CN115212142A - Method for preparing lanolin alcohol and lanolin acid from lanolin - Google Patents
Method for preparing lanolin alcohol and lanolin acid from lanolin Download PDFInfo
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- CN115212142A CN115212142A CN202211005388.5A CN202211005388A CN115212142A CN 115212142 A CN115212142 A CN 115212142A CN 202211005388 A CN202211005388 A CN 202211005388A CN 115212142 A CN115212142 A CN 115212142A
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- lanolin
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- alkali metal
- metal hydroxide
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- 235000019388 lanolin Nutrition 0.000 title claims abstract description 188
- 239000004166 Lanolin Substances 0.000 title claims abstract description 186
- 229940039717 lanolin Drugs 0.000 title claims abstract description 186
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000002253 acid Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 81
- 239000000243 solution Substances 0.000 claims abstract description 81
- 238000000605 extraction Methods 0.000 claims abstract description 55
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 33
- 239000003960 organic solvent Substances 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 25
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 24
- 239000000194 fatty acid Substances 0.000 claims abstract description 24
- 229930195729 fatty acid Natural products 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 239000012670 alkaline solution Substances 0.000 claims abstract description 21
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 19
- 238000004321 preservation Methods 0.000 claims abstract description 12
- 238000007127 saponification reaction Methods 0.000 claims description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000003208 petroleum Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 17
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 13
- -1 fatty acid salt Chemical class 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 239000000284 extract Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000003637 basic solution Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 150000004665 fatty acids Chemical class 0.000 abstract description 17
- 238000000926 separation method Methods 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000004519 grease Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 210000002268 wool Anatomy 0.000 description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 238000004945 emulsification Methods 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 238000005086 pumping Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 235000012000 cholesterol Nutrition 0.000 description 5
- 238000000199 molecular distillation Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 239000002537 cosmetic Substances 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229940099367 lanolin alcohols Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 229930003316 Vitamin D Natural products 0.000 description 1
- QYSXJUFSXHHAJI-XFEUOLMDSA-N Vitamin D3 Natural products C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C/C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-XFEUOLMDSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 210000001732 sebaceous gland Anatomy 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000019166 vitamin D Nutrition 0.000 description 1
- 239000011710 vitamin D Substances 0.000 description 1
- 150000003710 vitamin D derivatives Chemical class 0.000 description 1
- 229940046008 vitamin d Drugs 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/925—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of animal origin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Chemical & Material Sciences (AREA)
- Dermatology (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention provides a method for preparing lanolin alcohol and lanolin fatty acid from lanolin, and belongs to the technical field of grease processing. Firstly saponifying lanolin in a lower fatty alcohol alkaline solution containing alkali metal hydroxide to obtain a lanolin saponified substance solution, then carrying out heat preservation extraction on the lanolin saponified substance solution by using a low-polarity organic solvent, wherein an extraction liquid comprises lanolin alcohol, and a raffinate comprises a lanolin acid salt, so that the high-efficiency separation and preparation of the lanolin alcohol and the lanolin acid are realized. The method has the advantages of short process route, simple and convenient operation and easy industrial production.
Description
Technical Field
The invention belongs to the technical field of grease processing, and particularly relates to a method for preparing lanolin alcohol and lanolin fatty acid from lanolin.
Background
Lanolin is the fatty secretion of sebaceous glands of sheep deposited on wool fibers, and is mainly an ester compound composed of wool acid and lanonol. The wool acid is rich in branched chain fatty acid, has a structure very similar to that of fatty acid contained in human skin, and when the wool acid is applied to the skin, a surface oil film is porous, so that water vapor can smoothly pass through the skin without interfering normal physiological activities of the skin, and the wool acid is an excellent natural cosmetic raw material. The lanolate can be used as high-grade antirust grease, lubricant and the like. The main components of the lanonol are cholesterol (the content is about 12 percent of the total mass of the lanolin), triterpenoid sterol (about 6 percent) and fatty alcohol (about 20 percent), and the lanonol can be directly used as a raw material of high-grade cosmetics and hair care additives, can also be further refined to obtain NF-grade cholesterol which can be used as a raw material for synthesizing vitamin D, and can also be used as a liquid crystal material.
