CN101455238B - Highland barley bran oil preparation method from highland barley bran oil using solvent extraction method - Google Patents
Highland barley bran oil preparation method from highland barley bran oil using solvent extraction method Download PDFInfo
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Abstract
The present invention relates to a method for preparing highland barley bran oil from highland barley bran, specifically to a method for preparing highland barley bran oil from highland barley bran using a pressurized solvent extraction method, an ultrasonic solvent extraction method and a microwave solvent extraction method, pertaining to the field of grain and oil deep processing technique. The present inventive method is simple and easy use; the products have high yield; and because the raw material of the highland barley bran is natural traditional food plant, the raw material is rich and has low cost, the obtained produce has non-pollution, non-toxic side effects, safety and practicality. Therefore the invention method has stronger industrialization practicability and operability.
Description
Technical field
The present invention relates to a kind of method that adopts solvent extraction method from highland barley bran, to prepare highland barley bran, especially adopt pressurized solvent extraction, ultrasonic solvent extraction method and microwave solvent extraction from highland barley bran, to prepare the method for highland barley bran, belong to grain and oil deep process technology field.
Background technology
Highland barley (HordeumVulgareL.varnudumHook.f) belongs to one of grass family wheat family Hordeum barley mutation on plant classification.Highland barley is Qinghai-Tibet topmost cereal crops, but because process technology falls behind, the product mouthfeel is relatively poor, though in the problem of food and clothing that solves local peasants and herdsmen, played important function, the deep processing and the comprehensive utilization of development highland barley characteristic agricultural product, improve its added value, extremely more urgent.The highland barley bran is the processed side product that the highland barley flour factory owner wants, and contains many valuable materials equally, and as β one glucan, barley germ and highland barley bran wet goods, but the comprehensive utilization ratio of highland barley bran is very low at present, and is most of as feed.If it can be carried out further processing and utilization, then can improve its economic worth greatly.
This research unit carries out finding in the comprehensive utilizating research that in early stage the quality of the highland barley bran that the highland barley bran contains is higher, is rich in unrighted acid to the highland barley bran, wherein contain abundant linoleic acid, and linoleic acid content reaches more than 60%.Linoleic acid is that health is grown necessary and aliphatic acid that human body self can not synthesize, it has nourishing brain cell, regulate the effect of vegetative nerve function, synthetic and other physiological activity of the activity of enzyme, prostaglandin in the contraction of participation human smooth muscle, the lipid metabolism.Clinically be used to adjust serum cholesterol, arteriosclerotic treatment and prevention, prevent neurological disorders etc., can be rated as " nutrition oil ".At present, the higher vegetable oil of linoleic acid content mainly is: safflower oil, soybean oil, maize germ oil, sunflower oil, inexpensive relatively except soybean oil, it is few that other is resource, the oil that valency is high.Seeking linoleic acid content height and natural material cheap and easy to get has become the focus of domestic and international concern.Highland barley bran contains abundant linoleic acid, and is cheap and easy to get, and the research highland barley bran extracts the preparation method should have positive and bigger theory and the actual meaning of utilizing, and its product will bring considerable economic value.
At present, a lot of to highland barley bran research both at home and abroad, but mostly at glucan, functional components such as polypeptide, almost do not study at present the bibliographical information of highland barley bran, let alone the production technology of research and development highland barley bran, although solvent extraction method is a kind of extracting method of routine in addition, but it is applied to extract in the highland barley bran highland barley bran or reported first, especially in recent years along with extraction, improving constantly of analytical technology means, the pressurized solvent extraction method, ultrasonic solvent extraction method and microwave solvent extraction method are applied to field of phytochemistry more and more, do not appear in the newspapers at present but these methods are applied to the correlative study of extraction highland barley bran in the highland barley bran.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of method that adopts solvent extraction method from highland barley bran, to prepare highland barley bran, particularly, the invention provides pressurized solvent extraction method, ultrasonic solvent extraction method and microwave solvent extraction method prepare highland barley bran from highland barley bran method, in the highland barley bran that makes by said method, bran oil linoleic acid content 〉=60%, the quality of highland barley bran is good, the productive rate height.
