CN102731513B - Method for extracting sodium copper chlorophyllin from wild deyeuxia angustifolia forage grass - Google Patents

Method for extracting sodium copper chlorophyllin from wild deyeuxia angustifolia forage grass Download PDF

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CN102731513B
CN102731513B CN201210144911.2A CN201210144911A CN102731513B CN 102731513 B CN102731513 B CN 102731513B CN 201210144911 A CN201210144911 A CN 201210144911A CN 102731513 B CN102731513 B CN 102731513B
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chlorophyll
copper
extraction
saponification
filtrate
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CN102731513A (en
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姚德坤
姚德利
张亚红
万莉
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Daxing'an Mountainrange Lin Gebei psychrophile Science and Technology Co., Ltd.
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GREAT XINGAN MOUNTAINS LINGEBEI ORGANIC FOOD CO Ltd
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Abstract

The invention belongs to the field of natural organic chemistry, and relates to a method for extracting chlorophyll from wild deyeuxia angustifolia forage grass and converting the chlorophyll into sodium copper chlorophyllin, and particularly to a new method, wherein the new method comprises adopting a two-step method to extract chlorophyll and grass protein, carrying out alkaline solution saponification on the paste chlorophyll, and replacing copper with sodium copper chlorophyllin. The method has the following advantages that: 1, the two-step method is adopted to extract chlorophyll, such that the time is shortened compared with the conventional method, and the active ingredient chlorophyll extraction rate is improved; 2, wild forage grass deyeuxia angustifolia in Daxinganling is adopted as the raw material, such that the local wild resources are comprehensively utilized, and two substances of grass protein and sodium copper chlorophyllin can be obtained; and 3, the method of the present invention has characteristics of simpleness, easy operation, simple process, low investment, and low production cost, and is suitable for large-scale production. With the method of the present invention, the two-step extraction method is adopted to extract chlorophyll, the grass is grinded and extracted, the filter residue is soaked and extracted to obtain the glass protein and the paste chlorophyll, alkaline solution saponification is performed, acidification is performed after extraction is performed, copper is replaced, and purifying is performed to obtain the sodium copper chlorophyllin.

