CN102618069B - Method for extracting purified brown cotton pigment from cotton fiber - Google Patents
Method for extracting purified brown cotton pigment from cotton fiber Download PDFInfo
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Abstract
The invention relates to a method for extracting purified brown cotton pigment from cotton fiber, which comprises the steps of (1) cutting up and washing dried cotton fiber clean; (2) leaching the cotton fiber by using a sodium hydroxide solution; (3) performing reduced pressure distillation and filtration and extracting filtered fluid to obtain pigment preliminary purified liquid; (4) performing reduced pressure distillation and filtration once again and obtaining pigment liquid through alkali solution and acid isolation; (5) adding hydrochloric acid into the pigment liquid dropwise till precipitation is produced, separating the liquid, removing water phase, further adding sodium hydroxide dropwise till the pigment is dissolved, separating the liquid and retaining the water phase; and (6) adding hydrochloric acid into the water phase dropwise till the pigment is precipitated completely, removing supernatant through centrifugation and performing reduced pressure drying to obtain a brown pigment purified product. The method for extracting the purified brown cotton pigment from the cotton fiber is quick, effective, simple in operation, economic and practical, establishes the foundation for study on pigment chemical nature and forming mechanism and facilitates structural analysis of the pigment and breeding of brown cotton seeds.
Description
Technical field
The present invention relates to a kind of natural compounds extraction and purification process field, specifically a kind of method of from cotton fibre, extracting purifying brown cotton pigment.
Background technology
Natural color cotton is the cotton that contains the specific type of natural pigment in the cotton fibre, because its natural pigment avoids in the fabrication processes adding environmental pollution that chemical dye causes and chemical dye clothes to the harm of human body, favored by people.Studying the chemical nature of colored cotton pigment, and then measure its pathways metabolism, is the key that further improves the colorful cotton fibre quality.
Wang Xuede, Li Yueyou, 2002, the research of the extraction of colorful cotton fibre pigment and measuring method, journal of Zhejiang university, 28 (6): the mature fibers that once proposed in the 596-600 document with white cotton, brown cotton and green cotton is material, with organic solvent (ethanol, ether, dimethylbenzene), acid, basic solution, and HNO3/ ethanolic soln extract the pigment in the different colours fiber respectively.The result shows that 3 kinds of organic solvents all can not extract fiber pigment; All the coloring matter in the fiber can not be extracted with acid, alkaline solution and the processing of heating; Pigment in the brown and green fiber can use HNO3: ethanol (1: 4) extraction, pigment content in the extracting solution can the size according to absorption value be estimated under the 412nm wavelength, but for example containing protein and the non-pigmented phenolic compound of phenyl ring, the compound that contains phenyl ring all might form interference to this method, the extracting method that white cotton is identical, at the 412nm place certain absorption is arranged also, when measuring colored cotton pigment content, be difficult to find the white cotton consistent with the cotton hereditary basis of colour to compare, so this method has certain limitation in the scope of application.
The pigment of inquiring into the brown cotton fiber extracts, purifying, and the chemical property of pigment made preliminary evaluation, the preliminary chemical structure of inferring the brown cotton fiber pigment, for the chemical nature of research pigment is laid a good foundation, for next step formation mechanism of studying pigment provides theoretical foundation, and then help structural analysis and the brown cotton breeding of pigment.
Summary of the invention:
The technical problem to be solved in the present invention provides a kind of method of extracting purifying brown cotton pigment fast from cotton fibre.