Particularly, provided by the invention from highland barley bran the preparation highland barley bran technical scheme as follows:
Scheme one: adopt the pressurized solvent extraction method to prepare highland barley bran from highland barley bran, concrete steps are as follows:
Adopt batch (-type) batch extractor group, under 0.2-0.8MPa pressure, highland barley bran powder is carried out the several adverse current leach, to pulverize highland barley bran powder is raw material, and powder particle diameter is 20-150 μ m, and raw material is added batch extractor, inject extraction solvent, the solvent of selecting for use is absolute ethyl alcohol, benzinum or isopropyl alcohol; Adverse current lixiviate number of times 1-4 time; Extraction time 20min-3h; Extraction temperature 10-135 ℃; The weight ratio of solvent and raw material is 1-4: 1; Leach to finish the back to the precipitation that reduces pressure of the lixiviate oil in the batch extractor, obtain the highland barley bran that yield is 8.2-10.2%.
In the said method, pressure is preferably 0.3-0.6MPa, most preferably 0.4MPa; The powder particle diameter of highland barley bran powder is preferably 40-90 μ m, most preferably 70 μ m; The preferred absolute ethyl alcohol of solvent or isopropyl alcohol, most preferably isopropyl alcohol; The preferred 40min-2h of extraction time, most preferably 2 hours; The preferred 40-90 of extraction temperature ℃, most preferably 70 ℃; The preferred 1-3 of the weight ratio of solvent and raw material: 1, most preferably 3: 1.
The crucial part that adopts the pressurized solvent extraction from highland barley bran, to prepare highland barley bran be following some:
The selection of one, pressure, the selection that focuses on pressure of the present invention, in phytochemical extraction, adopt pressing mode can improve recovery rate usually, but the selection of pressure is a key point, the applicant proves by experimental study repeatedly, employing pressure is 0.2-0.8MPa, especially 0.3-0.6MPa, particularly during 0.4MPa, extraction effect is best.
Two, extract choice of Solvent, the applicant proves by experimental study repeatedly, adopt absolute ethyl alcohol, benzinum or isopropyl alcohol can from highland barley bran, extract highland barley bran effectively, especially adopt absolute ethyl alcohol or isopropyl alcohol, and especially preferably adopting isopropyl alcohol as extracting solvent, its extraction effect is better;
Three, the selection of the weight ratio of solvent and raw material studies have shown that through the applicant, and when the weight ratio of solvent and raw material is 1-4: in the time of 1, can extract product, especially weight ratio effectively is 1-3: 1, and in particular for 3: 1 o'clock, it can more effectively extract;
Four, the selection of extraction temperature, as a rule, difference according to the performance of raw material itself, extraction temperature differs greatly, the applicant proves that through experimental study repeatedly when adopting above-mentioned solvent to extract, extraction temperature is 10-135 ℃, especially 40-90 ℃, can extract the highland barley bran in the highland barley bran when being in particular 70 ℃ effectively.
The yield that adopts the pressurized solvent extraction to extract highland barley bran is between the 8.2-10.2%.
Table 1: the productive rate of the highland barley bran that is obtained when adopting different solvents to extract
| Solvent | The weight ratio of solvent and raw material | The productive rate of highland barley bran (%) |
| Absolute ethyl alcohol | 3∶1 | 8.8 |
| Benzinum | 3∶1 | 9.3 |
| Isopropyl alcohol | 3∶1 | 10.2 |
| Ethyl acetate | 3∶1 | 8.2 |
| 70% ethanol | 3∶1 | 7.8 |
| Acetone | 3∶1 | 8.5 |
In table 1, the pressure that this extracting method adopted is 0.4MPa, and the powder particle diameter of highland barley bran powder is 70 μ m, and extraction time is 2 hours, and extraction temperature is 70 degree.
Table 2: the productive rate of the highland barley bran that is obtained when adopting different pressures to extract
| Pressure | Solvent | The weight ratio of solvent and raw material | The productive rate of highland barley bran (%) |
| 0.2MPa | Isopropyl alcohol | 3∶1 | 9.0 |
| 0.8MPa | Isopropyl alcohol | 3∶1 | 9.4 |
| 0.4MPa | Isopropyl alcohol | 3∶1 | 10.2 |
In table 2, the solvent that this extracting method adopted and the weight ratio of raw material are 3: 1, and the powder particle diameter of highland barley bran powder is 70 μ m, and extraction time is 2 hours, and extraction temperature is 70 degree.