Description

A kind of from wild leaflet camphor herbage the method for chlorophyll copper sodium extracting
Technical field:
The invention belongs to natural organic chemistry field, relate to and a kind ofly from wild leaflet camphor herbage, extract the method that chlorophyll changes into sodium copper chlorophyllin, particularly relate to a kind of two-step approach extracting chlorophyll and vegetable protein of utilizing, chlorophyll paste is through alkali lye saponification, and copper is replaced as the novel method of sodium copper chlorophyllin.
Background technology:
Daxing'an Mountainrange leaflet camphor grass, also claims to cover room grass with mat, is the leafy fast-growing grass class of thin stem, general grows wild, and in forest zone, by the ditch pool on ground, be low-lyingly located in growth, very luxuriant, some places are grown in flakes, and the same like the wheatland of plantation, output is very high.According to surveying and determination, leaflet camphor more than 30%, is the good feed of milk cow containing crude protein 10%~16%, crude fat 1%~2%, nitrogen-free extract.Leaflet camphor chlorophyll is water insoluble, is dissolved in organic solvent, and available multiple organic solvent, as extractions such as acetone, ethanol or dimethyl sulfoxide (DMSO).The multiplex silkworm faeces of domestic chlorophyll copper sodium extracting, the leaf of bamboo, Leaf of Japanese Banana are made raw material, and with Daxing'an Mountainrange fresh wild herbage leaflet camphor grass, make the report that has no of raw material.Therefore, meaning of the present invention is not only to fully utilize local wild resource, exploitation food dye new variety, and to the reference frame that made full use of similar sylvan life Resource Supply.
Summary of the invention:
The present invention adopts two-step approach extracting chlorophyll, blade of grass milling and extracting, and filter residue soaks and extracts, and obtains vegetable protein and chlorophyll paste, then through alkali lye saponification, after extraction, copper is put in acidifying, purifying becomes sodium copper chlorophyllin.The present invention is raw materials used is that Daxing'an Mountainrange is wild, without worrying raw material supply problem
Invention advantage is as follows:
1, the present invention adopts two-step approach extracting chlorophyll, and chlorophyll effective component extraction rate is high.
2, adopt Daxing'an Mountainrange Wild Grass leaflet camphor to make raw material, fully utilize local wild resource, can obtain two kinds of materials of vegetable protein and sodium copper chlorophyllin.
3, the inventive method is simple to operation, and technique is simple, and be applicable to people and produce, less investment, production cost is low.
For achieving the above object, the technical solution used in the present invention is: a kind of two-step approach extracting chlorophyll and vegetable protein of utilizing, and chlorophyll paste is through alkali lye saponification, and copper is replaced as the novel method of sodium copper chlorophyllin.Its step is as follows:
(1) chlorophyll is just carried:
Fresh leaflet camphor grass cuts off 3-5cm, and 6-8 times of 80-90% ethanol extracts, and adds mortar to grind to form homogenate, standing, filters to get filtrate, and uses alcohol flushing mortar, and filtrate merges;
(2) filter residue second extraction:
Filter residue, through squeezing machine, must be remained to fresh juice, filter, after all filtrate is merged, add gasoline, fully stir, be placed in respectively separating funnel, more than sufficient standing 2-3h, liquid is divided into three layers.
(3) obtain primary extract
Upper strata is oil reservoir, is blackish green, and lower floor is that yellow liquid claims water layer, and middle level is suspended on water layer, under upper strata, claims the greyish white beds of precipitation.Water layer, the greyish white beds of precipitation, oil reservoir are filtered respectively, and filter residue merges, and with distilled water wash, drains, and in 90-100 ℃ of oven dry, obtains vegetable protein; By oil reservoir decompression recycling ethanol and gasoline, obtain chlorophyll paste;
(4) saponification: with the leaf of 4 volumes, practice the sodium hydroxide solution that vegetarian feast seminal fluid adds the 5%-10% of 1 volume and carry out saponification, temperature 50-60 ℃, saponification 1h, stratification, lower floor is water capacity chlorophyll saponification liquor;
(5) extraction:
By chlorophyll saponification liquor petroleum ether extraction oil-soluble impurities, extraction secondary adds in equivalent sherwood oil fourth alcohol saponification liquor at every turn, stirs stratification, emits petroleum ether layer, obtains extraction liquid;
(6) put copper
Extraction liquid regulates pH value to subacidity, adds 20% copper sulfate solution, then is adjusted to pH value 2-3, keeps 30-60min at 60 ℃, fully puts copper.
(7) purifying:
Filter, by 90% washing with alcohol 1-2 time, washings merges with filtrate, and the water that doubles dilutes, and chlorophyll cupric acid can be separated out, and dries that to obtain the green copper of solid leaf sour, uses the Diluted Alcohol solution washing of 40-50% several times, is filtered dry and gets final product purifying.
