CN108251214A - The separation method of Trace Phthalate Acid Esters class plasticiser in a kind of natural plants absolute oil - Google Patents
The separation method of Trace Phthalate Acid Esters class plasticiser in a kind of natural plants absolute oil Download PDFInfo
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- CN108251214A CN108251214A CN201611272241.7A CN201611272241A CN108251214A CN 108251214 A CN108251214 A CN 108251214A CN 201611272241 A CN201611272241 A CN 201611272241A CN 108251214 A CN108251214 A CN 108251214A
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- China
- Prior art keywords
- phthalate
- plasticiser
- absolute oil
- phthalate plasticiser
- natural plants
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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
- C11B9/00—Essential oils; Perfumes
- C11B9/02—Recovery or refining of essential oils from raw materials
- C11B9/022—Refining
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
The present invention provides a kind of separation method of Trace Phthalate Acid Esters class plasticiser in natural plants absolute oil, including using natural plants absolute oil as raw material, the light component A# of the no phthalate plasticiser and heavy constituent B# rich in phthalate plasticiser can be obtained after being detached using molecular distillation, column chromatography is further used for heavy constituent B#, it is eluted with the mixed liquor of nonpolar solvent and ethyl alcohol, collect the eluent without phthalate plasticiser, it is mixed after removing solvent with the light component A# of no phthalate plasticiser, up to the natural plants absolute oil of separated phthalate plasticiser.Using the method for phthalate plasticiser in separating natural plant absolute oil of the present invention, phthalate plasticiser in natural plants absolute oil can be efficiently separated, the total amount of phthalate plasticiser is less than 0.3mg/kg in natural plants absolute oil after refined, and Product Safety and application range increase substantially.This preparation method operating procedure is simple, at low cost, is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of separating technologies of Trace Phthalate Acid Esters class plasticiser in natural plants absolute oil, belong to fragrant
Expect finishing technology field.
Background technology
Plasticiser is also known as plasticizer or plasticizer, is a kind of additive for the flexibility or material liquefaction for increasing material.
Phthalate plasticiser is a kind of plasticiser most important in plasticiser and maximum dosage, but its molecular structure is similar
" hormone " is classified as suspected environmental hormone, and there is larger human body to endanger.At present it is both domestic and external research shows that, adjacent benzene two
Formate ester plasticiser may act on cell chromosome, and chromosome number and structure is made to change, so as to organize some, carefully
The growth of born of the same parents is out of control, generates tumour, causes genetic disease.Such as long-term intake phthalate plasticiser, people may interfere with
The secretion of body hormone causes child's gender that pregnant woman gives birth to occur abnormal, endangers male reproductive function, promotes female precocious puberty, the moon
Through the damage in terms of the reproductive systems such as disorderly, infertile, as reproduction rate reduction, miscarriage, congenital defect, exception sperm count,
Damage of testis causes deformed child etc..
After having broken out food plasticiser disturbance since Taiwan in 2011, countries in the world all improve police to plasticiser
It is cautious.To ensure food security, present countries in the world have all had limitation to provide phthalate compound：Europe food
Product security bureau has formulated several adjacent the daily of diformic ester can intake, i.e. 0.01 μ g/kg of DBP Limited Doses, BBP Limited Doses
0.5 μ g/kg, 0.01 μ g/kg of DEHP Limited Doses, 0.15 μ g/kg of diisooctyl phthalate (DIDP) Limited Doses, O-phthalic
0.15 μ g/kg of dioctyl phthalate (DOP) Limited Doses.The World Health Organization is limited to the amount of daily intaking of DMP within 500 μ g/kg.
