CN102304418A - Method of removing polluted phthalate ester material from animal and plant essential oil - Google Patents
Method of removing polluted phthalate ester material from animal and plant essential oil Download PDFInfo
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- CN102304418A CN102304418A CN201110210869A CN201110210869A CN102304418A CN 102304418 A CN102304418 A CN 102304418A CN 201110210869 A CN201110210869 A CN 201110210869A CN 201110210869 A CN201110210869 A CN 201110210869A CN 102304418 A CN102304418 A CN 102304418A
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- 239000000463 material Substances 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 79
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- 241001465754 Metazoa Species 0.000 title claims abstract description 68
- -1 phthalate ester Chemical class 0.000 title abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 140
- 238000000605 extraction Methods 0.000 claims abstract description 132
- 238000002156 mixing Methods 0.000 claims abstract description 13
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 86
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
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- 229940043232 butyl acetate Drugs 0.000 claims description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
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- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract 2
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 32
- 241000196324 Embryophyta Species 0.000 description 31
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- 241000229143 Hippophae Species 0.000 description 21
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 14
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 14
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 13
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 13
- 235000013305 food Nutrition 0.000 description 13
- 235000016425 Arthrospira platensis Nutrition 0.000 description 12
- 240000002900 Arthrospira platensis Species 0.000 description 12
- JEBFVOLFMLUKLF-IFPLVEIFSA-N Astaxanthin Natural products CC(=C/C=C/C(=C/C=C/C1=C(C)C(=O)C(O)CC1(C)C)/C)C=CC=C(/C)C=CC=C(/C)C=CC2=C(C)C(=O)C(O)CC2(C)C JEBFVOLFMLUKLF-IFPLVEIFSA-N 0.000 description 12
- 241000221030 Oenothera odorata Species 0.000 description 12
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- 235000014787 Vitis vinifera Nutrition 0.000 description 12
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- 239000001168 astaxanthin Substances 0.000 description 12
- MQZIGYBFDRPAKN-ZWAPEEGVSA-N astaxanthin Chemical compound C([C@H](O)C(=O)C=1C)C(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)[C@@H](O)CC1(C)C MQZIGYBFDRPAKN-ZWAPEEGVSA-N 0.000 description 12
- 229940022405 astaxanthin Drugs 0.000 description 12
- 229940082787 spirulina Drugs 0.000 description 12
- 235000015112 vegetable and seed oil Nutrition 0.000 description 12
- 239000003814 drug Substances 0.000 description 11
- 235000021323 fish oil Nutrition 0.000 description 11
- 240000008397 Ganoderma lucidum Species 0.000 description 9
- 235000001637 Ganoderma lucidum Nutrition 0.000 description 9
- 238000004040 coloring Methods 0.000 description 9
- PCZOHLXUXFIOCF-UHFFFAOYSA-N Monacolin X Natural products C12C(OC(=O)C(C)CC)CC(C)C=C2C=CC(C)C1CCC1CC(O)CC(=O)O1 PCZOHLXUXFIOCF-UHFFFAOYSA-N 0.000 description 8
- 235000009508 confectionery Nutrition 0.000 description 8
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 8
- PCZOHLXUXFIOCF-BXMDZJJMSA-N lovastatin Chemical compound C([C@H]1[C@@H](C)C=CC2=C[C@H](C)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)C[C@@H]1C[C@@H](O)CC(=O)O1 PCZOHLXUXFIOCF-BXMDZJJMSA-N 0.000 description 8
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 5
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 4
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 3
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 2
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- IPKKHRVROFYTEK-UHFFFAOYSA-N dipentyl phthalate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC IPKKHRVROFYTEK-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 210000004556 brain Anatomy 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000008172 hydrogenated vegetable oil Substances 0.000 description 1
- 229930185723 monacolin Natural products 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 238000009512 pharmaceutical packaging Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
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- 235000013555 soy sauce Nutrition 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000010497 wheat germ oil Substances 0.000 description 1
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- Fats And Perfumes (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention provides a method of removing a polluted phthalate ester material from animal and plant essential oil at high efficiency by using a back extraction agent. The method comprises the following steps of: using a solvent capable of dissolving and adsorbing the phthalate ester material as the back extraction agent, fully mixing the animal and plant essential oil containing the phthalate ester material and the back extraction agent, enabling the phthalate ester material contained in the animal and plant essential oil to be dissolved and adsorbed in the back extraction agent by using the dissolving and adsorption effect of the back extraction agent on the phthalate ester material, and then separating the back extraction agent and the animal and plant essential oil to obtain the animal and plant essential oil without the phthalate ester material. Through detection, the content of the phthalate ester material in the animal and plant essential oil processed by the method can meet the design requirement; the detection level of the phthalate ester material is reduced to below 0.15mg/kg; and the back-extraction agent in the animal and plant essential oil is not detected.
