CN107815348B - Method for removing safrole from borneol oil - Google Patents
Method for removing safrole from borneol oil Download PDFInfo
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- CN107815348B CN107815348B CN201710984757.2A CN201710984757A CN107815348B CN 107815348 B CN107815348 B CN 107815348B CN 201710984757 A CN201710984757 A CN 201710984757A CN 107815348 B CN107815348 B CN 107815348B
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/10—Refining fats or fatty oils by adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
- B01D15/206—Packing or coating
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- Oil, Petroleum & Natural Gas (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention provides a method for removing safrole from borneol oil, which comprises the following steps: (1) pretreating column separation filler and packing the column separation filler into a column, and then packing the naphtha into the column; (2) the borneol essential oil without safrole is obtained by eluting with an eluent and concentrating, the method has strong process operability and no three wastes, and can be directly expanded for production, the purified borneol essential oil has the advantages of obviously improved content of dextroborneol, purer fragrance, wide application prospect and higher application value.
Description
Technical Field
The invention belongs to the field of natural product separation, and relates to a method for removing safrole from borneol oil.
Background
Safrole belongs to a first-grade substance easy to prepare toxin, can form a strong carcinogen in the metabolic process of liver tissues, has strict limitations in daily chemicals, food and drug industries, and even is prohibited to be used. Safrole, also known as safrole, has very clear regulations in "technical Specifications for cosmetics": 100mg/kg of finished cosmetic; 50mg/kg in dental and oral hygiene products (prohibited in toothpastes intended for children). Therefore, the quality control of the borneol essential oil is necessary.
The safrole is colorless to light yellow liquid, and contains a benzene ring structure, and one end of a branched chain has an unsaturated bond. The borneol essential oil belongs to the class of components with relatively small polarity, and the polarity of the borneol essential oil is much smaller than that of borneol. Therefore, the nonpolar and weak-polarity macroporous resin containing the benzene ring skeleton can have a certain separation effect on safrole by materials which show nonpolar functions under certain environments. The separation of safrole is mostly concentrated on column chromatography materials, such as silica gel, which must be an anhydrous system during column chromatography and use various organic solvents with large polarity difference. Such materials theoretically achieve a crude separation according to the difference in polarity of the substances and the dissolving capacity in the solvent. The sample loading amount can be greatly reduced when the subdivision of the substances is realized, and the elution solvent is a composite solvent (anhydrous system) and is difficult to be recycled, so the cost is greatly improved, and the difficulty of industrial production is increased.
CN106867663A discloses a method for removing safrole from nutmeg, which is to use molecular distillation for crude separation and then silica gel for fine separation. Using organic solvent: eluting with petroleum ether, n-hexane, No. 6 solvent and ethyl acetate, and mixing with the essential oil without safrole. CN101415808B discloses a method for selectively removing safrole from nutmeg oil, which comprises the steps of carrying out polymerization reaction under the action of a cross-linking agent by using dihydrosafrole as a template and acrylamide as a monomer to obtain a molecularly imprinted copolymer, and repeatedly adsorbing and eluting the dihydrosafrole, wherein 97% of safrole can be removed to the maximum.
At present, a method for removing safrole from borneol essential oil is unavailable, and a method which is simple and suitable for industrial production is particularly lacked. Some of the organic solvents used in a limited manner involve residual amounts of solvent, and therefore are very cumbersome and time-consuming subsequent processing steps. Therefore, there is a need to develop an effective and reliable separation method for separating borneol essential oil.
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention aims to provide a method for removing safrole from borneol oil.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for removing safrole from borneol oil, which comprises the following steps:
(1) pretreating and filling column separation filler, and then filling borneol oil into the column;
(2) eluting with eluent, collecting, and concentrating to obtain Borneolum essential oil without safrole.
Preferably, the column separation packing in step (1) is non-polar macroporous resin or activated carbon.
In the present invention, the nonpolar macroporous resin has a polystyrene-type skeleton structure.
Preferably, the non-polar macroporous resin is any one of Diaion HP20, Diaion HP21 or Amberlite XAD-4.
Preferably, the activated carbon is any one of wood activated carbon, bamboo activated carbon, shell activated carbon and coal activated carbon.
Preferably, the pretreatment in step (1) is to soak the column separation packing with 50-95% ethanol (which may be 50%, 60%, 70%, 80%, 90% or 95%, for example).
