ES2304102A1 - Method for obtaining squalene - Google Patents
Method for obtaining squalene Download PDFInfo
- Publication number
- ES2304102A1 ES2304102A1 ES200700462A ES200700462A ES2304102A1 ES 2304102 A1 ES2304102 A1 ES 2304102A1 ES 200700462 A ES200700462 A ES 200700462A ES 200700462 A ES200700462 A ES 200700462A ES 2304102 A1 ES2304102 A1 ES 2304102A1
- Authority
- ES
- Spain
- Prior art keywords
- saponification
- squalene
- base
- acid
- oils
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 62
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- YYGNTYWPHWGJRM-UHFFFAOYSA-N (6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCC=C(C)CCC=C(C)CCC=C(C)C YYGNTYWPHWGJRM-UHFFFAOYSA-N 0.000 title claims abstract description 42
- BHEOSNUKNHRBNM-UHFFFAOYSA-N Tetramethylsqualene Natural products CC(=C)C(C)CCC(=C)C(C)CCC(C)=CCCC=C(C)CCC(C)C(=C)CCC(C)C(C)=C BHEOSNUKNHRBNM-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229940031439 squalene Drugs 0.000 title claims abstract description 42
- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000007127 saponification reaction Methods 0.000 claims abstract description 29
- 239000003921 oil Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000000199 molecular distillation Methods 0.000 claims abstract description 8
- 239000010686 shark liver oil Substances 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 22
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 239000000499 gel Substances 0.000 claims description 7
- 239000003752 hydrotrope Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229940048842 sodium xylenesulfonate Drugs 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- XDRMBCMMABGNMM-UHFFFAOYSA-N ethyl benzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=CC=C1 XDRMBCMMABGNMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005243 fluidization Methods 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- -1 methaxylenesulfonate Chemical compound 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229940047662 ammonium xylenesulfonate Drugs 0.000 claims 1
- LUAVFCBYZUMYCE-UHFFFAOYSA-N azanium;2-propan-2-ylbenzenesulfonate Chemical compound [NH4+].CC(C)C1=CC=CC=C1S([O-])(=O)=O LUAVFCBYZUMYCE-UHFFFAOYSA-N 0.000 claims 1
- HESSGHHCXGBPAJ-UHFFFAOYSA-N n-[3,5,6-trihydroxy-1-oxo-4-[3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyhexan-2-yl]acetamide Chemical compound CC(=O)NC(C=O)C(O)C(C(O)CO)OC1OC(CO)C(O)C(O)C1O HESSGHHCXGBPAJ-UHFFFAOYSA-N 0.000 claims 1
- 229940079842 sodium cumenesulfonate Drugs 0.000 claims 1
- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 claims 1
- YNBRSWNUNPAQOF-UHFFFAOYSA-M sodium;phenylmethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC1=CC=CC=C1 YNBRSWNUNPAQOF-UHFFFAOYSA-M 0.000 claims 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 1
- 241001465754 Metazoa Species 0.000 abstract description 6
- 229940069764 shark liver oil Drugs 0.000 abstract description 3
- 235000019198 oils Nutrition 0.000 description 22
- 239000003925 fat Substances 0.000 description 11
- 235000019197 fats Nutrition 0.000 description 11
- 241000251730 Chondrichthyes Species 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 210000004185 liver Anatomy 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 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 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000004508 fractional distillation Methods 0.000 description 4
- 239000004006 olive oil Substances 0.000 description 4
- 235000008390 olive oil Nutrition 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 240000007817 Olea europaea Species 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229940088597 hormone Drugs 0.000 description 3
- 239000005556 hormone Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000251729 Elasmobranchii Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 235000012000 cholesterol Nutrition 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229940032094 squalane Drugs 0.000 description 2
- 238000000194 supercritical-fluid extraction Methods 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000019737 Animal fat Nutrition 0.000 description 1
- 241000251188 Holocephali Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000405965 Scomberomorus brasiliensis Species 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ZZXDRXVIRVJQBT-UHFFFAOYSA-M Xylenesulfonate Chemical compound CC1=CC=CC(S([O-])(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-M 0.000 description 1
- 230000003187 abdominal effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- CIZKTTKIKAXNBA-UHFFFAOYSA-N azane;cumene Chemical compound N.CC(C)C1=CC=CC=C1 CIZKTTKIKAXNBA-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- NSFKBZXCXCJZDQ-UHFFFAOYSA-N cumene;sodium Chemical compound [Na].CC(C)C1=CC=CC=C1 NSFKBZXCXCJZDQ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- FMGSKLZLMKYGDP-USOAJAOKSA-N dehydroepiandrosterone Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC=C21 FMGSKLZLMKYGDP-USOAJAOKSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000926 neurological effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 238000000526 short-path distillation Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000010497 wheat germ oil Substances 0.000 description 1
- 229940071104 xylenesulfonate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/21—Alkatrienes; Alkatetraenes; Other alkapolyenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14833—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds
- C07C7/1485—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds oxides; hydroxides; salts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Procedimiento de obtención de escualeno.Procedure for obtaining squalene.