Description
Technical field
The present invention relates to a kind of method of removing contaminated phthalate material in the animals and plants essential oil.
Background technology
The phthalate material is one type of chemical that can play ramollescence, extensively as plastics and rubber and synthetic materials softening agent, is widely used in hundreds of products such as toy, food product pack, drug packaging, wallpaper, makeup and articles for washing.Usually the phthalate material that is used as softening agent refers to the ester of the alcohol formation of phthalic acid and 4～15 carbon, and wherein phthalic acid two (2-ethyl) own ester (DEHP), dibutyl phthalate (DBP) and diisobutyl phthalate (DIBP) are wherein modal kinds.
The phthalate material can cause great harm to human body, requires residual phthalic acid two (2-ethyl) own ester (DEHP), diisononyl phthalate (DINP) and the maximum detected level of dibutyl phthalate (DBP) to be respectively 1.5mg/kg, 9.0mg/kg and 0.3mg/kg in food and the foodstuff additive.Numerous food product, medicine or makeup are in production process; Because plastics, rubber item or wrapping material and the contaminated phthalate material of going up of phthalate are rich in contact; Cause a large amount of starting material and animals and plants essential oil, food, medicine and cosmetic product to be detected the phthalate substances content and exceed standard and discard, cause the significant wastage of resource.
Summary of the invention
The purpose of this invention is to provide a kind of method of removing contaminated phthalate material in the animals and plants essential oil.
The inventive method is through selecting for use the solvent that can dissolve and adsorb the phthalate material as reverse-extraction agent; Utilize dissolving and the adsorption function of reverse-extraction agent, realize the purpose that high efficiency separation is removed contained phthalate material in the animals and plants essential oil the phthalate material.
The inventive method can be applied to nearly all contaminated and contain the animals and plants essential oil of phthalate material.In the animals and plants essential oil after back extraction of the present invention (reextraction) art breading, the phthalate substances content can reach design requirements and not residual reverse-extraction agent, and has that technology simple possible and reverse-extraction agent separate easily are removed and characteristics such as reusable.
Method of the present invention is: the animals and plants essential oil that will contain the phthalate material is preheated to 35～99 ℃ respectively with reverse-extraction agent before mixing; Thorough mixing (normally fully stirring 1～10 minute) again; Utilize the function of reverse-extraction agent to the dissolving and the absorption of phthalate material, and adopt the ultrasonic oscillator vibration make the phthalate material that contains in the animals and plants essential oil dissolved be adsorbed in the reverse-extraction agent; Be easy to the isolating phenomenon of layering after utilizing the animals and plants essential oil then and reverse-extraction agent mixing, reverse-extraction agent layer (phase) is separated the animals and plants essential oil of the phthalate material that is removed with animals and plants essential oil layer (mutually).Can adopt common industrial vacuum distillatory method to remove reverse-extraction agent residual in the animals and plants essential oil at last.
The ratio of described animals and plants essential oil and reverse-extraction agent can be 1: 0.5～20 (weight ratios), and optimum proportion is 1: 1～6 (weight ratios); Described solvent as reverse-extraction agent comprises ethanol, isopropyl acetone, butanols, hexalin, acetone, butanone, pimelinketone or butylacetate etc., and working concentration is 50～99% usually, and optimum concn is 75～95%.