In the invention, after the resin is soaked in the ethanol, the resin is balanced, and the soaking is finished after the soaking solution is in a state without peculiar smell.
In the present invention, after the borneol oil is loaded into the column in the step (1), the column separation packing is washed with 2 to 3 times (for example, 2 times, 2.2 times, 2.4 times, 2.5 times, 2.7 times, 2.9 times or 3 times) the column volume of ethanol, wherein the flow rate of ethanol is 1 to 2 times (for example, 1 time, 1.2 times, 1.4 times, 1.5 times, 1.6 times, 1.8 times, 1.9 times or 2 times) the column volume per hour, and the concentration of ethanol is 50% to 95% (for example, 50%, 60%, 70%, 80% or 95%).
Preferably, the loading mass of the naphtha in the step (1) is 10-30 g relative to a column with a volume of 140 mL. In the present invention, the eluent in step (2) is a low polyhydric alcohol.
Preferably, the lower alcohol is one of methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol or a combination of at least two thereof.
Further, the lower alcohol is ethanol.
Preferably, the concentration of ethanol is 50% to 95%, and may be, for example, 50%, 60%, 70%, 80%, 90%, or 95%.
In the invention, the safrole with smaller polarity is selectively eluted from the borneol oil by using a large-polarity eluent and a non-polar filler. When ethyl acetate, acetone, petroleum ether and other eluents are used, safrole cannot be removed from borneol oil, and when low-alcohol is used as the eluent, a very good effect can be achieved.
In the present invention, when separation is performed by molecular distillation, a silica gel separation method, a molecular imprinting method, or the like, safrole in borneol oil cannot be selectively separated efficiently.
Preferably, the eluent low-alcohol is added in a volume of 1 to 2 times the column volume, for example, 1 time, 1.2 times, 1.4 times, 1.8 times, 1.9 times or 2 times.
Preferably, the eluent is a low polyol flow rate of 1 to 2 column volumes per hour, for example, 1, 1.2, 1.4, 1.8, 1.9 or 2.
In the present invention, the eluent in step (2) is the solution collected by eluting the eluent from the column.
In the present invention, the method for removing safrole from borneol oil further comprises column washing, and eluting the residual safrole.
Preferably, the column is washed with 2 to 3 times (e.g., 2 times, 2.2 times, 2.5 times, 2.7 times, 2.8 times, or 3 times) the column volume of ethanol.
Preferably, the column wash is performed with 95% ethanol.
Compared with the prior art, the invention has the following beneficial effects:
according to the method for removing the safrole from the borneol oil, the safrole in the borneol essential oil is adsorbed by utilizing the column separation filler with high safety, the components without the safrole are eluted by food-grade ethanol, the ethanol is removed by low-pressure concentration, and the safrole is not detected in the concentrated borneol essential oil. The method has strong operability and no three wastes, and can be directly expanded for production. The purified borneol essential oil has the advantages that the content of the d-borneol is obviously improved, the fragrance is purer, and the original borneol essential oil does not have unpleasant odor with slight fishy smell.
Drawings
FIG. 1 is a gas chromatogram of borneol essential oil eluted and separated in example 1.
FIG. 2 is a gas chromatogram of a control of borneol oil without elution separation.
FIG. 3 is a mass spectrum of borneol detected in example 1 of the present invention.
FIG. 4 is a mass spectrum of camphor detected in example 1 of the present invention.
FIG. 5 is a mass spectrum of safrole in borneol oil without separation treatment.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
Soaking 140mL of HP21 resin in ethanol, and eluting with 95% ethanol until the effluent has no odor. Then, 80% ethanol with 2 times of column volume is taken to replace the solvent in the filler for washing. Adsorbing 10g of borneol on a column, and collecting the effluent of the sample loading, wherein the flow rate of ethanol is 1 time of the column volume per hour. And after the sample loading is finished, adding 80% of 1-time column volume and 95% of 1-time column volume of ethanol for elution, wherein the flow rate is 2 times of column volume per hour, combining the elution effluent and the sample loading effluent, and concentrating to remove ethanol to obtain the borneol essential oil.
Column washing: adding 2 times column volume of 95% ethanol at a flow rate of 2 times column volume per hour, and washing adsorbed safrole and impurities. And preparing the next column separation after the elution is finished.
