CN101157731B - Preparation method for low agriculture remanet panax ginseng and American ginseng polysaccharide extractive - Google Patents

Preparation method for low agriculture remanet panax ginseng and American ginseng polysaccharide extractive Download PDF

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CN101157731B
CN101157731B CN2007100562846A CN200710056284A CN101157731B CN 101157731 B CN101157731 B CN 101157731B CN 2007100562846 A CN2007100562846 A CN 2007100562846A CN 200710056284 A CN200710056284 A CN 200710056284A CN 101157731 B CN101157731 B CN 101157731B
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刘智谋
李玲
冯涛
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JILIN HONGJIU BIOTECH CO Ltd
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Abstract

The present invention relates to a method for applying the macroporous resin to remove the pesticide residues by using the different parts of ginseng and panax quinquefolium as the raw materials. The quality of the present invention is mainly characterized in that: all the pesticide residues are less than 10PPb, and the content of galacturonic acid is 1.0 percent to 25.0 percent.

Description

The method for making of low agricultural residual genseng, Radix Panacis Quinquefolii polysaccharide extract
Technical field: the present invention relates to one and use the method that macroporous resin is removed pesticide residue.Its main qualitative characteristics is: each item farming is residual all less than 10PPb, galacturonic acid 1.0%~25.0%.
Background technology: the genseng of having found, Radix Panacis Quinquefolii activeconstituents mainly contain several big type of saponin(e, GPS, volatile oil, amino acid and polypeptide etc.Have enhance immunity power, anti-ageing, promote learning and Memory function, detoxifcation, multiple physiological action such as antibiotic, diseases such as cardiovascular disorder, tumour, inflammation and digestive tract ulcer are had good effects.
Along with the discovery of genseng, Radix Panacis Quinquefolii polysaccharide enhancing immunity, physiological function such as antitumor, also deep day by day to STUDY ON POLYSACHAROSE, the GPS of separation and purification has tens of kinds at present.See that from the source these polysaccharide can be divided into ginseng polysaccharide, Stem and leaf of Radix Ginseng polysaccharide and genseng fructose.Wherein ginseng mainly contains acid heteroglycan and VISOSE; And the Ginseng Leaf is mainly contained acid heteroglycan; These mixed polysaccharide are present in cell walls as structural polysaccharide, mainly are made up of galacturonic acid, semi-lactosi, rhamnosyl, my sugar and pectinose (Ara), and structure is very complicated.
Investigation result according to national Chinese medicinal materials plant protection problem; At present the pest species of Chinese medicinal materials endangers heavily more, loss is big, like known genseng, Radix Panacis Quinquefolii more than 40 kind of infectivity disease and pest is arranged, normal take place kind more than 20 just arranged; Basically take chemical pesticide control, spray medicine 20-30 time every year on average.GeneraI investigation was once done to the pesticide residue of 300 plurality of Chinese in all parts of the country by Shanghai Univ. of Traditional Chinese Medicine, and the whole samples of result all contain phenyl-hexachloride, and great majority contain the residual amount of DDT.Chinese medicine is the treasure of the Chinese nation, its world market proportion increasing.And the market sales revenue of China is only about 4%, and its major cause is exactly the pesticide residue height.Therefore this problem must solve early, otherwise will seriously restrict the development of Chinese medicinal materials.Present method is to adopt absorption with macroporous adsorbent resin to remove pesticide residue, is superior to other plant and removes the residual method of farming.For example adopt supercritical extraction to remove the residual method of genseng middle peasant.Step is earlier genseng to be pulverized or section, and genseng is put into abstraction pool, makes the carbonic acid gas state that reaches capacity.Adjustment flow velocity, temperature, pressure, volume, purification entrainment agent, agricultural chemicals scavenging agent etc. are removed the residual purpose of farming to reach.
Summary of the invention: the objective of the invention is to find a kind of method of effective removal pesticide residue, it does not promptly destroy its effective constituent, does not lose productive rate, can effectively reduce the residual quantity of agricultural chemicals again.