According to the invention described above method, its concrete steps can comprise:
1, animals and plants essential oil and the reverse-extraction agent that will contain the phthalate material is preheated to 35～99 ℃ respectively before stirring mixing, and optimum Preheating Temperature is 40～75 ℃; Animals and plants essential oil after preheating is added reverse-extraction agent; Stirred 1～10 minute; Make animals and plants essential oil and reverse-extraction agent thorough mixing, and the phthalate material thorough washing that adopts ultrasonic oscillator vibration 2～10min to make to contain in the animals and plants essential oil and dissolved be adsorbed in the reverse-extraction agent;
2, leave standstill, the animals and plants essential oil is separated with the reverse-extraction agent layering, the reverse-extraction agent that floats over the upper strata after the animals and plants essential oil that sinks to lower floor after the layering and the layering is separated; The dissolving that floats over the upper strata after the animals and plants essential oil that sinks to lower floor after can adopting common industrial siphonage or separating funnel partition method with layering and the layering separates with the reverse-extraction agent that is adsorbed with the phthalate material; Can adopt common industrial method of cooling to quicken the animals and plants essential oil and separate with the layering of reverse-extraction agent, cooling temperature is-15 ℃～10 ℃ usually, and best cooling temperature is-10 ℃～5 ℃;
This step 2 also can adopt common industrial centrifugal separating device directly just the animals and plants essential oil separate with reverse-extraction agent;
3, adopt common industrial vacuum distillatory method to remove reverse-extraction agent residual in the animals and plants essential oil, the vacuum tightness that vacuum distilling is adopted usually is-880～-550mbar, distillation temperature is 40～65 ℃; The animals and plants essential oil of phthalate material is removed in acquisition; Through detecting, can reach design requirements through phthalate substances content in the animals and plants essential oil of stripping process processing, phthalate material detected level is all reduced to below the 0.15mg/kg, and reverse-extraction agent does not detect in the animals and plants essential oil that purifies.
According to the inventive method; According to design demand; Can be with animals and plants essential oil through above-mentioned steps 1 and the processing of 2 stripping process; Carry out secondary according to above-mentioned steps 1 and 2 again or repeatedly (be generally 2～5 times) stripping process handling, obtain to reach the animals and plants essential oil of further removing the phthalate material of design requirements.
The reverse-extraction agent of in the stripping process of the inventive method, separating can reclaim or reuse through common industrial vacuum distillatory method.
The phthalate material that the inventive method relates to comprises phthalic acid two (2-ethyl) own ester (DEHP); Dibutyl phthalate (DBP); Diisobutyl phthalate (DIBP); Phthalic acid tolyl butyl ester (BBP); Diethyl phthalate (DEP); Dipropyl phthalate (DPrP); Diamyl phthalate (DPP); Dinoctyl phthalate (DNOP); Diisononyl phthalate (DINP); Di Iso Decyl Phthalate (DIDP); Dimethyl phthalate (DMP); Dihexyl phthalate (DHP); Dicyclohexyl phthalate (DCHP); Dimixo-octyl phthalate (DIOP) is or/and 2-nonyl-phthalate ester (DNNP);
The animals and plants essential oil that the inventive method relates to; Comprise raisin seed oil, Semen Juglandis oil, safflower oil, oenothera odorata oil, red Ganoderma lucidum spore oil, astaxanthin, Lyeopene, red colouring agent for food, also used as a Chinese medicine Monacolin K, Oleum Hippophae, sweet oil, Fructus Maydis oil, wheatgerm oil, peanut oil, sesame oil, fish oil, flake wo soy sauce, fis brain oil, seal oil, algal oil, spirulina oil, hydrogenated vegetable oil, cream, butter, lard or medicinal plant essential oil etc.;
The ultrasonic oscillator that the inventive method relates to is common industrial ultrasonic oscillator, and ultrasonic frequency is 20～40Khz.
The per-cent of the various amounts that the inventive method relates to (%) except other has explanation, all is weight percentage.
Embodiment
Below in conjunction with embodiment the present invention is done further explain.