The traditional method for preparing wool acid and lanonol by using lanolin has certain technical problems, so that the whole process is complex and the operation is difficult. First, lanolin is saponified with a strong base, and if an aqueous solution or an aqueous alcohol solution is used as a solvent, the raw lanolin and the formed products, a lanolin salt and lanolin alcohol, are difficult to dissolve, and the saponification reaction is a reaction in a heterogeneous solution and is slow. Secondly, the generated lanolin fatty acid is a good surfactant, a 'saponified substance film' consisting of oil-in-water droplets is formed on the surface of the lanolin, and the reaction of strong alkali and the lanolin in the droplets is prevented, so that the reaction is incomplete, the emulsification phenomenon is very serious, and the extraction operation is difficult.
In order to overcome the above difficulties, most of the processes for preparing lanolin alcohol and lanolin acid from lanolin utilize alkali metal hydroxide to heat and saponify lanolin in alcohol or alcohol water for a long time, and then utilize the characteristic that alkali earth metal salt of lanolin acid is hardly dissolved in organic solvent to prepare alkali earth metal salt of lanolin acid by calcium-transferring saponification reaction. After recovering the solvent, the saponification product solid is extracted by refluxing with lower aliphatic alcohol, the complex formed by lanonol and alkaline earth metal salt can be dissolved in lower aliphatic alcohol, but the lanonoate is not dissolved, thereby realizing the separation of lanonol and lanonoate. The wool acid alkaline earth metal salt is acidified, washed, dried and the like to obtain the wool acid. For example, patent CN1263769C saponifies with alcohol solution under alkaline condition, evaporates the saponified product to dryness and extracts with organic solvent, patent CN106851654B saponifies with calcium hydroxide as alkali in alcohol solution through pipeline saponification reaction device. Although the idea can avoid the emulsification phenomenon, the operation is complex and the yield is not high.
If lanolin is directly extracted by an organic solvent after saponification of lanolin with an aqueous alcohol solution of sodium hydroxide or potassium hydroxide without preparation of an alkaline earth metal salt of wool acid, serious problems of extraction and emulsification are encountered, resulting in difficulty in extraction operation. For example, patent US3526647 uses lanolin for heat saponification in aqueous isopropanol solution of sodium hydroxide or potassium hydroxide, followed by n-hexane or n-heptane extraction of the saponification product to give lanolin alcohol and lanolin acid salt. The saponification substance solution can also be acidified to convert the lanolate into the wool acid, so that the emulsification phenomenon can be reduced, but the generated wool acid and the lanonol have very close polarities and cannot be separated by using an extraction method, the obtained lanonol has very poor purity, and the subsequent separation workload is large. For example, patent CN107325144B uses an aqueous alcohol solution as a solvent for saponification, after which the pH of the saponification product solution is adjusted to 7-9 to convert the lanolate to wool acid, and the lanonol is extracted with an alkane.
Besides the separation of lanolin alcohol and lanolin fatty acid by organic solvent extraction or extraction, the separation of lanolin fatty acid and lanolin fatty acid can be realized by molecular distillation according to the difference of molecular free path of lanolin fatty acid and lanolin fatty alcohol. For example, patent CN1958596A uses transesterification to convert lanolin into lanolin esters and lanolin alcohols, then uses two-stage molecular distillation to obtain crude cholesterol (lanolin alcohols), and then uses chromatographic column to separate high-purity cholesterol. Patent CN102863315B adopts saponification with sodium hydroxide or potassium hydroxide in alcoholic solution, distilling off alcoholic solvent, molecular distillation, collecting light phase as lanolin alcohol, and heavy phase as lanolin acid salt. The molecular distillation method is used in the methods to solve the problem that wool acid and lanonol are difficult to separate, but the methods have the disadvantages of complex operation, high energy consumption and long process route.