The inventive method comprises following steps:
1, extract the method for purifying brown cotton pigment from cotton fibre, its feature is being carried out as follows,
A. peel off ripe cotton fibre, dry to constant weight for 80 ℃ in the placement baking oven;
B. take by weighing 0.5g steps A cotton fibre, shred the back and clean with ultrapure water, with 0.05mol/L-0.15mol/L salt acid soak 1-2h, distilled water flushing is to neutral;
C. the sodium hydroxide solution that adds 4-6 times of volumetric concentration 0.5%-1.5% in the step B, 55 ℃ of-65 ℃ of water-baths are extracted; Collect extracting solution when liquid color to be extracted is dark; Extract repeatedly by above-mentioned steps that to be collected into solution colourless, united extraction liquid is adjusted to neutrality with 0.05mol/L-0.15mol/L hydrochloric acid;
D. the extracting solution that step C collect is merged is removed moisture to crystalline particulate occurring with 55 ℃ of-65 ℃ of underpressure distillation of Rotary Evaporators, to be cooled after the room temperature filter paper filtering, get filtered liquid;
E. use trichloromethane, sherwood oil extracts filtered liquid 2-4 time respectively, and organic phase and water fully mix with magnetic agitation, and after leaving standstill, the water intaking phase obtains pigment preliminary purification liquid;
F. above-mentioned refined solution is stopped evaporation, filter paper filtering behind the cool to room temperature when 55 ℃ of-65 ℃ of reduction vaporizations extremely just crystallization occurred again;
G. progressively dripping 2mol/L-4mol/L hydrochloric acid to pigment in the step F filtrate precipitates fully, 8000r/min is centrifugal, and 10min removes supernatant, progressively dripping 0.5%-1.5% sodium hydroxide to pigementation again dissolves fully, the centrifugal 10min of 8000r/min goes precipitation, so " acid heavy alkali molten " 2-4 time gets pigment solution;
H. progressively drip 2mol/L-4mol/L hydrochloric acid to precipitation in the pigment solution and separate out, add isopyknic ethyl acetate, magnetic force fully stirs, the separating funnel phase of anhydrating; Progressively drip 0.5%-1.5% sodium hydroxide again till the pigment dissolving; And add an amount of ultrapure water, and make water and organic phase be equal-volume, magnetic force fully stirs, and separatory keeps water;
I. progressively drip 2mol/L-4mol/L hydrochloric acid to pigment to water at last and precipitate fully, 8000r/min is centrifugal, and 10min removes supernatant, with ultrapure water wash out 55 ℃ of-65 ℃ of decompressions of post precipitation dry brown pigments purifying thing.
Beneficial effect of the present invention is embodied in:
The progress of brown cotton breeding at present is slower, and key is not clear to the chemical nature of pigment and formation mechanism.About the heredity of brown cotton pigment, different scholar's conclusion differences, the reason of one of them is pigment not to be carried out quantitative analysis.The present invention for the chemical nature of research pigment is laid a good foundation, and then helps structural analysis and the brown cotton breeding of pigment by pigment extraction, purifying and UV spectroscopic analysis thereof to the brown cotton fiber, the inventive method is quick, weak point consuming time, and purity is higher, do not destroy brown pigments, economical and effective.
Embodiment:
The present invention will be further described in detail below in conjunction with embodiment:
Following embodiment material is No. 1, brown color selection in the dark brown kind, and hand pulls peels off ripe cotton fibre, places in the baking oven 80 ℃ and dries to constant weight, and is standby.
Embodiment 1:
Take by weighing 0.5g brown cotton fiber, clean, shred the back and clean with ultrapure water, with the 0.05mol/L-0.15mol/L salt acid soak 1-2h about 100ml, distilled water flushing is to neutral; Under 55 ℃ condition, sodium hydroxide lixiviate with 4-6 times of volumetric concentration 0.5%, when color is dark in the bottle to be extracted, filter, collect extracting solution, extract repeatedly by above-mentioned steps that to be collected into solution colourless, united extraction liquid, and extracting solution is adjusted to neutrality with the hydrochloric acid of 0.05mol/L, use 55 ℃ of reduction vaporizations of Rotary Evaporators to small volume again, stop evaporation when in revolving bottle, just crystallization having occurred, treat to filter under the pigment extract cool to room temperature, pigment extract changes in the separating funnel again, extract respectively 2 times with trichloromethane and sherwood oil, organic phase and water fully mix with magnetic agitation, leave standstill 1h again after, the water intaking phase obtains pigment preliminary purification liquid.With above-mentioned refined solution again 55 ℃ of reduction vaporizations to small volume, the cool to room temperature after-filtration.Progressively drip 2mol/L hydrochloric acid to pigment in the filtrate and precipitate fully, 8000r/min is centrifugal, and 10min removes supernatant.Progressively add 0.5% dissolution of sodium hydroxide again to the pigment perfect solution, the centrifugal 10min of 8000r/min goes precipitation, " the heavy alkali of acid is molten " like this 2 times.Drip 2mol/L hydrochloric acid to precipitation in the pigment solution and separate out, add isopyknic ethyl acetate, magnetic force fully stirs, the separating funnel phase of anhydrating.Drip 0.5% sodium hydroxide and an amount of ultrapure water in ethyl acetate, make water and organic phase be equal-volume, magnetic force fully stirs, and separatory keeps water.Drip 2mol/L salt Acid precipitation pigment to water at last, 8000r/min is centrifugal, and 10min removes supernatant, with ultrapure water wash out 55 ℃ of decompressions of post precipitation dry purifying thing 691.2 μ g; The purifying thing is carried out the UV spectral detection, determining instrument TU1800SPC (the general universal apparatus of analysing in Beijing)), 510nm, unimodal, absorbing by force and not having assorted peak just proves that gained is brown pigments purifying thing.