Embodiment one:
1, the pollution of the DEHP60mg/kg of containing to be detected, DINP28mg/kg, DBP39mg/kg there is the raisin seed oil of phthalate material and be preheated to 75 ℃ respectively as 90% acetone of reverse-extraction agent; Raisin seed oil after preheating is mixed the abundant stirring in back 1 minute with reverse-extraction agent; The ratio of raisin seed oil and 90% acetone is 1: 6 (weight ratio); Adopting ultrasonic frequency is the ultrasonic oscillator vibration 10min of 20Khz, the phthalate material that contains in the raisin seed oil is fully dissolved and is adsorbed in the reverse-extraction agent;
2, leave standstill; And adopt common industrial method of cooling to quicken raisin seed oil and separate with the layering of reverse-extraction agent; Cooling temperature is-15 ℃, adopts raisin seed oil that the separating funnel partition method will sink to lower floor and floats over the dissolving on upper strata and be adsorbed with the reverse-extraction agent acetone separation of phthalate material;
3, the raisin seed oil that step 2 is separated repeats the processing of secondary stripping process again by above step 1 and 2, obtains further to remove the raisin seed oil of phthalate material;
4, adopt common industrial vacuum distillatory method to remove reverse-extraction agent acetone residual in the raisin seed oil, it is-550mbar that temperature is 62 ℃ a condition that vacuum tightness is adopted in vacuum distilling; Reverse-extraction agent acetone can reclaim and reuse through common industrial vacuum distillatory method; Through detecting, after above-mentioned stripping process processing, the DEHP detected level in the raisin seed oil in the phthalate material is that 0.1mg/kg, DINP detected level are that 0.14mg/kg, DBP detected level are 0.12mg/kg, does not detect reverse-extraction agent acetone in the raisin seed oil.
Embodiment two:
1, respectively the pollution of the DEHP100mg/kg of containing to be detected, DINP26mg/kg, DBP35mg/kg there is the oenothera odorata oil of phthalate material and be preheated to 40 ℃ as 50% butanols of reverse-extraction agent; Oenothera odorata oil after preheating is mixed back stirring 8 minutes with reverse-extraction agent; The ratio of oenothera odorata oil and 50% butanols is 1: 20 (weight ratio); Adopting ultrasonic frequency is the ultrasonic oscillator vibration 5min of 40Khz, the phthalate material that contains in the oenothera odorata oil is fully dissolved and is adsorbed in the reverse-extraction agent;
2, leave standstill; Oenothera odorata oil is separated with the reverse-extraction agent butanols layering that is adsorbed with the phthalate material with dissolving, and the dissolving that floats over the upper strata after the oenothera odorata oil that adopts common industrial siphonage that layering is separated to sink to lower floor and the layering separate with the reverse-extraction agent butanols that is adsorbed with the phthalate material;
3, the oenothera odorata oil that step 2 is separated repeats the processing of secondary stripping process again by above step 1 and 2, obtains further to remove the oenothera odorata oil of phthalate material;
4, adopt common industrial vacuum distillatory method to remove reverse-extraction agent butanols residual in the oenothera odorata oil, it is-800mbar that temperature is 40 ℃ a condition that vacuum tightness is adopted in vacuum distilling; The reverse-extraction agent butanols can reclaim and reuse through common industrial vacuum distillatory method; Through detecting, after above-mentioned stripping process processing, the DEHP detected level in the oenothera odorata oil in the phthalate material is that 0.05mg/kg, DINP detected level are that 0.08mg/kg, DBP detected level are 0.03mg/kg, does not detect the reverse-extraction agent butanols in the oenothera odorata oil.
Embodiment three:
1, the pollution of the DEHP10mg/kg of containing to be detected, DINP15mg/kg, DBP18mg/kg there is the Oleum Hippophae of phthalate material and be preheated to 90 ℃ respectively as 80% ethanol of reverse-extraction agent; Oleum Hippophae after preheating is mixed the abundant stirring in back 10 minutes with reverse-extraction agent; Oleum Hippophae and 80% alcoholic acid ratio are 1: 4 (weight ratio); Adopting ultrasonic frequency is the ultrasonic oscillator vibration 3min of 30Khz, the phthalate material that contains in the Oleum Hippophae is fully dissolved and is adsorbed in the reverse-extraction agent;
2, leave standstill; Oleum Hippophae is separated with the reverse-extraction agent ethanol layering that is adsorbed with the phthalate material with dissolving, and the Oleum Hippophae that sinks to lower floor after adopting common industrial separating funnel partition method to mix separate with the reverse-extraction agent ethanol that is adsorbed with the phthalate material with the dissolving that floats over the upper strata;
3, the Oleum Hippophae that step 2 is separated repeats the processing of secondary stripping process again by above step 1 and 2, obtains further to remove the Oleum Hippophae of phthalate material;
4, adopt common industrial vacuum distillatory method to remove reverse-extraction agent ethanol residual in the Oleum Hippophae, it is-650mbar that temperature is 50 ℃ a condition that vacuum tightness is adopted in vacuum distilling; Reverse-extraction agent ethanol can reclaim and reuse through common industrial vacuum distillatory method; Through detecting, after above-mentioned stripping process processing, the DEHP detected level in the Oleum Hippophae in the phthalate material is that 0.09mg/kg, DINP detected level are that 0.05mg/kg, DBP detected level are 0.03mg/kg, does not detect reverse-extraction agent ethanol in the Oleum Hippophae.