In summary, although there are many methods for preparing lanolin alcohol and lanolin fatty acid from lanolin, the lanolin raw material and saponification product are difficult to dissolve in water, so that homogeneous saponification reaction is difficult to achieve, the generated lanolin acid salt is easy to emulsify, and lanolin alcohol and lanolin fatty acid salt are difficult to separate, which results in the disadvantages of complicated operation and long process route in the process for preparing lanolin alcohol and lanolin fatty acid from lanolin.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a method for preparing lanonol and wool acid by using lanolin.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing lanolin alcohol and lanolin acid from lanolin, which comprises the following steps:
s1, mixing lanolin and a lower fatty alcohol alkaline solution, and performing homogeneous saponification reaction to obtain a lanolin saponified substance solution; the lower fatty alcohol alkaline solution contains alkali metal hydroxide;
s2, taking lanolin saponified substance solution as heavy liquid and taking low-polarity organic solvent as light liquid to perform heat preservation extraction, and respectively collecting extraction liquid containing lanolin alcohol and raffinate containing lanolin acid salt;
the low-polarity organic solvent comprises one or more of n-hexane, cyclohexane, n-heptane, octane, petroleum ether and gasoline;
s3, carrying out reduced pressure evaporation concentration on the extract liquor obtained in the step S2, and recovering the solvent to obtain lanolin alcohol;
and (3) carrying out reduced pressure evaporation and concentration on the raffinate obtained in the step (S2), and recovering the solvent to obtain the lanolin fatty acid salt.
Preferably, in S1, the lower aliphatic alcohol includes one or more of methanol, ethanol, isopropanol and n-butanol.
Preferably, in S1, the mass volume ratio of the lanolin to the lower fatty alcohol alkaline solution is 1g: (1-100) ml.
Preferably, in S1, the alkali metal hydroxide includes sodium hydroxide or potassium hydroxide; the mass ratio of the alkali metal hydroxide to the lanolin is (0.01-1): 1.
preferably, in S1, the alkali metal hydroxide is added to the lower aliphatic alcohol alkaline solution in the form of a solid alkali metal hydroxide or an alkali metal hydroxide aqueous solution; the mass percentage concentration of the alkali metal hydroxide aqueous solution is 1-99%.
Preferably, in S1, the saponification reaction temperature is 50-100 ℃; the saponification reaction time is 1-24 h.
Preferably, in S2, the temperature for heat preservation extraction is 50-100 ℃.
Preferably, in S2, the volume ratio of the lanolin saponified product solution to the low-polarity organic solvent is (5.
Preferably, in S2, the petroleum ether is petroleum ether with a boiling range of 60-120 ℃.
Preferably, in S3, after the step of obtaining the lanolin fatty acid, the step of acidifying the lanolin fatty acid with an aqueous solution of an inorganic acid, washing, and drying to obtain the lanolin fatty acid.
The invention has the beneficial effects that:
the invention provides a method for preparing lanolin alcohol and lanolin fatty acid by using lanolin, which comprises the steps of saponifying lanolin in a lower fatty alcohol alkaline solution containing alkali metal hydroxide to obtain a lanolin saponified substance solution, then carrying out heat preservation extraction on the lanolin saponified substance solution by using a low-polarity organic solvent, wherein an extraction liquid comprises lanolin alcohol, and a raffinate comprises a lanolin acid salt, so that the high-efficiency separation preparation of the lanolin alcohol and the lanolin fatty acid is realized.
The method can realize the separation of the lanolin alcohol and the lanolin fatty acid salt in the lanolin by saponification, heat preservation and extraction, has short process route and simple and convenient operation, and is easy for continuous and industrial production.
The invention adopts lower alcohol as solvent of saponification reaction, so that the whole saponification reaction is carried out in homogeneous solution, the reaction rate is high, the saponification reaction is more thorough, the yield is effectively improved, and the procedure of removing unreacted lanolin raw material is also omitted. Compared with the process using alcohol water or water system as solvent for saponification reaction, the method effectively avoids emulsification, improves reaction rate and yield, and is easier and more efficient in subsequent solvent recovery. Compared with the transesterification reaction process, the complex pretreatment process is omitted, the crude lanolin usually contains moisture, metal ions and the like, the transesterification reaction requires anhydrous conditions, the content of other impurities is as low as possible, the wool grease needs to be washed and dried before the transesterification reaction, and the requirements on the quality of the wool grease are high. The invention has no requirement on the content of water and impurities in the lanolin, and the raw material application range is wider. In addition, the saponification reaction is to keep slight boiling under the condition of no pressure, reflux saponification is carried out, the operation is safe, the temperature control is convenient, and the accurate temperature control is not needed.