Scheme two: adopt ultrasonic solvent extraction method to prepare highland barley bran from highland barley bran, concrete steps are:
To pulverize highland barley bran powder is raw material, powder particle diameter is 20-150 μ m, add organic solvent at soaking at room temperature 1-12 hour, wherein, the weight ratio of highland barley bran powder and organic solvent is 1: 2-10, the highland barley bran powder and the organic solvent that mix are in proportion placed ultrasonic extraction still, at supersonic frequency 20-800KHz, ultrasound intensity 0.3-15W/cm
2, extract under the condition of 10-80 ℃ of temperature, extracted 0.2-3 hour, through centrifugal or suction filtration, get supernatant liquid through the extract after the ultrasonic extraction, reduce pressure to concentrate and reclaim solvent, obtain the highland barley bran that yield is 9.2-11.2%.
In the said method, organic solvent is selected from 95% or 100% ethanol, benzinum or isopropyl alcohol.
In the said method, the powder particle diameter of highland barley bran powder is preferably 40-90 μ m, most preferably 70 μ m; In ultrasonic extraction still, supersonic frequency is preferably 100-700KHz, most preferably is 400KHz, and ultrasound intensity is preferably 2-13W/cm
2, most preferably be 8W/cm
2The preferred absolute ethyl alcohol of organic solvent or isopropyl alcohol, most preferably isopropyl alcohol; Preferred 3-9h of soaking at room temperature time, most preferably 6 hours; Extract preferred 40-70 ℃ of temperature, most preferably 50 ℃; The weight ratio of highland barley bran powder and organic solvent preferred 1: 4-8, most preferably 1: 6.
The crucial part that adopts ultrasonic solvent extraction method from highland barley bran, to prepare highland barley bran be following some:
The selection of one, supersonic frequency and ultrasound intensity, as a rule, the applicant proves by experimental study repeatedly, when supersonic frequency is 20-800KHz, ultrasound intensity 0.3-15W/cm
2The time, can from highland barley bran, extract highland barley bran effectively, especially work as supersonic frequency and be preferably 100-700KHz, most preferably be 400KHz, ultrasound intensity is preferably 2-13W/cm
2, most preferably be 8W/cm
2The time, its extraction effect is better;
Two, extract choice of Solvent, the applicant proves by experimental study repeatedly, adopt ethanol, benzinum or isopropyl alcohol can from highland barley bran, extract highland barley bran effectively, especially adopt ethanol or isopropyl alcohol, and especially preferably adopting isopropyl alcohol as extracting solvent, its extraction effect is better;
Three, the selection of the weight ratio of solvent and raw material studies have shown that through the applicant, when the weight ratio of highland barley bran powder and organic solvent is 1: during 2-10, can extract product effectively, especially weight ratio is 1: 4-8, in particular for 1: 6 o'clock, it can more effectively extract.
The yield that adopts the inventive method to extract highland barley bran is between the 9.2-11.2%.
The productive rate of the highland barley bran that table 3 is obtained when adopting different supersonic frequencies and ultrasound intensity to extract
| Supersonic frequency (KHz) | Ultrasound intensity (W/cm 2) | The productive rate of highland barley bran (%) |
| 20 | 0.3 | 9.2 |
| 800 | 15 | 10.5 |
| 400 | 8 | 11.2 |
| 100 | 0.3 | 9.3 |
| 200 | 0.3 | 9.7 |
| 500 | 0.3 | 10.1 |
In table 3, it is 70 μ m that this extracting method adopts the powder particle diameter of highland barley bran powder, and organic solvent is an isopropyl alcohol, and the weight ratio of highland barley bran powder and organic solvent is 1: 6; 6 hours soaking at room temperature time, extracting temperature is 50 degree.
Scheme three: adopt the microwave solvent extraction to prepare highland barley bran from highland barley bran, concrete steps are:
To pulverize highland barley bran powder is raw material, and powder particle diameter is 20-150 μ m, puts into container handling, injects extraction solvent, carries out microwave treatment, and the solvent of selecting for use comprises ethanol, benzinum (boiling range: 30-60 or 60-90) or isopropyl alcohol; Microwave treatment conditions is: processing power 600W-1000W, and the processing time is 1-4min, solvent is 1-10 with the raw material weight ratio: 1.Microwave treatment finishes the back to leaching lixiviate oil in the container precipitation that reduces pressure, and obtains the highland barley bran that yield is 9.5-12.3%.