Embodiment four:
1, respectively the pollution of the DEHP50mg/kg of containing to be detected, DINP28mg/kg, DBP19mg/kg there is the fish oil of phthalate material and be preheated to 70 ℃ as 85% butanone of reverse-extraction agent; Fish oil after preheating is mixed the abundant stirring in back 2 minutes with reverse-extraction agent; The ratio of fish oil and 85% butanone is 1: 12 (weight ratio); Adopting ultrasonic frequency is the ultrasonic oscillator vibration 6min of 40Khz, the phthalate material that contains in the fish oil is fully dissolved and is adsorbed in the reverse-extraction agent;
2, the dissolving that is easy to float over after fish oil that the layering separation sinks to lower floor and the layering upper strata after adopting common industrial centrifugal separating device to mix separates with the reverse-extraction agent butanone that is adsorbed with the phthalate material;
3, the fish oil that step 2 is separated repeats three stripping process processing again by above step 1 and 2, obtains further to remove the fish oil of phthalate material;
4, adopt common industrial vacuum distillatory method to remove reverse-extraction agent butanone residual in the fish oil, it is-700mbar that temperature is 46 ℃ a condition that vacuum tightness is adopted in vacuum distilling; The reverse-extraction agent butanone can reclaim and reuse through common industrial vacuum distillatory method; Through detecting, after above-mentioned stripping process processing, the DEHP detected level in the fish oil in the phthalate material is that 0.1mg/kg, DINP detected level are that 0.08mg/kg, DBP detected level are 0.09mg/kg, does not detect the reverse-extraction agent butanone in the fish oil.
Embodiment five:
1, respectively the pollution of the DEHP2.1mg/kg of containing to be detected, DINP4.1mg/kg, DBP0.38mg/kg there is the red Ganoderma lucidum spore oil of phthalate material and be preheated to 52 ℃ as 82% acetone of reverse-extraction agent; Red Ganoderma lucidum spore oil after preheating is mixed the abundant stirring in back 9 minutes with reverse-extraction agent; Red Ganoderma lucidum spore oil is 1: 0.5 (weight ratio) with the ratio of 82% acetone; Adopting ultrasonic frequency is the ultrasonic oscillator vibration 4min of 30Khz, the phthalate material that contains in the red Ganoderma lucidum spore oil is fully dissolved and is adsorbed in the reverse-extraction agent;
2, adopt common industrial centrifugal separating device that red Ganoderma lucidum spore oil is effectively separated with the reverse-extraction agent acetone that is adsorbed with the phthalate material with dissolving;
3, adopt common industrial vacuum distillatory method to remove reverse-extraction agent acetone residual in the red Ganoderma lucidum spore oil, it is-750mbar that temperature is 43 ℃ a condition that vacuum tightness is adopted in vacuum distilling; Reverse-extraction agent acetone can reclaim and reuse through common industrial vacuum distillatory method; Through detecting; After above-mentioned stripping process processing; DEHP detected level in the red Ganoderma lucidum spore oil in the phthalate material is that 0.03mg/kg, DINP detected level are that 0.08mg/kg, DBP detected level are 0.09mg/kg, does not detect reverse-extraction agent acetone in the red Ganoderma lucidum spore oil.
