HCl and regulate pH to 2 ~ 3.Respectively with 80 DEG C of water-bath refluxing extraction 2h, normal temperature lixiviate 24h, supersound extraction 50min, filter, obtain extracting solution, detects absorbancy, calculates content.
Different Extraction Method gained extracting solution the results are shown in Table 1, and viewed from result, heating and refluxing extraction gained chlorophyll content is the highest, and supersound extraction is taken second place, and normal temperature lixiviate content is minimum.
Table 1 Different Extraction Method chlorophyll absorbancy result
* A
413, A
650represent the absorbancy of the Chlorophyll Cu that every g silkworm excrement extracts respectively, also same below
1.3 different solvents
Precision takes 5.0g silkworm excrement 5 parts, adds 50mL 80% acetone respectively, 70% ethanol, 80% ethanol, 90% ethanol, 95% ethanol, then adds 3mL2.5%CuSO successively
4, add HCl and regulate pH to 2 ~ 3.80 DEG C of water-bath refluxing extraction 2h, filter, obtain extracting solution, detect absorbancy, calculate content.
Different Extraction Method gained extracting solution the results are shown in Figure, and from the results are shown in, 90% extraction using alcohol gained Chlorophyll Cu content is the highest, and 80% extraction using alcohol takes second place, all higher than 80% acetone extraction.
Table 2 Different Extraction Method Chlorophyll Cu absorbancy result
2. the different eluting solvent of macroporous resin is selected
The preparation of 2.1 silkworm excrement chlorophyll extracting solutions
Take 100g silkworm excrement, add 90% ethanol 800ml after adding water-wet, add 12mL10%CuSO
4solution, hydrochloric acid regulates PH2-3,80 DEG C of heating and refluxing extraction 6 hours.Filter, extracting solution refrigeration leaves standstill, and again filters, obtains extracting solution.
The mensuration of 2.2 different solvents desorption efficiencies
Precision takes NaOH 0.1g totally 6 parts, adds 50%, 60%, 70%, 80%, 95% dissolve with ethanol respectively, is configured to the alkaline ethanol solution of different determining alcohol.
Take pretreated D101 dried resin 6g, put in triangular flask, precision pipettes 150.00 mL chlorophyll extracting solutions, 120rmin
-1vibration 24h, fully filters after absorption.To adsorb saturated resin, and take 6 parts respectively, every part of 1.000g, load in 6 triangular flasks, in triangular flask, precision adds 50%, 60%, 70%, 80%, 95% alkaline ethanol and each 25mL of ethyl acetate respectively.120rmin
-1vibration 24h, carries out desorption, filters, and measures the Chlorophyll Cu content in filtrate by preceding method.
Desorption amount (mgg
-1)=(stripping liquid chlorophyll ketone content × stripping liquid volume)/resin quality
Desorption efficiency (%)=desorption amount/adsorptive capacity × 100%
Table 2 different solvents is to the desorption effect of chlorophyll ketone
Each solvent is variant to chlorophyllous desorption effect.Table 2 result shows, and alkaline ethanol increases along with determining alcohol degree increases desorption rate, but after being increased to 70% alkaline ethanol, desorption rate is on a declining curve again, and 70% alkaline ethanol desorption rate is close with ethyl acetate.
Product embodiments 1:
Get silkworm excrement 1.0kg, rinse with water, remove silt, add the ethanol that 8L concentration is 90%, salt adding acid for adjusting pH 2, add 12g CuSO
4add in extracting solution with a small amount of water dissolution, 80 DEG C of heating and refluxing extraction 6 hours, filter, obtain extracting solution.Extracting solution refrigeration leaves standstill 24h, filters, obtains sample solution.Get 500g D101 macroporous resin, silkworm excrement chlorophyll extracting solution loading, first with water and 50% ethanol elution decon, be eluted to elutriant substantially colourless, discard elutriant.Separately get 70% ethanol, add NaOH and regulate PH to 11, become alkaline ethanol, carry out wash-out with 3Kg alkaline ethanol, collect elutriant.Elutriant is concentrated into determining alcohol 20-30%, filters insolubles.Add acid for adjusting pH to 2-3, the precipitation separated out filtered, be washed with water to pH in neutral, cryodrying, obtains chlorophyll ketone.The chlorophyll ketone of gained regulates PH10-11 with 10%NaOH solution, stirs, makes it fully react.Filter, filtrate spraying dry, obtains chlorophyll copper sodium 11.2g, and yield is 1.12%.According to GB 3262-1982, the quality of product is measured.Gained chlorophyll copper sodium pH=9.9, E
405nm=611, delustring ratio (E
405/ E
630)=3.39, total copper amount=5.4%, free copper=0.001%.After testing, product all items all meets national standard.