And (3) carrying out GC-MS component detection on the borneol essential oil obtained in the example 1 and untreated borneol oil, wherein the specific detection parameters are as follows: the instrument comprises the following steps: agilent 7890-; a chromatographic column: INNOWAX-19091N-10550 m 0.2mm 0.2 μm capillary column; detection conditions are as follows: temperature program (initial temperature 70 ℃, temperature rise rate of 5 ℃/min, rise to 220 ℃, and hold for 30 min). The results are shown in FIG. 1 (borneol essential oil obtained in example 1) and FIG. 2 (untreated borneol oil control).
FIG. 3 is a mass spectrum of borneol, FIG. 4 is a mass spectrum of camphor, and FIG. 5 is a mass spectrum of safrole in borneol oil without separation treatment.
From the results shown in fig. 1 and fig. 2, it can be concluded that the peak of safrole can not be detected by GC-MS of the borneol oil treated by the method, so as to remove the safrole from the borneol oil.
Example 2
Soaking 140mL of HP20 resin in ethanol, and eluting with 95% ethanol until the effluent has no odor. Then, 50% ethanol with 3 times of column volume is taken to replace the solvent in the filler for washing. Adsorbing 30g of borneol on a column, and collecting the effluent of the sample loading, wherein the flow rate of ethanol is 1.5 times of the column volume per hour. And after the sample loading is finished, adding 50% of methanol with the volume of 1 time of the column volume and 1.5 times of methanol with the volume of 85% of the column volume to perform gradient elution at the flow rate of 1 time of the column volume per hour, combining the elution effluent and the sample loading effluent, and concentrating to remove the solvent to obtain the borneol essential oil.
Column washing: adding 2 times column volume of 95% ethanol at a flow rate of 2 times column volume per hour, and washing adsorbed safrole and impurities. And preparing the next column separation after the elution is finished.
Example 3
140mL of Amberlite XAD-4 resin is taken, soaked by ethanol and eluted by 95 percent ethanol until effluent liquid has no peculiar smell. Then, 70% ethanol with 2.5 times of column volume is taken to replace the solvent in the filler for washing. Adsorbing 20g of borneol on a column, and collecting the effluent of the sample loading, wherein the flow rate of ethanol is 2 times of the column volume per hour. And after the sample loading is finished, adding 80% propanol with the volume being 2 times of that of the column for elution, wherein the flow rate is 1.5 times of that of the column per hour, combining elution effluent liquid and sample loading effluent liquid, and concentrating to remove the solvent to obtain the borneol essential oil.
Column washing: adding 95% ethanol with 3 times column volume, and washing adsorbed safrole and impurities at flow rate of 2 times column volume per hour. And preparing the next column separation after the elution is finished.
Example 4
140mL of wood activated carbon was soaked in 90% ethanol. Then 90% ethanol with 1 time of column volume is taken to replace the solvent in the filler. Adsorbing 30g of dragon's brain oil on a column, wherein the flow rate of ethanol is 1 time of the column volume per hour, and collecting the effluent of the sample loading. And after the sample loading is finished, adding 90% of 2 times of column volume of ethanol for elution, wherein the flow rate is 1.4 times of column volume per hour, combining elution effluent and sample loading effluent, and concentrating to remove ethanol to obtain borneol essential oil.
Column washing: adding 2 times column volume of 95% ethanol at a flow rate of 2 times column volume per hour, and washing adsorbed safrole and impurities. And preparing the next column separation after the elution is finished.
In the above examples 1-4, the same batch of borneol oil was used for GC analysis and detection, wherein the detection conditions were Agilent 7820A gas chromatograph, Agilent 19091J-413:1, HP-55% Phenyl methyl siloxan 30m 0.32mm 0.25 μm capillary column, temperature program (initial temperature 70 ℃, temperature rise rate of 5 ℃/min, up to 220 ℃, and hold for 5min), and the percentage of each component in the borneol essential oil was determined by area normalization, and the results are shown in table 1 below.
TABLE 1
As can be seen from table 1 above, safrole is not detected in the concentrated essential oil, and examples 1 to 4 all achieve good separation effect, and the yield (the ratio of the weight of the concentrated borneol essential oil to the weight of the loaded borneol oil) is high, which proves that the method of the present invention has very good separation effect.