In the said method, organic solvent is selected from 95% and 100% ethanol, benzinum or isopropyl alcohol.
In the said method, the powder particle diameter of highland barley bran powder is preferably 40-90 μ m, most preferably 70 μ m; The preferred absolute ethyl alcohol of organic solvent or isopropyl alcohol, most preferably isopropyl alcohol; Microwave treatment conditions is preferably: processing power 650-900W, and the processing time is 2-3min, most preferably is: processing power 800W, the processing time is 2.5min; Solvent is preferably 1-8 with the raw material weight ratio: 1, most preferably be 6: 1.
The crucial part that adopts the microwave solvent extraction from highland barley bran, to prepare highland barley bran be following some:
The selection of one, microwave treatment conditions, the applicant proves by experimental study repeatedly, when microwave treatment conditions is: processing power 600W-1000W, processing time can extract highland barley bran when being 1-4min effectively from highland barley bran, especially working as processing power is 650-900W, most preferably be 800W, processing time is 2-3min, and when most preferably being 2.5min, its extraction effect is better;
Two, extract choice of Solvent, the applicant proves by experimental study repeatedly, adopt ethanol, benzinum or isopropyl alcohol can from highland barley bran, extract highland barley bran effectively, especially adopt ethanol or isopropyl alcohol, and especially preferably adopting isopropyl alcohol as extracting solvent, its extraction effect is better;
Three, the selection of the weight ratio of solvent and raw material studies have shown that through the applicant, and when solvent and raw material weight ratio are 1-10: in the time of 1, can extract product effectively, especially weight ratio is 1-8: 1, and in particular for 6: 1 o'clock, it can more effectively extract.
The yield that adopts the inventive method to extract highland barley bran is between the 9.5-12.3%.
The productive rate of the highland barley bran that table 4 is obtained when adopting different microwave treatment conditions to extract
| Microwave treatment power (W) | Microwave treatment time (min) | The productive rate of highland barley bran (%) |
| ?600 | 1 | 9.7 |
| ?1000 | 4 | 11.0 |
| ?800 | 2.5 | 12.3 |
| ?600 | 0.5 | 8.5 |
| ?600 | 1.5 | 9.8 |
| ?600 | 2 | 10.2 |
In table 4, it is 70 μ m that this extracting method adopts the powder particle diameter of highland barley bran powder, and organic solvent is an isopropyl alcohol, the weight ratio of solvent and raw material 6: 1.
In above-mentioned three kinds of extractive technique schemes, the pulverizing highland barley bran powder that is adopted is to pulverize with pulverizer after highland barley bran is removed impurity, and 40 mesh sieves obtain excessively; The benzinum that is adopted can be two types the benzinum of 30-60 or 60-90 for boiling range in addition.
The highland barley bran fatty acid oil that said method is made carries out the GC-MS analysis, linoleic acid content in the highland barley bran 〉=60%, and arachidic acid monoenoic acid content is about 1.6%, and palmitic acid is about 18-20%, and stearic acid is about 1.4%.
By the bran oil of this method preparation, the recovery rate of oil can reach 70-92.6%.Be calculated as follows the recovery rate of oil:
Recovery rate=(extracting the contained oil quality of oil mass/wheat bran) * 100%
Wherein, be 100% in soxhlet extraction with the rice bran oil quality that n-hexane extracts.
After adopting conventional refinery practices such as grease winterization, alkali refining and decolouring to handle, the highland barley bran of method for preparing can obtain refining bran oil.Here the post-processing approach that is adopted all belongs to the conventional treatment method of oils product.
Highland barley bran by method for preparing can be used to prepare linoleic acid.
By method for preparing highland barley bran can be further used for preparation and grip linoleic acid altogether.
In addition, find after deliberation, adopt the prepared highland barley bran of the inventive method also to have following purposes:
1, directly edible: the highland barley bran of extraction can directly eat after making with extra care.
2, make ready-mixed oil: combined with some other edible base oil, make ready-mixed oil.
The present invention compared with prior art has following good effect:
Adopt pressurized solvent extraction method, ultrasonic solvent extraction method and microwave solvent extraction method can from highland barley bran, extract highland barley bran effectively, these methods are simple, and because the highland barley bran raw material is natural traditional food plant, abundant raw material is inexpensive, the product that is obtained is pollution-free, have no side effect, safe and practical, therefore method of the present invention has stronger industrialization practicality and operability.