The technical scheme that practical the present invention is adopted, its detailed process flow is following:
Low agricultural residual ginseng polyoses extract method for making: get ginseng, be ground into 8~40 purpose powder, add 4~15 times of amount 55%~85% alcohol reflux 1~3 time, each 1~5 hour; Extracting liquid filtering, the slag of getting it filled, oven dry; Add 5~15 times of water gagings and extract 1~3 time, extraction time is 1~3 hour, and extracting solution is centrifugal through tubular type; With the macroporous resin column absorption of centrifugate through anticipating, adsorptive capacity is 1~50 times of amount of resin volume, and the control flow velocity is 1~5ml/min/cm 2, effluent is concentrated into the fluid extract that specific density is about 1.0~1.3 (50 ℃ of surveys), drying promptly gets.
Low agricultural residual Stem and leaf of Radix Ginseng polyoses extract method for making: get Stem and leaf of Radix Ginseng and add 5~15 times of water gagings extractions 1~4 time, extraction time is 1~3 hour, extracting liquid filtering; Be concentrated into the fluid extract that specific density is about 1.0~1.3 (50 ℃ of surveys), add 1~5 times of amount ethanol and stir, leave standstill more than 4 hours; Take off a layer slag and add 4~15 times of water gaging dissolvings, centrifugal through tubular type, with the macroporous resin column absorption of centrifugate through anticipating; Adsorptive capacity is 1~50 times of amount of resin volume, and the control flow velocity is 1~5ml/min/cm 2, effluent is concentrated into the fluid extract that specific density is about 1.0~1.3 (50 ℃ of surveys), drying promptly gets.
Low agricultural residual Herba Herminii polyoses extract method for making: it is centrifugal to get the ginseng juice, centrifugate (1) and centrifugal slag, centrifugal slag adds 1~5 times of water gaging in 50 ℃~95 ℃ extractions 1~4 time; Extraction time is 1~3 hour, and extracting solution is through centrifugal, and centrifugate and centrifugate (1) merge; Be concentrated into the fluid extract that specific density is about 1.0~1.3 (50 ℃ of surveys), add 1~5 times of amount ethanol and stir, leave standstill more than 4 hours; Take off a layer slag and add 4~15 times of water gaging dissolvings, centrifugal with tubular type, through the macroporous resin column absorption of anticipating; Adsorptive capacity is 1~50 times of amount of resin volume, and the control flow velocity is 1~5ml/min/cm 2, effluent is concentrated into the fluid extract that specific density is about 1.0~1.3 (50 ℃ of surveys), drying promptly gets.
Low agricultural residual American ginseng root polyoses extract method for making: get American ginseng root, be ground into 8~40 purpose powder, add 4~15 times of amount 55%~85% alcohol reflux 1~3 time, each 1~5 hour; Extracting liquid filtering, the slag of getting it filled, oven dry; Add 5~15 times of water gagings and extract 1~3 time, extraction time is 1~3 hour, and extracting solution is centrifugal through tubular type; With the macroporous resin column absorption of centrifugate through anticipating, adsorptive capacity is 1~50 times of amount of resin volume, and the control flow velocity is 1~5ml/min/cm 2, effluent is concentrated into the fluid extract that specific density is about 1.0~1.3 (50 ℃ of surveys), drying promptly gets.
Low agricultural residual stem and leaf of Radix Panacis Quinquefolii polyoses extract method for making: get stem and leaf of Radix Panacis Quinquefolii and add 5~15 times of water gagings extractions 1~4 time, extraction time is 1~3 hour, extracting liquid filtering; Be concentrated into the fluid extract that specific density is about 1.0~1.3 (50 ℃ of surveys); Add 1~5 times of amount ethanol and stir, leave standstill more than 4 hours, take off a layer slag and add 4~15 times of water gaging dissolvings; Centrifugal through tubular type; With the macroporous resin column absorption of centrifugate through anticipating, adsorptive capacity is 1~50 times of amount of resin volume, and the control flow velocity is 1~5ml/min/cm 2, effluent is concentrated into the fluid extract that specific density is about 1.0~1.3 (50 ℃ of surveys), drying promptly gets.