(8) salify;
Add 5% sodium hydroxide solution, dissolved copper acid, is added to PH always and is till 11, and salification process is first early thick, with sodium hydroxide, adds, gradually thinning,, until during PH 11, retrogradation again again.After salify, filter, filter residue distilled water flushing 1-2 time, washings is incorporated in filtrate, 60-80 ℃ of vacuum hydro-extraction, obtains finished product.
Embodiment:
Embodiment 1: a kind of two-step approach extracting chlorophyll and vegetable protein of utilizing, and chlorophyll paste is through alkali lye saponification, and copper is replaced as the novel method of sodium copper chlorophyllin.Its step is as follows;
(1) fresh leaflet camphor grass 1000g cuts off 3cm, and 6 times of 80% ethanol extracts, and adds mortar to grind to form homogenate, standing, filters to get filtrate, and uses alcohol flushing mortar;
(2) by filter residue process squeezing machine, must remain fresh juice, filter, will after all filtrate merging, add gasoline, fully stir, be placed in respectively separating funnel, more than sufficient standing 2h, liquid is divided into three layers.
(3) upper strata is oil reservoir, is blackish green, and lower floor is that yellow liquid claims water layer, and middle level is suspended on water layer, under upper strata, claims the greyish white beds of precipitation.Water layer, the greyish white beds of precipitation, oil reservoir are filtered respectively, and filter residue merges, and with distilled water washing, drains, and in 90 ℃ of oven dry, obtains vegetable protein 82g; By oil reservoir decompression recycling ethanol and gasoline, obtain chlorophyll paste 5.89g;
(4) with 8% the sodium hydroxide solution that the chlorophyll alcohol liquid of 4 volumes adds 1 volume, carry out saponification, 55 ℃ of temperature, saponification 1h, stratification, lower floor is chlorophillins saponification liquor;
(5), by chlorophyll saponification liquor petroleum ether extraction oil-soluble impurities, extraction secondary adds equivalent sherwood oil in alcohol saponification liquor at every turn, stirs stratification, emits petroleum ether layer, obtains extraction liquid;
(6) extraction liquid regulates pH value to subacidity, adds 20% copper sulfate solution, then is adjusted at 2,60 ℃ of pH values and keeps 30min, fully puts copper.
(7) filter, with 90% washing with alcohol 1-2 time, washings and filtrate merging, the water that doubles dilutes, and chlorophyll cupric acid can be separated out, and dries that to obtain the green copper of solid leaf sour, and the Diluted Alcohol solution washing with 40% several times, is filtered dry and gets final product purifying.
(8) add 5% sodium hydroxide solution, dissolved copper acid, is added to PH always and is till 11, and salification process is first early thick, with sodium hydroxide, adds, gradually thinning,, until during PH 11, retrogradation again again.After salify, filter, filter residue distilled water flushing 1-2 time, washings is incorporated in filtrate, at 60 ℃, dries to obtain finished product 5.73g.
Case study on implementation 2:
(1) fresh leaflet camphor grass 1000g, cuts off 4cm, and 7 times of 85% ethanol extracts, and adds mortar to grind to form homogenate, standing, filters to get filtrate, and uses alcohol flushing mortar;
(2) by filter residue process squeezing machine, must remain fresh juice, filter, will after all filtrate merging, add gasoline, fully stir, be placed in respectively separating funnel, more than sufficient standing 3h, liquid is divided into three layers.
(3) upper strata is oil reservoir, is blackish green, and lower floor is that yellow liquid claims water layer, and middle level is suspended on water layer, under upper strata, claims the greyish white beds of precipitation.Water layer, the greyish white beds of precipitation, oil reservoir are filtered respectively, and filter residue merges, and with distilled water wash, drains, and in 90 ℃ of oven dry, obtains vegetable protein 83.7g; By oil reservoir decompression recycling ethanol and gasoline, obtain chlorophyll paste 5.93g;
(4) with 10% the sodium hydroxide solution that the chlorophyll alcohol liquid of 4 volumes adds 1 volume, carry out saponification, temperature 60 C, saponification 1h, stratification, lower floor is chlorophillins saponification liquor;
(5), by chlorophyll saponification liquor petroleum ether extraction oil-soluble impurities, extraction secondary adds equivalent sherwood oil in alcohol saponification liquor at every turn, stirs stratification, emits petroleum ether layer, obtains extraction liquid;
(6) extraction liquid regulates pH value to subacidity, adds 20% copper sulfate solution, then is adjusted at 3,60 ℃ of pH values and keeps 40min, fully puts copper.
(7) filter, with 90% washing with alcohol 1-2 time, washings and filtrate merging, the water that doubles dilutes, and chlorophyll cupric acid can be separated out, and dries that to obtain the green copper of solid leaf sour, and the Diluted Alcohol solution washing with 50% several times, is filtered dry and gets final product purifying