La presente invención se encuadra dentro del sector químico y agroalimentario, más concretamente la invención se refiere a un procedimiento para la obtención de escualeno a partir de un aceite de origen animal.The present invention fits within the chemical and agri-food sector, more specifically the invention is refers to a procedure for obtaining squalene from of an oil of animal origin.
El escualeno es el espinaceno (2,6,10,15,19,23-hexametil-2,6,10,14,16,18,20-tetracosahexaeno), un hidrocarburo alifático de fórmula (I)Squalane is spinazene (2,6,10,15,19,23-hexamethyl-2,6,10,14,16,18,20-tetracosahexane), an aliphatic hydrocarbon of formula (I)
Se trata de una materia prima natural que se encuentra en el sebo humano (5%) y en el aceite de hígado de tiburón como principal fuente de origen animal. También se encuentra en los aceites vegetales especialmente en el aceite de oliva.It is a natural raw material that found in human sebum (5%) and in liver oil from shark as the main source of animal origin. I also know found in vegetable oils especially in the oil of olive.
Es un producto de gran interés en investigación bioquímica y farmacéutica ya que es el precursor natural de la biosíntesis del colesterol in vivo. Además, es un producto de interés en el sector cosmético y médico donde se utiliza principalmente como vehículo para los principios activos.It is a product of great interest in biochemical and pharmaceutical research since it is the natural precursor of cholesterol biosynthesis in vivo . In addition, it is a product of interest in the cosmetic and medical sector where it is mainly used as a vehicle for active ingredients.
El escualeno es un precursor del colesterol y éste a su vez de la hormona Dehidroepiandrosterona (DHEA), lo cual le da un papel importante en la restitución de los valores normales de esta hormona, que con los años disminuye ostensiblemente en los humanos. A esta hormona se le atribuyen propiedades como la mejora del rendimiento neurológico, la concentración, la memoria y la disminución del acúmulo graso a nivel abdominal. El escualeno tiene además propiedades antioxidantes y capacidad para repolarizar las membranas celulares, controlando la reproducción de las mismas.Squalene is a precursor to cholesterol and this in turn of the hormone Dehydroepiandrosterone (DHEA), which It gives you an important role in restoring normal values of this hormone, which over the years decreases significantly in the humans. Properties such as improvement are attributed to this hormone. of neurological performance, concentration, memory and decreased fat accumulation at the abdominal level. The squalene has also antioxidant properties and ability to repolarize the cell membranes, controlling their reproduction.
En la preparación de escualeno, se han empleado diversas fuentes de materia prima, como aceite de hígado de tiburón, salvado de arroz, germen de trigo o aceituna, aceite de oliva, etc.In the preparation of squalene, they have been used various sources of raw material, such as liver oil from shark, rice bran, wheat germ or olive oil olive, etc.
En la solicitud de patente JP2000044496 se describe un proceso de purificación de escualeno a partir de aceites y grasas diversas, distintas del aceite de hígado de tiburón. El proceso consiste en someter la materia prima a una destilación simple, seguida de un proceso de destilación fraccionada e hidrogenación de la muestra.In patent application JP2000044496, describes a process of purification of squalene from various oils and fats, other than liver oil from shark. The process consists in subjecting the raw material to a simple distillation, followed by a fractional distillation process and hydrogenation of the sample.