Low agricultural residual Fructus Panacis Quinquefolii polyoses extract method for making: it is centrifugal to get Radix Panacis Quinquefolii fruit juice, gets centrifugate (1) and centrifugal slag, and centrifugal slag adds 1~5 times of water gaging and extracts 1~4 time in 50 ℃~95 ℃; Extraction time is 1~3 hour, and extracting solution is through centrifugal, and centrifugate and centrifugate (1) merge; Be concentrated into the fluid extract that specific density is about 1.0~1.3 (50 ℃ of surveys), add 1~5 times of amount ethanol and stir, leave standstill more than 4 hours; Take off a layer slag and add 4~15 times of water gaging dissolvings, centrifugal with tubular type, through the macroporous resin column absorption of anticipating; Adsorptive capacity is 1~50 times of amount of resin volume, and the control flow velocity is 1~5ml/min/cm 2, effluent is concentrated into the fluid extract that specific density is about 1.0~1.3 (50 ℃ of surveys), drying promptly gets.
The treatment process of resin is following:
(1) pre-treatment of resin and dress post: with 75% alcohol immersion resin 24 hours, after the immersion, water flushing replacement ethanol; Stir, remove little resin; Before the dress post, the column bottom is lined with screen cloth or the glass wool that prevents under the resin streak, in post, adds certain water before the dress post earlier; Pour the resin aqueous slurry in the post into through funnel; Emit excessive water through the column bottom, keep the water surface to be higher than resin bed more than 3 centimetres, all transfer in the post until all resins; Resin descends under action of gravity naturally, and the adjustment liquid level is to resin bed more than 3 centimetres.
(2) regeneration of resin is handled: after polymeric adsorbent runs to terminal point, with the water rinse resin post of 2 volumes, wash resin column with the 2-4% sodium hydroxide solution earlier; Be full of resin column (being that effluent is alkalescence) until sodium hydroxide solution and soak more than 4 hours, the water flushing makes effluent show neutral; With the hydrochloric acid soln flushing resin column of 2-4%, show acid again, soak more than 8 hours up to effluent; Water flushing resin column makes effluent show neutral, and resin column regeneration finishes.Regenerating resin can supply next production application immediately, or it is stored in 30% ethanolic soln.
Confirm the method for making of low agricultural residual genseng, Radix Panacis Quinquefolii polysaccharide extract below through specific embodiment
Specific embodiments
Embodiment 1: get ginseng 10kg, be ground into 20 purpose meal, add 7 times of amount 80% alcohol reflux 2 times, each 2 hours; Extracting liquid filtering, the slag of getting it filled, oven dry; Add 10 times of water gagings and extract 2 times, extraction time is 2 hours, and extracting solution is centrifugal through tubular type; With the D101-C macroporous resin column absorption of centrifugate through anticipating, adsorptive capacity is 30 times of amounts of resin volume, and the control flow velocity is 2ml/min/cm 2, effluent is concentrated into the fluid extract that specific density is about 1.15 (50 ℃ of surveys), spraying drying promptly gets and hangs down agricultural residual ginseng polyoses extract 1.61kg, censorship, it is residual following with the galacturonic acid result to detect farming:
Project The result
Pentachlorobenzene 0.88PPb
Tecnazene 5.34PPb
Tetrachlorobenzene -
Perchlorobenzene 3.54PPb
The a-phenyl-hexachloride 0.30PPb
Quintozene 7.66PPb
The r-phenyl-hexachloride 2.78PPb
Pentachloroaniline 2.45PPb
Pentachloro-methyl thioether 6.24PPb
The b-phenyl-hexachloride 6.09PPb
The d-phenyl-hexachloride 3.06PPb
Procymidone 8.78PPb
Galacturonic acid 9.4%
