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.