Annotate: when brown pigments concentration is big, brown pigments aqueous solution UV spectrum shows stronger absorption near wavelength 230nm, 316nm, 385nm, but these 3 absorption peaks are along with the variation of concentration is stable inadequately, these 3 absorption peaks are in the ultraviolet region simultaneously, be subjected to the influence of impurity bigger, if select 1 in these 3 wavelength, materials such as protein, carbohydrate all have certain interference in the pigment coarse body fluid, and buffered soln also has certain influence to measuring.Though wavelength 510nm place absorption peak is not too strong, but the content of pigment and linear relationship are good, the accuracy height, impurity in the pigment crude extract is noiseless to measuring thing simultaneously, the ammonia damping fluid is to measuring also not influence, so the crude extract of pigment can directly be measured pigment content, brings great convenience to mensuration.
Embodiment 2:
Take by weighing 0.5g brown cotton fiber, clean, shred the back and clean with ultrapure water, with the 0.05mol/L-0.15mol/L salt acid soak 1-2h about 100ml, distilled water flushing is to neutral; Under 60 ℃ condition, sodium hydroxide lixiviate with 4-6 times of volumetric concentration 1%, when color is dark in the bottle to be extracted, filter, collect extracting solution, extract repeatedly by above-mentioned steps that to be collected into solution colourless, united extraction liquid, and extracting solution is adjusted to neutrality with the hydrochloric acid of 0.1mol/L, use 60 ℃ of reduction vaporizations of Rotary Evaporators to small volume again, stop evaporation when in revolving bottle, just crystallization having occurred, treat to filter under the pigment extract cool to room temperature, pigment extract changes in the separating funnel again, extract respectively 3 times with trichloromethane and sherwood oil, organic phase and water fully mix with magnetic agitation, leave standstill 1h again after, the water intaking phase obtains pigment preliminary purification liquid.With above-mentioned refined solution again 60 ℃ of reduction vaporizations to small volume, the cool to room temperature after-filtration.Drip 3mol/L salt Acid precipitation pigment in filtrate, 8000r/min is centrifugal, and 10min removes supernatant.Add 1% dissolution of sodium hydroxide pigementation again, the centrifugal 10min of 8000r/min goes precipitation, " the heavy alkali of acid is molten " like this 3 times.Drip 3mol/L hydrochloric acid to precipitation in the pigment solution and separate out, add isopyknic ethyl acetate, magnetic force fully stirs, the separating funnel phase of anhydrating.Drip 1% sodium hydroxide and an amount of ultrapure water in ethyl acetate, make water and organic phase be equal-volume, magnetic force fully stirs, and separatory keeps water.Drip 3mol/L salt Acid precipitation pigment to water at last, 8000r/min is centrifugal, and 10min removes supernatant, with ultrapure water wash out 60 ℃ of decompressions of post precipitation dry brown pigments purifying thing 703.6 μ g.