Embodiment 2: get Stem and leaf of Radix Ginseng 50kg, add 12 times of water gagings and extract 2 times, extraction time is 2 hours; Extracting liquid filtering is concentrated into the fluid extract that specific density is about 1.15 (50 ℃ of surveys), adds 4 times of amount ethanol and stirs; Left standstill 12 hours, and took off a layer slag and add 10 times of water gaging dissolvings, centrifugal through tubular type; With the D101-C macroporous resin column absorption of centrifugate through anticipating, adsorptive capacity is 25 times of amounts of resin volume, and the control flow velocity is 2ml/min/cm 2, effluent is concentrated into the fluid extract that specific density is about 1.22 (50 ℃ of surveys), spraying drying promptly gets and hangs down agricultural residual Stem and leaf of Radix Ginseng polyoses extract 5.89kg, censorship, it is residual following with the galacturonic acid result to detect farming:
Project The result
Pentachlorobenzene 1.44PPb
Tecnazene 3.35PPb
Tetrachlorobenzene 1.04PPb
Perchlorobenzene 4.45PPb
The a-phenyl-hexachloride 0.20PPb
Quintozene 4.17PPb
The r-phenyl-hexachloride 0.79PPb
Pentachloroaniline 1.87PPb
Pentachloro-methyl thioether 4.42PPb
The b-phenyl-hexachloride -
The d-phenyl-hexachloride 3.45PPb
Procymidone 4.93PPb
Galacturonic acid 12.1%
Embodiment 3: get ginseng juice 150kg, and centrifugal, get centrifugate (1) and centrifugal slag; Centrifugal slag adds 2 times of water gagings in 95 ℃ of extractions 1 time, and extraction time is 2 hours, and is centrifugal; Centrifugate and centrifugate (1) merge, and are concentrated into the fluid extract that specific density is about 1.15 (50 ℃ of surveys), add 4 times of amount ethanol and stir; Left standstill 12 hours, and took off a layer slag and add 10 times of water gaging dissolvings, centrifugal through tubular type; Through the D101-C macroporous resin column absorption of anticipating, adsorptive capacity is 24 times of amounts of resin volume, and the control flow velocity is 2ml/min/cm 2, effluent is concentrated into the fluid extract that specific density is about 1.20 (50 ℃ of surveys), spraying drying promptly gets and hangs down agricultural residual Herba Herminii polyoses extract 5.14kg, censorship, it is residual following with the galacturonic acid result to detect farming:
Project The result
Pentachlorobenzene -
Tecnazene 7.41PPb
Tetrachlorobenzene -
Perchlorobenzene 0.83PPb
The a-phenyl-hexachloride 4.47PPb
Quintozene 4.47PPb
The r-phenyl-hexachloride 1.32PPb
Pentachloroaniline 4.32PPb
Pentachloro-methyl thioether 6.51PPb
The b-phenyl-hexachloride -
The d-phenyl-hexachloride 0.24PPb
Procymidone 7.98PPb
Galacturonic acid 17.5%
Embodiment 4: get American ginseng root 10kg, be ground into 20 purpose meal, add 7 times of amount 80% alcohol reflux 2 times, each 2 hours; Extracting liquid filtering, the slag of getting it filled, oven dry; Add 10 times of water gagings and extract 2 times, extraction time is 2 hours, and extracting solution is centrifugal through tubular type; With the D101-C macroporous resin column absorption of centrifugate through anticipating, adsorptive capacity is 30 times of amounts of resin volume, and the control flow velocity is 2ml/min/cm 2, effluent is concentrated into the fluid extract that specific density is about 1.15 (50 ℃ of surveys), spraying drying promptly gets and hangs down agricultural residual American ginseng root polyoses extract 2.01kg, censorship, it is residual following with the galacturonic acid result to detect farming:
Project The result
Pentachlorobenzene 1.81PPb
Tecnazene 2.04PPb
Tetrachlorobenzene -
Perchlorobenzene 3.50PPb
The a-phenyl-hexachloride 0.30PPb
Quintozene 2.61PPb
The r-phenyl-hexachloride 0.87PPb
Pentachloroaniline 3.45PPb
Pentachloro-methyl thioether 2.64PPb
The b-phenyl-hexachloride 3.39PPb
The d-phenyl-hexachloride 5.46PPb
Procymidone 1.70PPb
Galacturonic acid 17.4%