The Ministry of Public Health of China is in publication in 2011 about announce in food may the non-edible material from soybeans of illegal addition and easily indiscriminate
The bulletin (2011 No. 16) of food additives list (the 6th batch) list in food may illegal addition non-food
The phthalate food additives list with substance and easily abused, including phthalic acid two (2- ethyls) own ester
(DEHP), diisononyl phthalate (DINP), diphenyl phthalate, repefral (DMP), adjacent benzene two
Formic acid diethylester (DEP), dibutyl phthalate (DBP), diamyl phthalate (DPP), dihexyl phthalate
(DHXP), dinonyl phthalate (DNP), diisobutyl phthalate (DIBP), dicyclohexyl phthalate
(DCHP), di-n-octyl phthalate (DNOP), butyl benzyl phthalate (BBP), (the 2- methoxies of phthalic acid two
Base) ethyl ester (DMEP), phthalic acid two (2- ethyoxyls) ethyl ester (DEEP), phthalic acid two (2- butoxy) ethyl ester
(DBEP), phthalic acid two (4- methyl -2- amyls) ester (BMPP) etc..The same year is issued《General office of the Ministry of Public Health is about notification
Essence for food fragrance is applicable in the letter of phthalate substance maximum residue limit relevant issues》It (defends and does supervision letter [2011]
551) maximum residue limit that, the inside defines DEHP, DINP, DBP in food and food additives be respectively 1.5mg/kg,
9.0mg/kg、0.3mg/kg；Later defend do supervision letter [2011] 773 the inside again in clear stipulaties essence for food fragrance on
It states 17 kinds of phthalate substance total contents and must not exceed 60mg/kg.
Natural plants absolute oil refers to be extracted with ethyl alcohol or with extraction plant fresh flower or leaf, and concentrate made from immersion liquid
Medicinal extract, chilled processing are filtered off insoluble in the total material (being wax mostly) in ethyl alcohol, are then distilled back under low-temperature reduced-pressure
Oily liquids with plant characteristics fragrance obtained from receiving ethyl alcohol.In its raw material planting processing, extraction and cleaning, packed and transported etc.
Link is it is possible that bring plasticiser into：1) phthalate be naturally occurring in or raw material in doped with plastic products, through work
Cause content exceeded after skill enrichment；2) it extracts the solvent used in process and is not inconsistent standardization requirement；3) it produces or stores
It contacts and brings into plastic products in the process.It can pass through reinforcement process generally, for the plasticiser pollution in production, extraction processing
Quality control is avoided, but as the plasticizing in the getting worse of China's environmental pollution, empty gas and water, soil etc. is more or less
It accumulates in plant itself, extracted and concentration, plasticiser therein certainly will be enriched with and migrate into product.Therefore, for dirty
The natural plants absolute oil of plasticiser is contaminated, screening suitable technique reduces the content of its plasticiser, has important practical significance.
At present, country's document of Selective Separation phthalate plasticiser from natural plants absolute oil does not appear in the newspapers
Road, also there has been no meet industrial production and have the separation method of economically application value for fragrance industry.How separating natural is planted
Phthalate plasticiser in object absolute oil, to promote its safety and application range, it has also become one is worth urgently to be resolved hurrily
The problem of.
Invention content
For the country there has been no can in the separating plant absolute oil of industrialization phthalate plasticizing agent method present situation,
The method that the present invention provides phthalate plasticiser in a kind of separating natural plant absolute oil.
The technical solution adopted in the present invention is phthalate plasticiser in a kind of removal separating plant absolute oil
Method, specially first carries out component separation using molecularly distilled to natural plants absolute oil, is then directed to rich in phthalic acid
The further chromatography of component of esters plasticiser, phthalate plasticiser is total in the natural plants absolute oil finally obtained
Measure ＜ 5mg/kg.
This method is as follows：
(1) natural plants absolute oil is subjected to molecular distillation separation, obtains the light component of no phthalate plasticiser
The A# and heavy constituent B# rich in phthalate plasticiser；
(2) the heavy constituent B# that phthalate plasticiser is rich in step (1) is subjected to column chromatography, it is molten with nonpolarity
Agent and alcohol mixeding liquid elution, collect the eluent of no phthalate plasticiser, remove after solvent with nothing in step (1)
The light component A# of phthalate plasticiser mixes net to get the natural value object of separated phthalate plasticiser
Oil.
Temperature is 80~120 DEG C in the step (1), and vacuum degree is 50~200Pa；
Chromatographic stuffing in the step (2) is any one in silica gel, aluminium oxide；
Filler mesh number in the step (2) is 80~200 mesh；
Nonpolar solvent and ethyl acetate mixtures are mixed according to 40: 1~20: 1 ratio of volume ratio in the step (2)
Mixed liquor；
The nonpolar solvent is petroleum ether, any one solvent in n-hexane, No. 6 solvent naphthas.