The invention uses low-polarity organic solution to extract lanolin alcohol in saponified substance (low-grade alcohol solution) of lanolin through heat preservation, and both phases are organic solution, so that the phase separation speed is high, and the emulsification phenomenon in the extraction process can be effectively avoided; meanwhile, the precipitation of solids caused by temperature reduction can be avoided; and the extraction efficiency is low due to the extraction of the solid, and the operation is very simple. Compared with the molecular distillation process, the method has the advantages of less equipment investment and simple operation. Compared with the traditional extraction process, the method has the advantages of effectively reduced emulsification phenomenon, high extraction efficiency, high product yield and simpler and more convenient operation. Compared with the calcium-conversion saponification process, the method simplifies the operation steps, avoids the use of calcium chloride, and has higher yield than the calcium-conversion saponification process.
Therefore, the invention realizes the high-efficiency saponification of the lanolin and the high-efficiency separation of the lanolin alcohol and the wool acid by saponifying the lanolin in the lower fatty alcohol alkaline solution and extracting the saponified product by using the low-polarity organic solvent in a heat preservation way. The method has the advantages of rapid and thorough saponification reaction, mild saponification conditions, capability of avoiding emulsification in the saponification reaction of the lanolin, no emulsification in the extraction process, high phase separation speed, good separation effect and high product yield. The method has the advantages of short process route, simple and convenient operation, easy continuous and industrial production and low production cost. The lanolin alcohol separated by the method can be further purified to obtain high-purity cholesterol, and the lanolin fatty acid can be used as a raw material of high-grade cosmetics, so that the comprehensive development of the lanolin is realized.
Detailed Description
The invention provides a method for preparing lanonol and wool acid, which comprises the following steps:
s1, mixing lanolin and a lower fatty alcohol alkaline solution, and performing homogeneous saponification reaction to obtain a lanolin saponified substance solution; the lower fatty alcohol alkaline solution contains alkali metal hydroxide;
s2, taking lanolin saponified substance solution as heavy liquid and taking low-polarity organic solvent as light liquid to perform heat preservation extraction, and respectively collecting extraction liquid containing lanolin alcohol and raffinate containing lanolin acid salt;
the low-polarity organic solvent comprises one or more of n-hexane, cyclohexane, n-heptane, octane, petroleum ether and gasoline;
s3, carrying out reduced pressure evaporation concentration on the extraction liquid obtained in the step S2, and recovering the solvent to obtain lanolin alcohol;
and (3) carrying out reduced pressure evaporation and concentration on the raffinate obtained in the step (S2), and recovering the solvent to obtain the lanolin fatty acid salt.
Firstly, mixing lanolin and a lower fatty alcohol alkaline solution, and carrying out homogeneous saponification reaction to obtain a lanolin saponified substance solution; the lower aliphatic alcohol alkaline solution contains alkali metal hydroxide.
In the present invention, the lower aliphatic alcohol is preferably selected from one or more of methanol, ethanol, isopropanol and n-butanol, and more preferably a mixed solution of methanol and isopropanol; the volume ratio of the methanol to the isopropanol is preferably (3 to 5): 1, more preferably 4:1.
in the present invention, the mass-to-volume ratio of the lanolin to the lower fatty alcohol basic solution is preferably 1g: (1-100) ml, more preferably 1g: (5-30) ml, most preferably 1g: (10-20) ml. In the present invention, the lower aliphatic alcohol alkaline solution contains an alkali metal hydroxide; the alkali metal hydroxide preferably comprises sodium hydroxide or potassium hydroxide; the mass ratio of the alkali metal hydroxide to lanolin is preferably (0.01 to 1): 1, more preferably (0.1 to 0.3): 1. in the present invention, the alkali metal hydroxide is added to the lower aliphatic alcohol alkaline solution in the form of a solid alkali metal hydroxide or an alkali metal hydroxide aqueous solution; the concentration of the alkali metal hydroxide aqueous solution is preferably 1 to 99% by mass, more preferably 5 to 50% by mass, and most preferably 10 to 30% by mass.