Embodiment six:
1, respectively the pollution of the DEHP28mg/kg of containing to be detected, DINP20mg/kg, DBP24mg/kg there is the astaxanthin of phthalate material and be preheated to 72 ℃ as 88% pimelinketone of reverse-extraction agent; Astaxanthin after preheating is mixed the abundant stirring in back 4 minutes with reverse-extraction agent; The ratio of astaxanthin and 88% pimelinketone is 1: 14 (weight ratio); Adopting ultrasonic frequency is the ultrasonic oscillator vibration 8min of 40khz, the phthalate material that contains in the astaxanthin is fully dissolved and is adsorbed in the reverse-extraction agent;
2, leave standstill; Astaxanthin is separated with the reverse-extraction agent pimelinketone layering that is adsorbed with the phthalate material with dissolving, and adopt the dissolving that floats over the upper strata after astaxanthin that common industrial siphonage will sink to lower floor and the layering to separate with the reverse-extraction agent pimelinketone that is adsorbed with the phthalate material;
3, the astaxanthin that step 2 is separated repeats the processing of secondary stripping process again by above step 1 and 2,, the astaxanthin of phthalate material is further removed in acquisition;
4, adopt common industrial centrifugal separating device to remove reverse-extraction agent pimelinketone residual in the astaxanthin, it is-550mbar that temperature is 60 ℃ a condition that vacuum tightness is adopted in vacuum distilling; The reverse-extraction agent pimelinketone can reclaim and reuse through common industrial vacuum distillatory method; Through detecting, after above-mentioned stripping process processing, the DEHP detected level in the astaxanthin in the phthalate material is that 0.11mg/kg, DINP detected level are that 0.14mg/kg, DBP detected level are 0.13mg/kg, does not detect the reverse-extraction agent pimelinketone in the astaxanthin.
Embodiment seven:
1; Respectively with the DEHP1.9mg/kg that contains to be detected; DINP10.2mg/kg; The pollution of DBP0.5mg/kg has the red colouring agent for food, also used as a Chinese medicine Monacolin K of phthalate material and is preheated to 45 ℃ as 80% butanone of reverse-extraction agent; Red colouring agent for food, also used as a Chinese medicine Monacolin K after preheating is mixed the abundant stirring in back 10 minutes with reverse-extraction agent; The ratio of red colouring agent for food, also used as a Chinese medicine Monacolin K and 80% butanone is 1: 1.2 (weight ratio); Adopting ultrasonic frequency is the ultrasonic oscillator vibration 8min of 40Khz, the phthalate material that contains among the red colouring agent for food, also used as a Chinese medicine Monacolin K is fully dissolved and is adsorbed in the reverse-extraction agent;
2, adopt common industrial centrifugal separating device that red colouring agent for food, also used as a Chinese medicine Monacolin K is separated with the reverse-extraction agent butanone that is adsorbed with the phthalate material with dissolving;
3, adopt common industrial vacuum distillatory method to remove reverse-extraction agent butanone residual among the red colouring agent for food, also used as a Chinese medicine Monacolin K, it is-750mbar that temperature is 42 ℃ a condition that vacuum tightness is adopted in vacuum distilling; The reverse-extraction agent butanone can reclaim and reuse through common industrial vacuum distillatory method; Through detecting; After above-mentioned stripping process processing; DEHP detected level among the red colouring agent for food, also used as a Chinese medicine Monacolin K in the phthalate material is that 0.12mg/kg, DINP detected level are that 0.09mg/kg, DBP detected level are 0.11mg/kg, and red colouring agent for food, also used as a Chinese medicine Monacolin does not detect the reverse-extraction agent butanone.
Embodiment eight:
1, respectively the pollution of the DEHP1.95mg/kg of containing to be detected, DINP12.1mg/kg, DBP0.32mg/kg there is the Oleum Hippophae of phthalate material and be preheated to 68 ℃ as 90% ethanol of reverse-extraction agent; Oleum Hippophae after preheating is mixed the abundant stirring in back 2 minutes with reverse-extraction agent; Oleum Hippophae and 90% alcoholic acid ratio are 1: 2 (weight ratio); Adopting ultrasonic frequency is the ultrasonic oscillator vibration 3min of 35Khz, the phthalate material that contains in the Oleum Hippophae is fully dissolved and is adsorbed in the reverse-extraction agent;
2, leave standstill; Oleum Hippophae is separated with the reverse-extraction agent ethanol layering that is adsorbed with the phthalate material with dissolving, and adopt the dissolving that floats over the upper strata after Oleum Hippophae that common industrial siphonage will sink to lower floor and the layering to separate with the reverse-extraction agent ethanol that is adsorbed with the phthalate material;
3, adopt common industrial vacuum distillatory method to remove reverse-extraction agent ethanol residual in the Oleum Hippophae, it is-680mbar that temperature is 52 ℃ a condition that vacuum tightness is adopted in vacuum distilling; Reverse-extraction agent ethanol can reclaim and reuse through common industrial vacuum distillatory method; Through detecting, after above-mentioned stripping process processing, the DEHP detected level in the Oleum Hippophae in the phthalate material is that 0.14mg/kg, DINP detected level are that 0.13mg/kg, DBP detected level are 0.14mg/kg, does not detect reverse-extraction agent ethanol in the Oleum Hippophae.