The applicant states that the present invention is illustrated by the above examples to describe a method for removing safrole from borneol oil, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (12)
1. A method for removing safrole from borneol oil, comprising the steps of:
(1) pretreating and filling column separation filler, and then filling borneol oil into the column;
(2) eluting with eluent, and concentrating the eluent to obtain Borneolum essential oil without safrole;
wherein, the column separation filler in the step (1) is nonpolar macroporous resin or activated carbon;
the eluent in the step (2) is low-polyalcohol;
the pretreatment of the step (1) is to soak the column separation filler by ethanol, and the concentration of the ethanol is 50-95 percent;
the step (1) also comprises the step of flushing the column separation filler with 2-3 times of column volume of ethanol, wherein the flow rate of the ethanol is 1-2 times of column volume per hour, and the concentration of the ethanol is 50-95%.
2. The method for removing safrole from naphtha as claimed in claim 1, wherein said non-polar macroporous resin is any one of Diaion HP20, Diaion HP21 or Amberlite XAD-4.
3. The method for removing safrole from dragon's oil according to claim 1, wherein the activated carbon is any one of wood activated carbon, bamboo activated carbon, shell activated carbon or coal activated carbon.
4. The method for removing safrole from dragon oil according to claim 1, wherein the loading mass of the dragon oil in step (1) is 10-30 g relative to a column with a volume of 140 mL.
5. The method for removing safrole from borneol oil according to any one of claims 1-4, wherein the low-alcohol in step (2) is one or a combination of at least two of methanol, ethanol, propanol, isopropanol, n-butanol and sec-butanol.
6. The method of claim 5, wherein the lower alcohol is ethanol.
7. The method of claim 6, wherein the concentration of ethanol is between 50% and 95%.
8. The method for removing safrole from borneol oil according to claim 1 or 7, wherein the addition volume of the lower alcohol is 1-2 times of the column volume.
9. The method for removing safrole from borneol oil according to claim 1 or 7, wherein the flow rate of the low-alcohol is 1-2 column volumes per hour.
10. The method for removing safrole from borneol oil according to any of claims 1-4 and 7, wherein the method further comprises column washing.
11. The method of claim 10, wherein the column washing is performed with 2 to 3 column volumes of ethanol.
12. The method for removing safrole from borneol oil according to claim 11, wherein the concentration of ethanol is 95%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710984757.2A CN107815348B (en) | 2017-10-20 | 2017-10-20 | Method for removing safrole from borneol oil |
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| CN201710984757.2A CN107815348B (en) | 2017-10-20 | 2017-10-20 | Method for removing safrole from borneol oil |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619062A (en) * | 2009-07-02 | 2010-01-06 | 华宝食用香精香料（上海）有限公司 | Natural fibrauretine crystal and macroporous adsorbent resin preparation method thereof |
| CN106867663A (en) * | 2015-12-10 | 2017-06-20 | 华芳烟用香料有限公司 | A kind of method of safrole in removal mace oil |
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2017
- 2017-10-20 CN CN201710984757.2A patent/CN107815348B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619062A (en) * | 2009-07-02 | 2010-01-06 | 华宝食用香精香料（上海）有限公司 | Natural fibrauretine crystal and macroporous adsorbent resin preparation method thereof |
| CN106867663A (en) * | 2015-12-10 | 2017-06-20 | 华芳烟用香料有限公司 | A kind of method of safrole in removal mace oil |
Non-Patent Citations (2)
| Title |
|---|
| 《功能性吸附树脂的制备与性能研究》;张斯;《中国优秀硕士学位论文全文数据库》;20150601;全文 * |
| 《樟树籽油甘油酯分离纯化及抑菌活性》;洪学斌;《中国优秀硕士学位论文全文数据库》;20150603;全文 * |
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Effective date of registration: 20211103 Address after: 510460 No.63, guoya Road, Shenshan management area, Jianggao Town, Baiyun District, Guangzhou City, Guangdong Province Patentee after: GUANGDONG AISHENG DAILY CHEMICAL CO.,LTD. Address before: No.68 Jinghu Avenue, Xinya street, Huadu District, Guangzhou, Guangdong 510800 Patentee before: GUANGZHOU RIDGEPOLE BIOLOGICAL TECHNOLOGY Co.,Ltd. |