In the present invention, the temperature of the saponification reaction is preferably 50 to 100 ℃, more preferably 70 to 80 ℃; the saponification reaction time is preferably 1-24 h, more preferably 5-20 h, and most preferably 10-15 h; the saponification reaction is preferably carried out under stirring conditions, and the rotation speed of the stirring is preferably 100 to 500rpm, more preferably 200 to 300rpm.
After obtaining lanolin saponified substance solution, the method takes the lanolin saponified substance solution as heavy liquid and takes low-polarity organic solvent as light liquid for heat preservation and extraction, and respectively collects extraction liquid containing lanolin alcohol and raffinate containing lanolin acid salt; the low-polarity organic solvent comprises one or more of n-hexane, cyclohexane, n-heptane, octane, petroleum ether and gasoline.
In the invention, the temperature of the heat preservation extraction is 50-100 ℃, and more preferably 60-80 ℃.
In the present invention, the low-polarity organic solvent is preferably petroleum ether; the petroleum ether is petroleum ether with a boiling range of 60-120 ℃, and is more preferably petroleum ether with a boiling range of 90-120 ℃.
In the present invention, the ratio by volume of the lanolin saponified product solution to the low-polarity organic solvent is preferably (5: (3 to 8), most preferably (2 to 3): (3-5).
In the present invention, the number of extraction times in the ordinary temperature-maintaining extraction operation is preferably 2 to 4, and more preferably 3. In the present invention, the flow rate ratio of the heavy liquid to the light liquid in the heat-retaining countercurrent extraction operation is preferably (5: (3 to 8), most preferably (2 to 3): 5.
in one embodiment of the invention, the temperature-maintained extraction is carried out in an extraction column; the heat-preserving extraction preferably comprises heat-preserving liquid drop countercurrent extraction; pumping the lanolin saponified substance solution as a heavy liquid from the top of the tower; the low-polarity organic solvent is pumped from the bottom of the tower as light liquid; the lanolin alcohol and a small part of the lanolin fatty acid salt are extracted into the low polarity organic solvent, and the low polarity organic solvent flows out from the top of the tower, and most of the lanolin fatty acid salt is remained in the low polarity alcohol solution and flows out from the bottom of the tower. Respectively collecting extract and raffinate, wherein the substance extracted from the low-polarity organic solvent mainly comprises lanolin alcohol, and the raffinate mainly comprises lanolin acid salt. After the extract liquid is obtained, the invention preferably further comprises pumping the extract liquid from the bottom of the tower by taking the extract liquid as light liquid, pumping the newly prepared alkali solution of the lower aliphatic alcohol containing the alkali metal hydroxide from the top of the tower by taking the newly prepared alkali solution of the lower aliphatic alcohol containing the alkali metal hydroxide as heavy liquid, and carrying out heat preservation liquid drop countercurrent washing. The method comprises the steps of back extracting the lanolin acid salt and a small amount of lanolin alcohol contained in light liquid into heavy liquid by an alkali metal hydroxide alcohol solution, wherein the light liquid mainly contains the lanolin alcohol without the lanolin acid salt and flows out from the top of a tower, and the heavy liquid mainly contains a small amount of lanolin acid salt and lanolin alcohol, and collecting the light liquid and the heavy liquid respectively. The heavy liquid is continuously used as the alkali alcohol solution of the next saponification reaction; the preparation method and concentration of the newly prepared lower fatty alcohol alkaline solution containing the alkali metal hydroxide aqueous solution are the same as those of the lower fatty alcohol alkaline solution containing the alkali metal hydroxide required for the saponification reaction in the scheme, and the newly prepared lower fatty alcohol alkaline solution containing the alkali metal hydroxide aqueous solution can be continuously used as a lower fatty alcohol alkaline solution for the next saponification reaction.