Product embodiments 2:
Get silkworm excrement 1.0kg, rinse with water, remove silt, add the ethanol that 4L concentration is 95%, salt adding acid for adjusting pH 1, add 10g CuSO
4add in extracting solution with a small amount of water dissolution, 70 DEG C of heating and refluxing extraction 4 hours, filter, obtain extracting solution.Extracting solution refrigeration leaves standstill 24h, filters, obtains sample solution.Get 330g HPD-100 macroporous resin, silkworm excrement chlorophyll extracting solution loading, first with water and 30% ethanol elution decon, be eluted to elutriant substantially colourless, discard elutriant.Separately get 70% ethanol, add NaOH and regulate PH to 10, become alkaline ethanol, carry out wash-out with 3.3Kg alkaline ethanol, collect elutriant.Elutriant is concentrated into determining alcohol 20-30%, filters insolubles.Add acid for adjusting pH to 2-3, the precipitation separated out filtered, be washed with water to pH in neutral, cryodrying, obtains chlorophyll ketone.The chlorophyll ketone of gained regulates PH10-11 with 10%NaOH solution, stirs, makes it fully react.Filter, filtrate is dry with concentrating under reduced pressure, and obtain chlorophyll copper sodium 10.1g, yield is 1.01%.According to GB 3262-1982, the quality of product is measured.Gained chlorophyll copper sodium pH=10.2, E
405nm=591, delustring ratio (E
405/ E
630)=3.51, total copper amount=5.0%, free copper=0.002%.After testing, product all items all meets national standard.
Product embodiments 3:
Get silkworm excrement 1.0kg, rinse with water, remove silt, add the ethanol that 10L concentration is 80%, salt adding acid for adjusting pH 4, add 30g CuSO
4add in extracting solution with a small amount of water dissolution, 80 DEG C of heating and refluxing extraction 6 hours, filter, obtain extracting solution.Extracting solution refrigeration leaves standstill 12h, filters, obtains sample solution.Get 1000g NKA macroporous resin, silkworm excrement chlorophyll extracting solution loading, first with water and 50% ethanol elution decon, be eluted to elutriant substantially colourless, discard elutriant.Separately get 60% ethanol, add NaOH and regulate PH to 11, become alkaline ethanol, carry out wash-out with 3Kg alkaline ethanol, collect elutriant.Elutriant is concentrated into determining alcohol 10-20%, filters insolubles.Add acid for adjusting pH to 2-3, the precipitation separated out filtered, be washed with water to pH in neutral, cryodrying, obtains chlorophyll ketone.The chlorophyll ketone of gained regulates PH10-11 with 10%NaOH solution, stirs, makes it fully react.Filter, filtrate spraying dry, obtains chlorophyll copper sodium 9.94g, and yield is 0.99%.According to GB 3262-1982, the quality of product is measured.Gained chlorophyll copper sodium pH=10.2, E
405nm=581, delustring ratio (E
405/ E
630)=3.83, total copper amount=4.7%, free copper=0.003%.After testing, product all items all meets national standard.
Product embodiments 4:
Get silkworm excrement 1.0kg, rinse with water, remove silt, add the ethanol that 8L concentration is 90%, salt adding acid for adjusting pH 3, add 20g CuSO
4add in extracting solution with a small amount of water dissolution, 60 DEG C of heating and refluxing extraction 4 hours, filter, obtain extracting solution.Extracting solution refrigeration leaves standstill 24h, filters, obtains sample solution.Get 1000g X-5 macroporous resin, silkworm excrement chlorophyll extracting solution loading, first with water and 50% ethanol elution decon, be eluted to elutriant substantially colourless, discard elutriant.Separately get 60% ethanol, add NaOH and regulate PH to 10, become alkaline ethanol, carry out wash-out with 3Kg alkaline ethanol, collect elutriant.Elutriant is concentrated into determining alcohol 20-30%, filters insolubles.Add acid for adjusting pH to 2-3, the precipitation separated out filtered, be washed with water to pH in neutral, cryodrying, obtains chlorophyll ketone.The chlorophyll ketone of gained regulates PH10-11 with 5%NaOH solution, stirs, makes it fully react.Filter, filtrate spraying dry, obtains chlorophyll copper sodium 9.74g, and yield is 0.97%.According to GB 3262-1982, the quality of product is measured.Gained chlorophyll copper sodium pH=10.4, E
405nm=582, delustring ratio (E
405/ E
630)=3.76, total copper amount=4.9%, free copper=0.004%.After testing, product all items all meets national standard.
Product embodiments 5:
Get silkworm excrement 1.0kg, rinse with water, remove silt, add the ethanol that 8L concentration is 90%, salt adding acid for adjusting pH 2, add 30g CuSO
4add in extracting solution with a small amount of water dissolution, 80 DEG C of heating and refluxing extraction 8 hours, filter, obtain extracting solution.Extracting solution refrigeration leaves standstill 24h, filters, obtains sample solution.Get 1000gAB-8 macroporous resin, silkworm excrement chlorophyll extracting solution loading, first with water and 50% ethanol elution decon, be eluted to elutriant substantially colourless, discard elutriant.Separately get 80% ethanol, add NaOH and regulate PH to 12, become alkaline ethanol, carry out wash-out with 3Kg alkaline ethanol, collect elutriant.Elutriant is concentrated into determining alcohol 10-20%, filters insolubles.Add acid for adjusting pH to 2-3, the precipitation separated out filtered, be washed with water to pH in neutral, cryodrying, obtains chlorophyll ketone.The chlorophyll ketone of gained regulates PH10-11 with 10%NaOH solution, stirs, makes it fully react.Filter, filtrate spraying dry, obtains chlorophyll copper sodium 9.94g, and yield is 9.94%.According to GB 3262-1982, the quality of product is measured.Gained chlorophyll copper sodium pH=10.5, E
405nm=586, delustring ratio (E
405/ E
630)=3.61, total copper amount=4.8%, free copper=0.003%.After testing, product all items all meets national standard.