The method of phthalate plasticiser, can efficiently separate day in separating natural plant absolute oil using the present invention
Phthalate plasticiser in right plant absolute oil, simple for process, at low cost, adjacent benzene two in natural plants absolute oil after processing
The total amount ＜ 0.3mg/kg of formate ester plasticiser, safety and application range increase substantially.
Specific embodiment
The following examples are that the present invention is further described.
Embodiment 1
(1) FLOS CHRYSANTHEMI ALBA from Haizhou of China oil is subjected to molecular distillation separation, controlled at 120 DEG C, vacuum degree 200Pa is collected respectively
Light component A# and heavy constituent B#；
(2) the heavy constituent B# that phthalate plasticiser is rich in step (1) is subjected to silica gel column chromatography, using mixed
Bonding solvent elutes, and collects the eluent of no phthalate plasticiser, remove after solvent in step (1) without O-phthalic
The light component A# of esters of gallic acid plasticiser mixes the FLOS CHRYSANTHEMI ALBA from Haizhou of China oil to get separated phthalate plasticiser, wherein used
Silica gel mesh number for 80~100 mesh, mixed solvent is VPetroleum ether∶VEthyl alcohol=40: 1 solvent being uniformly mixed, petroleum ether used
Boiling point is 60~90 DEG C；
(3) above-mentioned sample is taken, gas chromatography-mass spectrography detects, phthalate plasticiser total amount in FLOS CHRYSANTHEMI ALBA from Haizhou of China oil
0.27mg/kg is down to by original 105.61mg/kg.
Embodiment 2
(1) tree moss absolute is subjected to molecular distillation separation, controlled at 100 DEG C, vacuum degree 120Pa is collected respectively
Light component A# and heavy constituent B#；
(2) the heavy constituent B# that phthalate plasticiser is rich in step (1) is subjected to alumina column chromatography, used
Mixed solvent elutes, and collects the eluent of no phthalate plasticiser, remove after solvent in step (1) without adjacent benzene two
The light component A# of formate ester plasticiser mixes the tree moss absolute to get separated phthalate plasticiser, wherein institute
Aluminium oxide mesh number is 80~100 mesh, and mixed solvent is VNo. 6 solvents∶VEthyl alcohol=30: 1 solvent being uniformly mixed；
(3) above-mentioned sample is taken, gas chromatography-mass spectrography detects, phthalate plasticiser total amount in tree moss absolute
0.16mg/kg is down to by original 92.85mg/kg.
Embodiment 3
(1) absolute of jasmine is subjected to molecular distillation separation, controlled at 80 DEG C, vacuum degree 50Pa, collected respectively light
Component A# and heavy constituent B#；
(2) the heavy constituent B# that phthalate plasticiser is rich in step (1) is subjected to silica gel column chromatography, using mixed
Bonding solvent elutes, and collects the eluent of no phthalate plasticiser, remove after solvent in step (1) without O-phthalic
The light component A# of esters of gallic acid plasticiser mixes the absolute of jasmine to get separated phthalate plasticiser, wherein used
Silica gel mesh number for 100~200 mesh, mixed solvent is VHexane∶VEthyl alcohol=20: 1 solvent being uniformly mixed；
(3) above-mentioned sample is taken, gas chromatography-mass spectrography detects, phthalate plasticiser total amount in absolute of jasmine
0.23mg/kg is down to by original 137.14mg/kg.
Claims (5)
1. a kind of separation method of Trace Phthalate Acid Esters class plasticiser in natural plants absolute oil, it is characterised in that：
(1) it carries out molecular distillation separation using natural plants absolute oil as raw material, can obtain without the light of phthalate plasticiser
The component A# and heavy constituent B# rich in phthalate plasticiser；
(2) for the heavy constituent B# rich in phthalate plasticiser, column chromatography is carried out, with nonpolar solvent and ethyl alcohol
Mixed liquor elutes, and collects the eluent of no phthalate plasticiser, is moulded after removing solvent with no phthalate
The light component A# of agent mixes the natural plants absolute oil to get separated phthalate plasticiser.