In one embodiment of the invention, the incubation extraction is performed in a centrifugal counter-current extraction apparatus; the lanolin saponified product and the extractant are heated and preserved in advance, a certain temperature is maintained, lanolin saponified product solution serving as heavy liquid is pumped from a heavy liquid inlet, a low-polarity organic solvent serving as light liquid is pumped from a light liquid inlet, centrifugal countercurrent extraction is carried out, and at the moment, the light liquid and the heavy liquid can still maintain a certain temperature in a centrifugal countercurrent extraction device, so that no solid is separated out. The lanolin alcohol and a small part of the lanolin acid salt are extracted into a low-polarity organic solvent, the light liquid flows out from a light liquid outlet, most of the lanolin acid salt is still kept in the lower alcohol, the heavy liquid flows out from a heavy liquid outlet, an extract liquid (light liquid) and a raffinate liquid (heavy liquid) are respectively collected, the low-polarity organic solvent extracted substance mainly comprises the lanolin alcohol, and the raffinate liquid mainly comprises the lanolin acid salt. After the extraction liquid is obtained, the invention preferably further comprises the steps of respectively heating and preserving the extraction liquid and the newly prepared lower aliphatic alcohol alkaline solution containing the alkali metal hydroxide aqueous solution, pumping in the centrifugal countercurrent extraction device from a light liquid inlet by taking the extraction liquid as the light liquid, pumping in the centrifugal countercurrent extraction device from a heavy liquid inlet by taking the newly prepared alkali alcohol solution as the heavy liquid, and carrying out centrifugal countercurrent washing. The light liquor, which contains predominantly the lanolin alcohol from which the lanolin is removed, is washed with an alkaline alcohol solution into a heavy liquor, which contains predominantly the lanolin and a small amount of the lanolin alcohol from a light liquor outlet and a heavy liquor, which contains predominantly the lanolin and the lanolin alcohol from a heavy liquor outlet. And respectively collecting light liquid and heavy liquid, and continuously using the heavy liquid as an alkali alcohol solution for the next saponification reaction.
After the extraction liquid and the raffinate are obtained, the invention carries out reduced pressure evaporation and concentration on the extraction liquid, and recovers the solvent to obtain the lanolin alcohol; and (3) carrying out reduced pressure evaporation and concentration on the raffinate, recovering the solvent to obtain a lanolin acid salt, acidifying the lanolin acid salt by adopting an inorganic acid aqueous solution, washing and drying to obtain lanolin acid.
In the present invention, the concentration of the inorganic acid in the aqueous solution of the inorganic acid is preferably 1 to 6mol/L, and more preferably 3 to 5mol/L.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1. To 25g of lanolin, 200mL of methanol and 50mL of isopropyl alcohol were added, and the mixture was stirred with heating to dissolve the lanolin. 2.5g of the solid sodium hydroxide was dissolved in 25mL of water and added to the lanolin solution for homogeneous saponification. Heating and stirring at 80 ℃, refluxing, and reacting for 24 hours to obtain a dark brown lanolin saponified substance solution.
2. Adding 250mL of petroleum ether with the boiling range of 90-120 ℃ into lanolin saponified substance solution at the temperature of 80 ℃, stirring and extracting for 30min, stopping stirring, and extracting an upper petroleum ether layer by using an injector after the liquid is static. The same extraction operation was performed with 250mL of petroleum ether for 3 total extractions, and the petroleum ether layers were combined to obtain a crude lanonool solution. The lower layer solution after extraction is a sodium lanolate solution.
3. And (3) respectively carrying out reduced pressure concentration on the sodium lanolate alcohol solution and the lanolate alcohol solution obtained in the step (2) on a rotary film evaporator, and recovering the solvent to respectively obtain sodium lanolate and lanolate.
4. Acidifying the sodium lanolate obtained in the step 3 with 2mol/L concentrated hydrochloric acid to pH =5, then washing with water to neutrality, and drying to obtain the wool acid.
Example 2
1. Adding 8L methanol and 2L isopropanol into 500g lanolin, heating and stirring to dissolve lanolin. 40g of the solid potassium hydroxide was dissolved in 200mL of water and added to the lanolin solution to conduct a homogeneous saponification reaction. Heating and stirring at 80 ℃, refluxing, and reacting for 5 hours to obtain a dark brown lanolin saponified substance solution.