The specific embodiment:
The present invention further illustrates by the following example, but is not any restriction to protection domain of the present invention.
(1) preparation embodiment
Embodiment 1
Adopt batch (-type) batch extractor group, highland barley bran powder is carried out 1 adverse current to be leached: pulverizing highland barley bran powder with 100g is raw material, powder particle diameter is 20 μ m, add batch extractor, inject extraction solvent absolute ethyl alcohol 400g, under 0.2MPa pressure, extraction time 3h, 135 ℃ of extraction temperatures, adverse current lixiviate number of times 1 time; Leach to finish the back to the precipitation that reduces pressure of the lixiviate oil in the batch extractor, obtain highland barley bran 8.6g, yield is 8.6%.
Embodiment 2
Adopt batch (-type) batch extractor group, highland barley bran powder is carried out 4 adverse currents to be leached: pulverizing highland barley bran powder with 100g is raw material, powder particle diameter is 150 μ m, add batch extractor, injection extraction solvent benzinum (boiling range: 60-90) 100g, under 0.8MPa pressure, extraction time 20min, 10 ℃ of extraction temperatures, adverse current lixiviate number of times 4 times; Leach to finish the back to the precipitation that reduces pressure of the lixiviate oil in the batch extractor, obtain highland barley bran 9.0g, yield is 9.0%.
Embodiment 3
Adopt batch (-type) batch extractor group, highland barley bran powder is carried out 3 adverse currents to be leached: pulverizing highland barley bran powder with 100g is raw material, powder particle diameter is 70 μ m, add batch extractor, inject extraction solvent isopropyl alcohol 300g, under 0.4MPa pressure, extraction time 20min, 70 ℃ of extraction temperatures, adverse current lixiviate number of times 4 times; Leach to finish the back to the precipitation that reduces pressure of the lixiviate oil in the batch extractor, obtain highland barley bran 10.2g, yield is 10.2%.
Embodiment 4
Pulverizing highland barley bran powder with 100g is raw material, and powder particle diameter is 20 μ m, adds 95% ethanol 200g and soaks 1 hour in room temperature, the highland barley bran powder and the organic solvent that mix are in proportion placed ultrasonic extraction still, at supersonic frequency 20KHz, ultrasound intensity 0.3W/cm2 extracts under the condition of 80 ℃ of temperature, extracted 3 hours, through suction filtration, get supernatant liquid through the extract after the ultrasonic extraction, reduce pressure to concentrate and reclaim solvent, obtain highland barley bran 9.1g, yield is 9.1%.
Embodiment 5
Pulverizing highland barley bran powder with 100g is raw material, and powder particle diameter is 150 μ m, adds benzinum 1000g and soaks 12 hours in room temperature, and highland barley bran powder and the organic solvent that mixes in proportion placed ultrasonic extraction still, at supersonic frequency 800KHz, and ultrasound intensity 15W/cm
2, extract under the condition of 10 ℃ of temperature, extracted 1 hour, through centrifugal, get supernatant liquid through the extract after the ultrasonic extraction, reduce pressure to concentrate and reclaim solvent, obtain highland barley bran 10.3g, yield is 10.3%.
Embodiment 6
Pulverizing highland barley bran powder with 100g is raw material, and powder particle diameter is 70 μ m, adds isopropyl alcohol 600g and soaks 6 hours in room temperature, the highland barley bran powder and the organic solvent that mix are in proportion placed ultrasonic extraction still, at supersonic frequency 400KHz, ultrasound intensity 8W/cm2 extracts under the condition of 50 ℃ of temperature, extracted 1.5 hours, through centrifugal or suction filtration, get supernatant liquid through the extract after the ultrasonic extraction, reduce pressure to concentrate and reclaim solvent, the highland barley bran 11.2g that obtains, yield are 11.2%.
Embodiment 7
Pulverizing highland barley bran powder with 100g is raw material, and powder particle diameter is 20 μ m, puts into container handling, injects extraction solvent absolute ethyl alcohol 1000g; Microwave treatment conditions is: processing power 600W, and time 1min, microwave treatment finishes the back to leaching lixiviate oil in the container precipitation that reduces pressure, and obtains highland barley bran 9.5g, and yield is 9.5%.