2. the method for phthalate plasticiser in the separating natural plant absolute oil according to claims 1, special
Sign is that the temperature in step (1) is 80~120 DEG C, and vacuum degree is 50~200Pa.
3. the method for phthalate plasticiser in the separating natural plant absolute oil according to claims 1, special
Sign is column chromatography filler used in step (2) for any one in silica gel, aluminium oxide, and mesh number is 80~200 mesh.
4. the method for phthalate plasticiser in the separating natural plant absolute oil according to claims 1, special
Sign is in mixed liquor used in step (2) that the volume ratio of nonpolar solvent and ethyl alcohol is 40: 1~20: 1.
5. the method for phthalate plasticiser in the separating natural plant absolute oil according to claims 1, special
Sign is nonpolar solvent used in step (2) for any one solvent in petroleum ether, normal hexane, No. 6 solvent naphthas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611272241.7A CN108251214A (en) | 2016-12-29 | 2016-12-29 | The separation method of Trace Phthalate Acid Esters class plasticiser in a kind of natural plants absolute oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611272241.7A CN108251214A (en) | 2016-12-29 | 2016-12-29 | The separation method of Trace Phthalate Acid Esters class plasticiser in a kind of natural plants absolute oil |
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| Publication Number | Publication Date |
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| CN108251214A true CN108251214A (en) | 2018-07-06 |
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| CN201611272241.7A Withdrawn CN108251214A (en) | 2016-12-29 | 2016-12-29 | The separation method of Trace Phthalate Acid Esters class plasticiser in a kind of natural plants absolute oil |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109022145A (en) * | 2018-08-14 | 2018-12-18 | 杨富尧 | A kind of preparation method of the serial grease of zero plasticiser Ω -3 of low-peroxide value, Ω -6 |
| CN112029581A (en) * | 2020-09-08 | 2020-12-04 | 贵州航天乌江机电设备有限责任公司 | Method for removing phthalate plasticizer in vegetable oil |
| CN113201397A (en) * | 2021-04-08 | 2021-08-03 | 四川国为制药有限公司 | Method for reducing plasticizer content in fish oil product |
| CN113604279A (en) * | 2020-12-16 | 2021-11-05 | 贵州玄德生物科技股份有限公司 | Method and equipment for removing plasticizer from zanthoxylum oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586022A (en) * | 2012-01-12 | 2012-07-18 | 中山大学 | Method for removing plasticizer in plant essential oil |
| WO2016132354A1 (en) * | 2015-02-17 | 2016-08-25 | Enzymotec Ltd. | Oil blends, processes for the preparation thereof and their use in formulas |
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2016
- 2016-12-29 CN CN201611272241.7A patent/CN108251214A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586022A (en) * | 2012-01-12 | 2012-07-18 | 中山大学 | Method for removing plasticizer in plant essential oil |
| WO2016132354A1 (en) * | 2015-02-17 | 2016-08-25 | Enzymotec Ltd. | Oil blends, processes for the preparation thereof and their use in formulas |
Non-Patent Citations (1)
| Title |
|---|
| 曾锋，等: "硅胶-氧化铝层析柱-气相色谱法测定沉积物中邻苯二甲酸酯类有机物", 《分析化学》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109022145A (en) * | 2018-08-14 | 2018-12-18 | 杨富尧 | A kind of preparation method of the serial grease of zero plasticiser Ω -3 of low-peroxide value, Ω -6 |
| CN112029581A (en) * | 2020-09-08 | 2020-12-04 | 贵州航天乌江机电设备有限责任公司 | Method for removing phthalate plasticizer in vegetable oil |
| CN113604279A (en) * | 2020-12-16 | 2021-11-05 | 贵州玄德生物科技股份有限公司 | Method and equipment for removing plasticizer from zanthoxylum oil |
| CN113201397A (en) * | 2021-04-08 | 2021-08-03 | 四川国为制药有限公司 | Method for reducing plasticizer content in fish oil product |
| CN113201397B (en) * | 2021-04-08 | 2024-02-23 | 四川国为制药有限公司 | Method for reducing plasticizer content in fish oil product |
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Application publication date: 20180706 |