(8) add 5% sodium hydroxide solution, dissolved copper acid, is added to PH always and is till 11, and salification process is first early thick, with sodium hydroxide, adds, gradually thinning,, until during PH 11, retrogradation again again.After salify, filter, filter residue distilled water flushing 1-2 time, washings is incorporated in filtrate, at 80 ℃, dries to obtain finished product 5.78g.
Case study on implementation 3:
(1) fresh leaflet camphor grass 1000g, cuts off 5cm, and 8 times of 90% ethanol extracts, and adds mortar to grind to form homogenate, standing, filters to get filtrate, and uses alcohol flushing mortar;
(2) by filter residue process squeezing machine, must remain fresh juice, filter, will after all filtrate merging, add gasoline, fully stir, be placed in respectively separating funnel, more than sufficient standing 3h, liquid is divided into two layers.
(3) upper strata is oil reservoir, is blackish green, and lower floor is that yellow liquid claims water layer, and middle level is suspended on water layer, under upper strata, claims the greyish white beds of precipitation.Water layer, the greyish white beds of precipitation, oil reservoir are filtered respectively, and filter residue merges, and with distilled water wash, drains, and in 100 ℃ of oven dry, obtains vegetable protein 81.2g; By oil reservoir decompression recycling ethanol and gasoline, obtain chlorophyll paste 5.88g;
(4) with 5% the sodium hydroxide solution that the chlorophyll alcohol liquid of 4 volumes adds 1 volume, carry out saponification, temperature 50 C, saponification 1h, stratification, lower floor is chlorophillins saponification liquor;
(5), by chlorophyll saponification liquor petroleum ether extraction oil-soluble impurities, extraction secondary adds equivalent sherwood oil in alcohol saponification liquor at every turn, stirs stratification, emits petroleum ether layer, obtains extraction liquid;
(6) extraction liquid regulates pH value to subacidity, adds 20% copper sulfate solution, then is adjusted to pH value 2-5, keeps 50min at 60 ℃, fully puts copper.
(7) filter, with 90% washing with alcohol 1-2 time, washings and filtrate merging, the water that doubles dilutes, and chlorophyll cupric acid can be separated out, and dries to obtain the green copper acid 5.758 of solid leaf, and the Diluted Alcohol solution washing with 50% several times, is filtered dry and gets final product purifying.
(8) add 5% sodium hydroxide solution, dissolved copper acid, is added to PH always and is till 11, and salification process is first early thick, with sodium hydroxide, adds, gradually thinning,, until during PH 11, retrogradation again again.After salify, filter, filter residue distilled water flushing 1-2 time, washings is incorporated in filtrate, at 70 ℃, dries to obtain finished product 5.63g.
Case study on implementation 4:
(1) fresh leaflet camphor grass 1000g, cuts off 4cm, and 7 times of 90% ethanol extracts, and adds mortar to grind to form homogenate, standing, filters to get filtrate, and uses alcohol flushing mortar;
(2) by filter residue process squeezing machine, must remain fresh juice, filter, will after all filtrate merging, add gasoline, fully stir, be placed in respectively separating funnel, more than sufficient standing 2.5h, liquid is divided into three layers.
(3) upper strata is oil reservoir, is blackish green, and lower floor is that yellow liquid claims water layer, and middle level is suspended on water layer, under upper strata, claims the greyish white beds of precipitation.Water layer, the greyish white beds of precipitation, oil reservoir are filtered respectively, and filter residue merges, and with distilled water wash, drains, and in 100 ℃ of oven dry, obtains vegetable protein 82.1g; By oil reservoir decompression recycling ethanol and gasoline, obtain chlorophyll paste 5.91g;
(4) with 10% the sodium hydroxide solution that the chlorophyll alcohol liquid of 4 volumes adds 1 volume, carry out saponification, temperature 60 C, saponification 1h, stratification, lower floor is chlorophillins saponification liquor;
(5), by chlorophyll saponification liquor petroleum ether extraction oil-soluble impurities, extraction secondary adds equivalent sherwood oil in alcohol saponification liquor at every turn, stirs stratification, emits petroleum ether layer, obtains extraction liquid;
(6) extraction liquid regulates pH value to subacidity, adds 20% copper sulfate solution, then is adjusted at 3,60 ℃ of pH values and keeps 60min, fully puts copper.
(7) filter, with 90% washing with alcohol 1-2 time, washings and filtrate merging, the water that doubles dilutes, and chlorophyll cupric acid can be separated out, and dries and to obtain the sour 5.77g of the green copper of solid leaf, and the Diluted Alcohol solution washing with 40% several times, is filtered dry and gets final product purifying
(8) add 5% sodium hydroxide solution, dissolved copper acid, is added to PH always and is till 11, and salification process is first early thick, with sodium hydroxide, adds, gradually thinning,, until during PH 11, retrogradation again again.After salify, filter, filter residue rinses 1-2 time with distilled water, and washings is incorporated in filtrate, at 80 ℃, dries to obtain finished product 5.59g.