Claims (6)
1. silkworm excrement prepares a preparation method for Chlorophyll Cu and sodium salt thereof, it is characterized in that: the method comprises the following steps:
(1) silkworm excrement use water is rinsed, remove silt;
(2) with containing CuSO
4acidic ethanol be solvent extraction silkworm excrement, extracting solution refrigeration leave standstill, filter; Described acidic ethanol consumption is 4-10 times of silkworm excrement medicinal material amount;
(3) get macroporous resin, by the extracting solution loading obtained in step (2), with water and ethanol elution, discard elutriant, then use alkaline ethanol solution wash-out, collect alkaline ethanol elutriant; Described alcohol concn is 30-50%; The determining alcohol of described alkaline ethanol is 60%-80%, and the pH scope of alkaline ethanol is 10-12;
(4) the concentrated most alcoholic degree 10-30% of alkaline ethanol elutriant step (3) obtained, filters insolubles; Filtrate adds acid for adjusting pH to 2-3, the precipitation separated out is filtered, and be washed with water to pH in neutral, cryodrying, obtains Chlorophyll Cu;
(5) Chlorophyll Cu of step (4) gained 5-10%NaOH solution is regulated PH10-11, stir, make it fully react, filter, filtrate is dry with concentrating under reduced pressure, or spraying dry, obtains chlorophyll copper sodium.
2. silkworm excrement according to claim 1 prepares the method for Chlorophyll Cu and sodium salt thereof, it is characterized in that: the described acidic ethanol pH of step (2) is 1-4.
3. silkworm excrement according to claim 1 prepares the method for Chlorophyll Cu and sodium salt thereof, it is characterized in that: the CuSO added in acidic ethanol in step (2)
4be 1:100-3:100 with the ratio of silkworm excrement weight in step (1).
4. silkworm excrement according to claim 1 prepares the method for Chlorophyll Cu and sodium salt thereof, it is characterized in that: the macroporous resin described in step (3) is nonpolar or low-pole macroporous resin, and macroporous resin model is selected from as D101, HPD-100, AB-8, X-5, NKA.
5. the method for Chlorophyll Cu and sodium salt thereof is prepared according to the arbitrary described silkworm excrement of Claims 1-4, it is characterized in that: in step (2), extracting method is the ethanolic soln that every kilogram of silkworm excrement adds that 4-10L concentration is 80-95%, add hydrochloric acid or sulfuric acid adjustment pH1-4, get 10-30g CuSO
4add extracting solution after adding a small amount of water dissolution, 60-80 DEG C of refluxing extraction 4-8 hour, united extraction liquid, extracting solution refrigeration leaves standstill, and filters.
6. the method for Chlorophyll Cu and sodium salt thereof is prepared according to the arbitrary described silkworm excrement of Claims 1-4, it is characterized in that: in step (3), the weight ratio of macroporous resin and the middle silkworm excrement of step (1) is 1:1-1:3, first adopt water and 30-50% alcoholic degree ethanol elution, be eluted to elutriant substantially colourless, discard elutriant, again with macroporous resin weight 3-10 60-80% alkaline ethanol solution wash-out doubly, collect alkaline ethanol elutriant.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103641837B (en) * | 2013-11-15 | 2016-03-23 | 云南瑞宝生物科技股份有限公司 | A kind of method of chlorophyll copper sodium extracting from silkworm excrement |
| CN106924250A (en) * | 2015-12-31 | 2017-07-07 | 武汉联合药业有限责任公司 | Purposes of the silkworm excrement sodium zinc chlorophyllin in treatment chronic inflam matory anemia medicine is prepared |
| CN106924247A (en) * | 2015-12-31 | 2017-07-07 | 武汉联合药业有限责任公司 | Purposes of the silkworm excrement sodium chromium chlorophyllin in treatment chronic inflam matory anemia medicine is prepared |
| CN106924248A (en) * | 2015-12-31 | 2017-07-07 | 武汉联合药业有限责任公司 | Purposes of the silkworm excrement sodium copper chlorophyllin in treatment chronic inflam matory anemia medicine is prepared |
| CN106924249A (en) * | 2015-12-31 | 2017-07-07 | 武汉联合药业有限责任公司 | Purposes of the silkworm excrement chlorophyll in treatment chronic inflam matory anemia medicine is prepared |
| CN107796684B (en) * | 2017-12-14 | 2021-01-12 | 汤臣倍健股份有限公司 | Method for detecting content of sodium copper chlorophyllin |
| CN113754671B (en) * | 2021-10-14 | 2022-08-09 | 云南博瑞生物科技有限公司 | Preparation method of sodium copper chlorophyllin |
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