Embodiment nine:
1, respectively the pollution of the DEHP3.2mg/kg of containing to be detected, DINP12.2mg/kg, DBP2.4mg/kg there is the sweet oil of phthalate material and be preheated to 35 ℃ as 83% butylacetate of reverse-extraction agent; Sweet oil after preheating is mixed the abundant stirring in back 7 minutes with reverse-extraction agent; The ratio of sweet oil and 83% butylacetate is 1: 3 (weight ratio); Adopting ultrasonic frequency is the ultrasonic oscillator vibration 3min of 20Khz, the phthalate material that contains in the sweet oil is fully dissolved and is adsorbed in the reverse-extraction agent;
2, adopt common industrial centrifugal separating device that sweet oil is separated with the reverse-extraction agent butylacetate that is adsorbed with the phthalate material with dissolving;
3, adopt common industrial vacuum distillatory method to remove residual reverse-extraction agent butylacetate, it is-720mbar that temperature is 43 ℃ a condition that vacuum tightness is adopted in vacuum distilling; The reverse-extraction agent butylacetate can reclaim and reuse through common industrial vacuum distillatory method; Through detecting, after above-mentioned stripping process processing, the DEHP detected level in the sweet oil in the phthalate material is that 0.08mg/kg, DINP detected level are that 0.14mg/kg, DBP detected level are 0.14mg/kg, does not detect the reverse-extraction agent butylacetate in the sweet oil.
Embodiment ten:
1, respectively the pollution of the DEHP65mg/kg of containing to be detected, DINP33mg/kg, DBP45mg/kg there is the spirulina oil of phthalate material and be preheated to 99 ℃ as 93% pimelinketone of reverse-extraction agent; Spirulina oil after preheating is mixed the abundant stirring in back 3 minutes with reverse-extraction agent; Spirulina oil is 1: 10 (weight ratio) with the ratio of 93% pimelinketone; Adopting ultrasonic frequency is the ultrasonic oscillator vibration 7min of 20Khz, the phthalate material that contains in the spirulina oil is fully dissolved and is adsorbed in the reverse-extraction agent;
2, leave standstill; Spirulina oil is separated with the reverse-extraction agent pimelinketone layering that is adsorbed with the phthalate material with dissolving, and adopt the dissolving that floats over the upper strata after spirulina oil that common industrial separating funnel partition method will sink to lower floor and the layering to separate with the reverse-extraction agent pimelinketone that is adsorbed with the phthalate material;
3, the spirulina oil of step 2 being separated carries out four stripping process again by above step 1 and 2 to be handled, and the spirulina oil of the purification of phthalate material is further removed in acquisition;
4, adopt common industrial vacuum distillatory method to remove reverse-extraction agent pimelinketone residual in the spirulina oil, it is-680mbar that temperature is 51 ℃ a condition that vacuum tightness is adopted in vacuum distilling; The reverse-extraction agent pimelinketone can reclaim and reuse through common industrial vacuum distillatory method; Through detecting; After above-mentioned stripping process processing; Phthalate material single index DEHP detected level is that 0.01mg/kg, DINP detected level are that 0.02mg/kg, DBP detected level are 0.01mg/kg in the spirulina oil, does not detect the reverse-extraction agent pimelinketone in the spirulina oil.
Claims (9)
1. method of removing phthalate material in the animals and plants essential oil; It is characterized in that the animals and plants essential oil that will contain the phthalate material is preheated to 35～99 ℃ respectively with reverse-extraction agent before mixing; Thorough mixing again, and adopt the ultrasonic oscillator vibration will make the phthalate material that contains in the animals and plants essential oil dissolved be adsorbed in the reverse-extraction agent; Be easy to the isolating phenomenon of layering after utilizing the animals and plants essential oil then and reverse-extraction agent mixing, the reverse-extraction agent layer separated the animals and plants essential oil of the phthalate material that is removed with animals and plants essential oil layer; Adopt common industrial vacuum distillatory method to remove reverse-extraction agent residual in the animals and plants essential oil at last; The ratio of described animals and plants essential oil and reverse-extraction agent is 1: 0.5～20 weight ratios, and described reverse-extraction agent comprises ethanol, isopropyl acetone, butanols, hexalin, acetone, butanone, pimelinketone or butylacetate, and working concentration is 50～99%.