Claims (1)

1. utilize two-step approach extracting chlorophyll and a vegetable protein, chlorophyll paste is through alkali lye saponification, and copper is replaced as the novel method of sodium copper chlorophyllin, and its step is as follows:
(1) chlorophyll is just carried: fresh leaflet camphor grass cuts off 3-5cm, and 6-8 times of 80-90% ethanol extracts, and adds mortar to grind to form homogenate, standing, filters to get filtrate, and uses alcohol flushing mortar, and filtrate merges;
(2) filter residue second extraction: filter residue, through squeezing machine, must be remained to fresh juice, filter, after all filtrate is merged, add gasoline, fully stir, be placed in separating funnel, sufficient standing 2-3h, liquid is divided into three layers;
(3) obtain primary extract: upper strata is oil reservoir, be blackish green, lower floor is that yellow liquid claims water layer, middle level is suspended on water layer, under upper strata, claims the greyish white beds of precipitation, water layer, the greyish white beds of precipitation, oil reservoir are filtered respectively, filter residue merges, and with distilled water wash, drains, and in 90-100 ℃ of oven dry, obtains vegetable protein; By oil reservoir decompression recycling ethanol and gasoline, obtain chlorophyll paste;
(4) saponification: the sodium hydroxide solution of processing the 5%-10% of 1 volume with the chlorophyll alcohol liquid of 4 volumes carries out saponification, temperature 50-60 ℃, saponification 1h, stratification, lower floor is chlorophillins saponification liquor;
(5) extraction: by chlorophyll saponification liquor petroleum ether extraction oil-soluble impurities, extract three times, add equivalent sherwood oil at every turn in alcohol saponification liquor, stir stratification, emit petroleum ether layer, obtain extraction liquid;
(6) put copper: extraction liquid regulates pH value to subacidity, add 20% copper sulfate solution, then be adjusted to pH value 2-3, keep 30-60min at 60 ℃, fully put copper;
(7) purifying: filter, by 90% washing with alcohol 1-2 time, washings merges with filtrate, and the water that doubles dilutes, and chlorophyll cupric acid can be separated out, dries that to obtain the green copper of solid leaf sour, uses the Diluted Alcohol solution washing of 40-50% several times, is filtered dry and gets final product purifying;
(8) salify: add 5% sodium hydroxide solution, dissolved copper acid, is added to pH always and is till 11, and it is thick that salification process is first, with sodium hydroxide, add, gradually thinning, until pH is 11 o'clock, retrogradation again again, after salify, filter, filter residue distilled water flushing 1-2 time, washings is incorporated in filtrate, 60-80 ℃ of vacuum hydro-extraction, obtains finished product.
CN201210144911.2A 2011-12-25 2012-05-06 Method for extracting sodium copper chlorophyllin from wild deyeuxia angustifolia forage grass Active CN102731513B (en)

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CN103509028B (en) * 2013-10-11 2015-08-12 中国科学院烟台海岸带研究所 The preparation method of a kind of chlorophyll cupric acid and copper sodium
CN105086502A (en) * 2015-09-08 2015-11-25 湖州宏鑫绸厂 Novel nanometer titania/chlorophyll derivative dye and preparation method thereof
CN105230963A (en) * 2015-11-02 2016-01-13 湖北民族学院 Method for comprehensively extracting leaf protein and chlorophyll from ginger leaves
CN109705127B (en) * 2018-12-24 2020-04-14 南京斯拜科生化实业有限公司 Anti-emulsification preparation method of plant-derived sodium copper chlorophyllin

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Owner name: GREATER KHINGAN MOUNTAIN LINGONBERRY BIOTECHNOLOGY

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Patentee after: Daxing'an Mountainrange Lin Gebei psychrophile Science and Technology Co., Ltd.

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Patentee before: Great Xingan Mountains Lingebei Organic Food Co., Ltd.