2. The temperature-controlled countercurrent liquid drop extraction tower is maintained at 80 ℃ in advance, lanolin saponified substance solution is pumped from the top of the tower as heavy liquid, petroleum ether with the boiling range of 90-120 ℃ is pumped from the bottom of the tower as light liquid, and the flow rate ratio of the heavy liquid to the light liquid is 2:3. and performing countercurrent extraction on the two phases in a tower body, extracting the lanolin alcohol into a low-polarity organic solvent, flowing out from the tower top to obtain a crude lanolin alcohol solution, and flowing out from the tower bottom to obtain a potassium lanolin solution, wherein most of potassium lanolin is still in the low-polarity alcohol solution.
3. At the temperature of 80 ℃, newly prepared potassium hydroxide alcohol solution (with the same proportion as the potassium hydroxide alcohol solution in the saponification reaction) is used as a detergent in a temperature-controlled countercurrent liquid drop extraction tower, and potassium lanolate is extracted from the wool alcohol solution. The potassium hydroxide alcohol solution is pumped in from the top of the tower as the heavy phase, the lanolin alcohol solution is pumped in from the bottom of the tower as the light phase, and the flow rate ratio of the heavy phase to the light phase is 2. The two phases are washed in the tower body, and the potassium lanolate is washed into the alcohol solution and flows out from the bottom of the tower. Purified lanolin alcohol solution flows out of the tower top.
4. And (3) respectively concentrating the potassium lanolate alcohol solution obtained in the step (2) and the lanolate solution obtained in the step (3), and recovering the solvent to respectively obtain potassium lanolate and lanolate.
5. Acidifying the potassium lanolate obtained in the step 4 by using 5mol/L concentrated hydrochloric acid until the pH is =5, then washing the potassium lanolate to be neutral, and drying the potassium lanolate to obtain the wool acid.
Example 3
1. 1000L of methanol was added to the saponification reaction tank, heated and stirred, and 100kg of molten lanolin solid was slowly added. 12kg of solid sodium hydroxide was dissolved in 100L of water and charged into a saponification reaction tank to conduct a homogeneous saponification reaction. Heating and stirring at the temperature of 80 ℃, refluxing, and reacting for 8 hours to obtain a dark brown lanolin saponified substance solution.
2. Heating petroleum ether with the boiling range of 90-120 ℃ to 80 ℃ in a heating and heat-preserving transfer tank, and preserving the heat of the lanolin saponified substance solution in the step 1. Setting the rotating speed of a centrifugal countercurrent extraction device at 2200rpm, pumping lanolin saponifying product solution serving as heavy liquid from a heavy liquid inlet, pumping petroleum ether with the boiling range of 90-120 ℃ serving as light liquid from a light liquid inlet, and enabling the flow rate ratio of the heavy liquid to the light liquid to be 1:2. the lanolin alcohol and a small amount of sodium lanolate are extracted into petroleum ether, and flow out from a light liquid outlet to obtain a crude lanolin alcohol solution, and most of the sodium lanolate is still in the low-level alcohol solution and flows out from a heavy liquid outlet to obtain a sodium lanolate solution.
3. And (3) heating the wool alcohol solution extracted in the step (2) and a newly prepared sodium hydroxide alcohol solution (the proportion of the sodium hydroxide alcohol solution is the same as that of the saponification reaction) to 80 ℃ in a heating and heat-preserving transfer tank, and preserving heat. Sodium lanolate is extracted from the lanolate solution by taking a sodium hydroxide alcoholic solution as a detergent. Setting the rotating speed of the centrifugal countercurrent extraction device to be 1500rpm, pumping the sodium hydroxide alcohol solution as heavy liquid from a heavy liquid inlet, pumping the lanolin alcohol solution obtained in the step 2 as light liquid from a light liquid inlet, and enabling the flow rate ratio of the heavy liquid to the light liquid to be 1. The sodium lanolate is washed into an alkaline alcoholic solution, which flows out of the heavy liquor outlet, and the purified lanolate solution flows out of the light liquor outlet.