Embodiment 5: get stem and leaf of Radix Panacis Quinquefolii 50kg, add 12 times of water gagings and extract 2 times, extraction time is 2 hours; Extracting liquid filtering is concentrated into the fluid extract that specific density is about 1.12 (50 ℃ of surveys), adds 4 times of amount ethanol and stirs; Left standstill 12 hours, and took off a layer slag and add 10 times of water gaging dissolvings, centrifugal through tubular type; With the D101-C macroporous resin column absorption of centrifugate through anticipating, adsorptive capacity is 25 times of amounts of resin volume, and the control flow velocity is 3ml/min/cm 2, effluent is concentrated into the fluid extract that specific density is about 1.22 (50 ℃ of surveys), spraying drying promptly gets and hangs down agricultural residual stem and leaf of Radix Panacis Quinquefolii polyoses extract 4.85kg, censorship, it is residual following with the galacturonic acid result to detect farming:
Project The result
Pentachlorobenzene 1.40PPb
Tecnazene 3.35PPb
Tetrachlorobenzene 4.41PPb
Perchlorobenzene 1.04PPb
The a-phenyl-hexachloride 4.24PPb
Quintozene 4.45PPb
The r-phenyl-hexachloride 2.20PPb
Pentachloroaniline 4.47PPb
Pentachloro-methyl thioether 3.33PPb
The b-phenyl-hexachloride 4.01PPb
The d-phenyl-hexachloride 4.40PPb
Procymidone 3.31PPb
Galacturonic acid 6.1%
Embodiment 6: get Radix Panacis Quinquefolii fruit juice 150kg, and centrifugal, get centrifugate (1) and centrifugal slag; Centrifugal slag adds 2 times of water gagings in 95 ℃ of extractions 1 time, and extraction time is 2 hours, and is centrifugal; Centrifugate and centrifugate (1) merge, and are concentrated into the fluid extract that specific density is about 1.15 (50 ℃ of surveys), add 4 times of amount ethanol and stir; Left standstill 12 hours, and took off a layer slag and add 10 times of water gaging dissolvings, centrifugal through tubular type; Through the D101-C macroporous resin column absorption of anticipating, adsorptive capacity is 24 times of amounts of resin volume, and the control flow velocity is 2ml/min/cm 2, effluent is concentrated into the fluid extract that specific density is about 1.21 (50 ℃ of surveys), spraying drying promptly gets and hangs down agricultural residual Herba Herminii polyoses extract 4.54kg, censorship, it is residual following with the galacturonic acid result to detect farming:
Project The result
Pentachlorobenzene 3.27PPb
Tecnazene 1.12PPb
Tetrachlorobenzene -
Perchlorobenzene 1.13PPb
The a-phenyl-hexachloride 3.43PPb
Quintozene 2.42PPb
The r-phenyl-hexachloride 2.02PPb
Pentachloroaniline 4.34PPb
Pentachloro-methyl thioether 4.01PPb
The b-phenyl-hexachloride 3.43PPb
The d-phenyl-hexachloride 2.24PPb
Procymidone 3.98PPb
Galacturonic acid 12.5%

Claims (4)

1. adopting root, cauline leaf or the fruit of genseng, Radix Panacis Quinquefolii be raw material, uses macroporous adsorption resin technology and removes pesticide residue and make a kind of method of hanging down agricultural residual genseng, Radix Panacis Quinquefolii polysaccharide extract, said low farming is residual be agricultural residual content less than 10PPb, this method comprises:
Low agricultural residual ginseng polyoses extract method for making: get ginseng, be ground into 8~40 purpose powder, add 4~15 times of amount 55%~85% alcohol reflux 1~3 time, each 1~5 hour; Extracting liquid filtering, the slag of getting it filled, oven dry; Add 5~15 times of water gagings and extract 1~3 time, extraction time is 1~3 hour, and extracting solution is centrifugal through tubular type; With the macroporous resin column absorption of centrifugate through anticipating, adsorptive capacity is 1~50 times of amount of resin volume, and the control flow velocity is 1~5ml/min/cm 2, it is 1.0~1.3 fluid extract that effluent is concentrated into specific density, drying promptly gets;
Low agricultural residual Stem and leaf of Radix Ginseng polyoses extract method for making: get Stem and leaf of Radix Ginseng and add 5~15 times of water gagings extractions 1~4 time, extraction time is 1~3 hour, extracting liquid filtering; Be concentrated into specific density and be 1.0~1.3 fluid extract, add 1~5 times of amount ethanol and stir, leave standstill more than 4 hours; Take off a layer slag and add 4~15 times of water gaging dissolvings, centrifugal through tubular type, with the macroporous resin column absorption of centrifugate through anticipating; Adsorptive capacity is 1~50 times of amount of resin volume, and the control flow velocity is 1~5ml/min/cm 2, it is 1.0~1.3 fluid extract that effluent is concentrated into specific density, drying promptly gets;