Embodiment 8
Pulverizing highland barley bran powder with 100g is raw material, and powder particle diameter is 150 μ m, puts into container handling, injects extraction solvent benzinum (boiling range: 60-90) 100g; Microwave treatment conditions is: processing power 1000W, and time 4min, microwave treatment finishes the back to leaching lixiviate oil in the container precipitation that reduces pressure, and obtains highland barley bran 10.9g, and yield is 10.9%.
Embodiment 9
Pulverizing highland barley bran powder with 100g is raw material, and powder particle diameter is 70 μ m, puts into container handling, injects extraction solvent isopropyl alcohol 600g; Microwave treatment conditions is: processing power 800W, and time 2.5min, microwave treatment finishes the back to leaching lixiviate oil in the container precipitation that reduces pressure, and obtains highland barley bran 12.3g, and yield is 12.3%.
(2) refining embodiment
Embodiment 10
With acid number is 12 highland barley bran after filtration after the removal of impurities, regulates highland barley bran oil concentration to 75%, under 55 ℃ of conditions, add mix oil mass 0.25%, concentration is that 85% phosphoric acid mixes, and evenly behind the stirring reaction 30min, enters alkali pretreatment.Press G
NaOH=G
0* V
A* 40/56.11 * 10
-3, theory of computation caustic soda consumption is added to the above-mentioned highland barley bran that comes unstuck by 100.2% theoretical alkali number, fully mix, after slowly stirring (30rpm) reaction flocculation (30min) under 55 ℃ the condition, centrifugation, the miscella after the separation is warming up to 65 ℃ again, it is an amount of evenly to add 85 ℃ of hot water in 8 minutes, and with 60 rev/mins of stirrings, after water injection stirred 20 minutes with 30 rev/mins the back, left standstill 3 hours, emit soap water, wash 2-3 time so repeatedly.Oil is sucked in the T/DLYS vacuum dehydration pot again and be heated to 110 ℃, with 30 rev/mins of stirrings, made pot interior vacuum reach 0.09/MP in 30 minutes, the edible vegetable oil pressure after will dewatering at last is 3.5Kg/cm
2The time compressed air be pressed onto plate type pressure filter and filter, oily temperature control is at 92 ℃, the oil that leaches is the lurid refining highland barley bran of outward appearance, acid value 0.48.
Embodiment 11
Getting acid number and be 18 highland barley bran 500g drops in the 1000ml flask, stir and add the 8g diethanol amine down, continued stirring reaction 50 minutes, centrifugation, bran oil changes in the beaker, and the soft water that adds the heavy 7-15% of oil stirs washing, centrifugation again, filtrate is left standstill, and obtains the refining highland barley bran of 370g outward appearance clear, acid number 4.1.
The preparation method of highland barley bran of the present invention is described by specific embodiment.Those skilled in the art can use for reference links such as content appropriate change raw material of the present invention, process conditions and realize corresponding other purpose, its relevant change does not all break away from content of the present invention, all similar replacements and change will become apparent to those skilled in the art that and all be regarded as comprising within the scope of the present invention.
Claims (2)
1. a method that adopts the pressurized solvent extraction to prepare highland barley bran from highland barley bran is characterized in that this method comprises the steps:
Adopt batch (-type) batch extractor group, under 0.2-0.8MPa pressure, highland barley bran powder is carried out the several adverse current leach; Be raw material to pulverize highland barley bran powder promptly, powder particle diameter is 20-150 μ m, and raw material is added batch extractor, injects extraction solvent, and selected solvent is ethanol, benzinum or isopropyl alcohol; Adverse current lixiviate number of times 1-4 time; Extraction time 20min-3h; Extraction temperature 10-135 ℃; The weight ratio of solvent and raw material is 1-4: 1; Leach to finish the back to the precipitation that reduces pressure of the lixiviate oil in the batch extractor.
2. according to the method for claim 1, it is characterized in that pressure is 0.3-0.6MPa, solvent is ethanol or isopropyl alcohol, and the weight ratio of solvent and raw material is 1-3: 1.
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| CN101317652A (en) * | 2007-12-22 | 2008-12-10 | 兰州奇正健康日用品有限公司 | Preparation method for highland barley essential oil and solvent extraction |
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| CN101317652A (en) * | 2007-12-22 | 2008-12-10 | 兰州奇正健康日用品有限公司 | Preparation method for highland barley essential oil and solvent extraction |
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