En la patente JP7309785 se describe un proceso de purificación de escualeno que comprende tres etapas: destilación, fraccionamiento e hidrogenación de la materia prima (aceites y grasas).A process is described in JP7309785 of squalene purification comprising three stages: distillation, fractionation and hydrogenation of the raw material (oils and fats).
En la patente ES2162742 se describe un procedimiento de obtención de escualeno a partir del subproducto que se obtiene del refinado físico (destilación neutralizante/desodoración) del aceite de oliva, utilizando extracciones con disolventes polares y apolares.Patent ES2162742 describes a procedure for obtaining squalene from the by-product which is obtained from physical refining (distillation neutralizer / deodorization) of olive oil, using extractions with polar solvents and apolar.
La patente ES8602102 hace referencia a un procedimiento de obtención de escualeno y escualeno a partir de subproductos de la refinación física y/o desodorización de aceites vegetales. El procedimiento descrito consiste en someter los subproductos del refino físico y/o desodorización de aceites vegetales de oliva y orujo, previamente hidrogenados catalíticamente, a una saponificación alcalina seguida de una extracción en continuo con disolventes del escualeno y/o escualeno de la masa de jabón.The ES8602102 patent refers to a procedure for obtaining squalene and squalene from by-products of physical refining and / or oil deodorization vegetables. The procedure described consists in submitting the by-products of physical refining and / or oil deodorization olive and pomace vegetables, previously hydrogenated catalytically, an alkaline saponification followed by a Continuous extraction with squalene and / or squalene solvents of the soap mass.
En la solicitud de patente estadounidense US2004015033 se emplea la misma materia prima que en las patentes citadas anteriormente, diferenciándose el procedimiento en que se lleva a cabo una extracción supercrítica.In the US patent application US2004015033 uses the same raw material as in patents cited above, differentiating the procedure in which Performs a supercritical extraction.
En la solicitud de patente WO 9426683 se describe un procedimiento para la obtención de escualeno a partir de residuos del aceite de oliva, donde el procedimiento comprende una etapa de esterificación y otra etapa de extracción supercrítica con dióxido de carbono.In patent application WO 9426683, describes a procedure for obtaining squalene from of olive oil residues, where the procedure includes an esterification stage and another supercritical extraction stage with carbon dioxide.
En el artículo de Serra Masiá, A. y col., Grasas y Aceites, Vol. 32(5): 313-317 (1981), se describe la separación y obtención de escualeno a partir de las oleínas procedentes de la refinación física del aceite de oliva. En este artículo se describen tres procesos diferentes:In the article by Serra Masiá, A. et al., Fats and Oils, Vol. 32 (5): 313-317 (1981), is describes the separation and obtaining of squalene from the oleins from the physical refining of olive oil. In This article describes three different processes:
(a) Separación mediante complejos de tiourea. La tiourea forma complejos de adición con el escualeno, pero según Angla (B. Angla, Ann. Chim., (12) 4, 667, 1.949) las estructuras con dobles enlaces tienen un efecto desfavorable sobre la adición con tiourea. La relativa estabilidad de estos complejos unido al cambio de escala lo hacen inviable como procedimiento industrial.(a) Separation by thiourea complexes. The Thiourea forms addition complexes with squalene, but according to Angla (B. Angla, Ann. Chim., (12) 4, 667, 1949) structures with double bonds have an unfavorable effect on the addition with thiourea. The relative stability of these complexes together with change of scale make it unfeasible as a procedure industrial.
(b) Separación mediante destilación fraccionada. La destilación fraccionada no da ni las purezas ni los rendimientos comentados a escala de laboratorio. Además como técnica no es la adecuada para purezas tan elevadas, hay muchas fracciones que son arrastradas junto con el escualeno. En el propio artículo de Serra Masiá en este apartado se dice que las experiencias a escala de laboratorio no fueron esperanzadoras, en cuanto a las condiciones de operación, fueron muy difíciles de conseguir y de estabilizar. En consecuencia no se lograron buenas separaciones.(b) Separation by fractional distillation. Fractional distillation gives neither purities nor yields commented on laboratory scale. Also as a technique it is not the suitable for purities so high, there are many fractions that are dragged along with squalene. In Serra's own article Masiá in this section it is said that experiences at the scale of laboratory were not hopeful, in terms of conditions of operation, they were very difficult to achieve and stabilize. In consequently no good separations were achieved.