Low agricultural residual Herba Herminii polyoses extract method for making: it is centrifugal to get the ginseng juice, centrifugate (1) and centrifugal slag, centrifugal slag adds 1~5 times of water gaging in 50 ℃~95 ℃ extractions 1~4 time; Extraction time is 1~3 hour, and extracting solution is through centrifugal, and centrifugate and centrifugate (1) merge; Be concentrated into specific density and be 1.0~1.3 fluid extract, add 1~5 times of amount ethanol and stir, leave standstill more than 4 hours; Take off a layer slag and add 4~15 times of water gaging dissolvings, centrifugal with tubular type, through the macroporous resin column absorption of anticipating; Adsorptive capacity is 1~50 times of amount of resin volume, and the control flow velocity is 1~5ml/min/cm 2, it is 1.0~1.3 fluid extract that effluent is concentrated into specific density, drying promptly gets;
Low agricultural residual American ginseng root polyoses extract method for making: get American ginseng root, be ground into 8~40 purpose powder, add 4~15 times of amount 55%~85% alcohol reflux 1~3 time, each 1~5 hour; Extracting liquid filtering, the slag of getting it filled, oven dry; Add 5~15 times of water gagings and extract 1~3 time, extraction time is 1~3 hour, and extracting solution is centrifugal through tubular type; With the macroporous resin column absorption of centrifugate through anticipating, adsorptive capacity is 1~50 times of amount of resin volume, and the control flow velocity is 1~5ml/min/cm 2, it is 1.0~1.3 fluid extract that effluent is concentrated into specific density, drying promptly gets;
Low agricultural residual stem and leaf of Radix Panacis Quinquefolii polyoses extract method for making: get stem and leaf of Radix Panacis Quinquefolii and add 5~15 times of water gagings extractions 1~4 time, extraction time is 1~3 hour, extracting liquid filtering; Be concentrated into specific density and be 1.0~1.3 fluid extract, add 1~5 times of amount ethanol and stir, leave standstill more than 4 hours; Take off a layer slag and add 4~15 times of water gaging dissolvings, centrifugal through tubular type, with the macroporous resin column absorption of centrifugate through anticipating; Adsorptive capacity is 1~50 times of amount of resin volume, and the control flow velocity is 1~5ml/min/cm 2, it is 1.0~1.3 fluid extract that effluent is concentrated into specific density, drying promptly gets;
Low agricultural residual Fructus Panacis Quinquefolii polyoses extract method for making: it is centrifugal to get Radix Panacis Quinquefolii fruit juice, gets centrifugate (1) and centrifugal slag, and centrifugal slag adds 1~5 times of water gaging and extracts 1~4 time in 50 ℃~95 ℃; Extraction time is 1~3 hour, and extracting solution is through centrifugal, and centrifugate and centrifugate (1) merge; Be concentrated into specific density and be 1.0~1.3 fluid extract, add 1~5 times of amount ethanol and stir, leave standstill more than 4 hours; Take off a layer slag and add 4~15 times of water gaging dissolvings, centrifugal with tubular type, through the macroporous resin column absorption of anticipating; Adsorptive capacity is 1~50 times of amount of resin volume, and the control flow velocity is 1~5ml/min/cm 2, it is 1.0~1.3 fluid extract that effluent is concentrated into specific density, drying promptly gets;
Said specific density is 50 ℃ a test value.
2. the described method of claim 1, it is characterized in that: said macroporous adsorbent resin is D101, AB-8, NKA, DM130 or D101-C macroporous adsorbent resin.
3. prepared genseng, Radix Panacis Quinquefolii polysaccharide extract in the claim 1, its main qualitative characteristics is: galacturonic acid is 1.0%~25.0%.
4. the preparation method of an oral prepns comprises:
Prepared genseng, Radix Panacis Quinquefolii polysaccharide extract add pharmaceutical excipient or carrier in the claim 1, are prepared into oral prepns.
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