4. And (3) respectively concentrating the sodium lanolate alcohol solution obtained in the step (2) and the lanolate solution obtained in the step (3), and recovering the solvent to respectively obtain sodium lanolate and lanolate.
5. Acidifying the sodium lanolate obtained in the step 4 with 3mol/L concentrated hydrochloric acid to pH =5, then washing with water to be neutral, and drying to obtain the wool acid.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing lanolin alcohol and lanolin acid from lanolin, comprising the steps of:
s1, mixing lanolin and a lower fatty alcohol alkaline solution, and performing homogeneous saponification reaction to obtain a lanolin saponified substance solution; the lower fatty alcohol alkaline solution contains alkali metal hydroxide;
s2, taking lanolin saponified substance solution as heavy liquid and low-polarity organic solvent as light liquid to perform heat preservation extraction, and respectively collecting an extraction liquid containing lanolin alcohol and a raffinate containing lanolin acid salt;
the low-polarity organic solvent comprises one or more of n-hexane, cyclohexane, n-heptane, octane, petroleum ether and gasoline;
s3, carrying out reduced pressure evaporation concentration on the extract liquor obtained in the step S2, and recovering the solvent to obtain lanolin alcohol;
and (3) carrying out reduced pressure evaporation and concentration on the raffinate obtained in the step (S2), and recovering the solvent to obtain the lanolin fatty acid salt.
2. The method as claimed in claim 1, wherein in S1, the lower aliphatic alcohol comprises one or more of methanol, ethanol, isopropanol and n-butanol.
3. The method according to claim 1 or 2, characterized in that the mass-to-volume ratio of lanolin to basic solution of lower fatty alcohol is 1g: (1-100) ml.
4. The method according to claim 1, wherein in S1, the alkali metal hydroxide comprises sodium hydroxide or potassium hydroxide; the mass ratio of the alkali metal hydroxide to the lanolin is (0.01-1): 1.
5. the method according to claim 1 or 4, wherein the alkali metal hydroxide is added to the lower aliphatic alcohol alkaline solution in the form of a solid alkali metal hydroxide or an alkali metal hydroxide aqueous solution; the mass percentage concentration of the alkali metal hydroxide aqueous solution is 1-99%.
6. The method according to claim 1, wherein the saponification reaction in S1 is carried out at a temperature of 50-100 ℃; the saponification reaction time is 1-24 h.
7. The method of claim 1, wherein the temperature of the heat-preserving extraction in S2 is 50-100 ℃.
8. The method according to claim 1 or 7, characterized in that the volume ratio of lanolin saponificate solution to low-polarity organic solvent is (5.
9. The method according to claim 1 or 7, wherein the petroleum ether is petroleum ether having a boiling range of 60 to 120 ℃.
10. The method of claim 1, wherein obtaining the lanolin acid salt further comprises acidifying the lanolin acid salt with an aqueous solution of a mineral acid, washing, and drying to obtain lanolin acid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2036120A1 (en) * | 1970-07-21 | 1972-01-27 | Malmstrom Chemical Corp., Linden, N.J. (V.StA.) | Production of wool wax alcohols and acids - from wool grease |
| CN1911881A (en) * | 2006-08-18 | 2007-02-14 | 浙江大学 | Method of separating wool acid and lanonol from wool grease |
| CN101085716A (en) * | 2007-06-22 | 2007-12-12 | 厦门金达威维生素股份有限公司 | Method for separating lanonol and lanolin fatty acid from lanolin saponified substrate |
-
2022
- 2022-08-22 CN CN202211005388.5A patent/CN115212142A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2036120A1 (en) * | 1970-07-21 | 1972-01-27 | Malmstrom Chemical Corp., Linden, N.J. (V.StA.) | Production of wool wax alcohols and acids - from wool grease |
| CN1911881A (en) * | 2006-08-18 | 2007-02-14 | 浙江大学 | Method of separating wool acid and lanonol from wool grease |
| CN101085716A (en) * | 2007-06-22 | 2007-12-12 | 厦门金达威维生素股份有限公司 | Method for separating lanonol and lanolin fatty acid from lanolin saponified substrate |
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