2. according to the described method of claim 1, the ratio that it is characterized in that said animals and plants essential oil and reverse-extraction agent is 1: 1～6 weight ratios; The concentration of said reverse-extraction agent is 75～95%.
3. according to the described method of claim 1, it is characterized in that described ultrasonic oscillator is common industrial ultrasonic oscillator, ultrasonic frequency is 20～40Khz.
4. according to the described method of one of claim 1 to 3, it is characterized in that concrete steps comprise:
(1), animals and plants essential oil and the reverse-extraction agent that will contain the phthalate material is preheated to 35～99 ℃ respectively before stirring mixing; Animals and plants essential oil after preheating is added reverse-extraction agent; Stirred 1～10 minute; Make animals and plants essential oil and reverse-extraction agent thorough mixing, and the phthalate material thorough washing that adopts ultrasonic oscillator vibration 2～10min to make to contain in the animals and plants essential oil and dissolved be adsorbed in the reverse-extraction agent;
(2), leave standstill, the animals and plants essential oil is separated with the reverse-extraction agent layering, the reverse-extraction agent that floats over the upper strata after the animals and plants essential oil that sinks to lower floor after the layering and the layering is separated;
(3), adopt common industrial vacuum distillatory method to remove reverse-extraction agent residual in the animals and plants essential oil, the vacuum tightness that vacuum distilling is adopted usually is-880～-550mbar, distillation temperature is 40～65 ℃; The animals and plants essential oil of phthalate material is removed in acquisition.
5. according to the described method of claim 4; It is characterized in that will be through the animals and plants essential oil of step (1) and the processing of (2) stripping process; Carry out secondary or repeatedly stripping process processing according to step (1) and (2) again, obtain further to remove the animals and plants essential oil of phthalate material.
6. according to the described method of claim 5, it is characterized in that in step (2), adopting common industrial method of cooling to quicken the animals and plants essential oil and separate with the layering of reverse-extraction agent, cooling temperature is-15 ℃～10 ℃ usually.
7. according to the described method of claim 4, it is characterized in that described animals and plants essential oil of step (1) and reverse-extraction agent mix stir before respectively the temperature of preheating be 40～75 ℃.
8. according to the described method of one of claim 1 to 3, it is characterized in that concrete steps comprise:
(1), animals and plants essential oil and the reverse-extraction agent that will contain the phthalate material is preheated to 35～99 ℃ respectively before stirring mixing; Animals and plants essential oil after preheating is added reverse-extraction agent; Stirred 1～10 minute; Make animals and plants essential oil and reverse-extraction agent thorough mixing, and the phthalate material thorough washing that adopts ultrasonic oscillator vibration 2～10min to make to contain in the animals and plants essential oil and dissolved be adsorbed in the reverse-extraction agent:
(2), adopt common industrial centrifugal separating device that the animals and plants essential oil is separated with reverse-extraction agent;
(3), adopt common industrial vacuum distillatory method to remove reverse-extraction agent residual in the animals and plants essential oil, the vacuum tightness that vacuum distilling is adopted usually is-880～-550mbar, distillation temperature is 40～65 ℃; The animals and plants essential oil of phthalate material is removed in acquisition.
9. according to the described method of claim 8; It is characterized in that will be through the animals and plants essential oil of step (1) and the processing of (2) stripping process; Carry out secondary or repeatedly stripping process processing according to step (1) and (2) again, obtain further to remove the animals and plants essential oil of phthalate material.
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| CN103242953A (en) * | 2013-05-20 | 2013-08-14 | 广州理和健康产品科技有限公司 | Method for removing plasticizer from fructus schizandrae oil or ganoderma spore oil |
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| CN108219930A (en) * | 2018-01-11 | 2018-06-29 | 辽宁晟麦实业股份有限公司 | A kind of method of content of plasticizing agent in reduction vegetable oil |
| CN108219930B (en) * | 2018-01-11 | 2021-08-06 | 辽宁晟麦实业股份有限公司 | Method for reducing plasticizer content in vegetable oil |
| CN110959830A (en) * | 2019-12-18 | 2020-04-07 | 宁波杰顺生物科技有限公司 | Bee product and preparation method thereof |
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