Embodiment 3:
Take by weighing 0.5g brown cotton fiber, clean, shred the back and clean with ultrapure water, with the 0.05mol/L-0.15mol/L salt acid soak 1-2h about 100ml, distilled water flushing is to neutral; Under 65 ℃ condition, sodium hydroxide lixiviate with 1.5%, when color is dark in the bottle to be extracted, filter, collect extracting solution, extract repeatedly by above-mentioned steps that to be collected into solution colourless, united extraction liquid, and extracting solution is adjusted to neutrality with the hydrochloric acid of 0.15mol/L, use 65 ℃ of reduction vaporizations of Rotary Evaporators to small volume again, stop evaporation when in revolving bottle, just crystallization having occurred, treat to filter under the pigment extract cool to room temperature, pigment extract changes in the separating funnel again, extract respectively 4 times with trichloromethane and sherwood oil, organic phase and water fully mix with magnetic agitation, leave standstill 1h again after, the water intaking phase obtains pigment preliminary purification liquid.With above-mentioned refined solution again 65 ℃ of reduction vaporizations to small volume, the cool to room temperature after-filtration.Drip 4mol/L salt Acid precipitation pigment in filtrate, 8000r/min is centrifugal, and 10min removes supernatant.Add 1.5% dissolution of sodium hydroxide pigementation again, the centrifugal 10min of 8000r/min goes precipitation, " the heavy alkali of acid is molten " like this 4 times.Drip 4mol/L hydrochloric acid to precipitation in the pigment solution and separate out, add isopyknic ethyl acetate, magnetic force fully stirs, the separating funnel phase of anhydrating.Drip 1.5% sodium hydroxide and an amount of ultrapure water in ethyl acetate, make water and organic phase be equal-volume, magnetic force fully stirs, and separatory keeps water.Drip 4mol/L salt Acid precipitation pigment to water at last, 8000r/min is centrifugal, and 10min removes supernatant, with ultrapure water wash out 65 ℃ of decompressions of post precipitation dry brown pigments purifying thing 687.1 μ g.
Claims (1)
1. extract the method for purifying brown cotton pigment from cotton fibre, its feature is being carried out as follows,
A. peel off ripe cotton fibre, dry to constant weight for 80 ℃ in the placement baking oven;
B. take by weighing 0.5g steps A cotton fibre, shred the back and clean with ultrapure water, with 0.05 mol/L-0.15 mol/L salt acid soak 1-2h, distilled water flushing is to neutral;
C. the sodium hydroxide solution that adds 4-6 times of volumetric concentration 0.5%-1.5% in the step B, 55 ℃ of-65 ℃ of water-baths are extracted; Collect extracting solution when liquid color to be extracted is dark; Extract repeatedly by above-mentioned steps that to be collected into solution colourless, united extraction liquid is adjusted to neutrality with 0.05 mol/L-0.15 mol/L hydrochloric acid;
D. the extracting solution that step C collect is merged is removed moisture to crystalline particulate occurring with 55 ℃ of-65 ℃ of underpressure distillation of Rotary Evaporators, to be cooled after the room temperature filter paper filtering, get filtered liquid;
E. extract filtered liquid 2-4 time respectively with trichloromethane, sherwood oil, organic phase and water fully mix with magnetic agitation, and after leaving standstill, the water intaking phase obtains pigment preliminary purification liquid;
F. above-mentioned refined solution is stopped evaporation, filter paper filtering behind the cool to room temperature when 55 ℃ of-65 ℃ of reduction vaporizations extremely just crystallization occurred again;
G. progressively dripping 2 mol/L-, 4 mol/L hydrochloric acid to pigments in the step F filtrate precipitates fully, 8000 r/min are centrifugal, and 10min removes supernatant, progressively dripping 0.5%-1.5% sodium hydroxide to pigementation again dissolves fully, the centrifugal 10min of 8000 r/min goes precipitation, so " acid heavy alkali molten " 2-4 time gets pigment solution;
H. progressively drip 2 mol/L-, 4 mol/L hydrochloric acid to precipitation in the pigment solution and separate out, add isopyknic ethyl acetate, magnetic force fully stirs, the separating funnel phase of anhydrating; Progressively dripping 0.5%-1.5% sodium hydroxide to pigment again is dissolved in till the water; And add an amount of ultrapure water, and make water and organic phase be equal-volume, magnetic force fully stirs, and separatory keeps water;
I. progressively drip 2 mol/L-, 4 mol/L hydrochloric acid to pigments to water at last and precipitate fully, 8000 r/min are centrifugal, and 10min removes supernatant, with ultrapure water wash out 55 ℃ of-65 ℃ of decompressions of post precipitation dry brown pigments purifying thing.
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| JP3262875B2 (en) * | 1992-12-01 | 2002-03-04 | 宏樹 宮松 | Manufacturing method of tea-dyed fiber products |
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| CN1912010A (en) * | 2005-08-11 | 2007-02-14 | 青岛海联植物科技研究所 | Method for extracting natural dye from rheum officinate root, leaf |
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