(c) Separación mediante saponificación en presencia de un hidrótropo. En este procedimiento se separa en la fracción insaponificable el escualeno en presencia de otros compuestos, con lo que se hace más complejo su aislamiento. Además, se emplean ácidos minerales fuertes como el ácido sulfúrico para la fluidización de los geles formados durante el proceso de saponificación, lo cual es indeseable por su efecto corrosivo y altamente peligroso en su manipulación.(c) Separation by saponification in presence of a hydrotrope. In this procedure it is separated in the unsaponifiable fraction squalene in the presence of others compounds, which makes their isolation more complex. Further, strong mineral acids such as sulfuric acid are used for fluidization of gels formed during the process of saponification, which is undesirable due to its corrosive effect and highly dangerous in its handling.
De acuerdo con lo anterior, sería deseable disponer de un procedimiento de obtención de escualeno que minimice los inconvenientes anteriores y permita obtener escualeno con un grado de pureza adecuado.In accordance with the above, it would be desirable have a procedure to obtain squalene that minimizes the above disadvantages and allow to obtain squalene with a adequate degree of purity.
La invención proporciona un procedimiento de obtención de escualeno, a partir de aceites de origen animal. Más concretamente, la materia prima utilizada son aceites de hígado de escualo.The invention provides a method of Obtaining squalene, from oils of animal origin. Plus specifically, the raw material used are liver oils of it
De acuerdo con un primer aspecto de la invención, éste proporciona un procedimiento para la obtención de escualeno a partir de aceites de origen animal como materia prima, caracterizado porque comprende las etapas de:According to a first aspect of the invention, this provides a method for obtaining squalene from oils of animal origin as raw material, characterized in that it comprises the stages of:
- a)to)
- saponificación alcalina de la materia prima:alkaline saponification of matter cousin:
- b)b)
- separación física de la fracción saponificable e insaponificable; yphysical separation of the fraction saponifiable and unsaponifiable; Y
- c)C)
- destilación molecular a alto vacío.molecular distillation at high empty.
En una realización preferida de la invención, el aceite de origen animal empleado es un aceite de hígado de escualo. De un modo más preferido, el aceite de hígado de escualo comprende una mezcla de aceites provenientes de diferentes tipos de escualo. Entre los diferentes tipos de escualo de donde es posible obtener el escualeno, se encuentran aquellos tiburones y rayas pertenecientes a la Subclase Elasmobranchii y las quimeras de la Subclase Holocephali.In a preferred embodiment of the invention, the Animal oil used is a liver oil from shark. More preferably, the shark liver oil comprises a mixture of oils from different types of shark. Among the different types of shark from where it is possible to obtain the squalene, there are those sharks and rays belonging to Subclass Elasmobranchii and the chimeras of the Holocephali subclass.
De acuerdo con una realización preferida de la invención, la etapa de saponificación (a) se realiza en presencia de un hidrótropo.According to a preferred embodiment of the invention, the saponification stage (a) is performed in the presence of a hydrotrope.
Los hidrótopos (del griego tropos volver), que se llaman también agentes de acoplamiento, son sustancias muy hidrosolubles capaces de co-solubizar surfactantes de alto peso molecular y de poca solubilidad. Como su nombre lo indica, "vuelven" hidrofílicas a las demás sustancias.Hydropos (from the Greek tropos back), which are also called coupling agents, are very water-soluble substances capable of co-solubilizing high molecular weight and low solubility surfactants. As the name implies, they "return" hydrophilic to the other substances.
De modo preferido el hidrótropo se selecciona entre el grupo formado por xilensulfonato sódico, xilensulfonato amónico, metaxilensulfonato, etilbenceno sulfonato, urea, cumeno sulfonato sódico, cumeno sulfonato amónico, ácido paratoluen sulfónico y toluen sulfonato sódico. Es particularmente preferido, el xilensulfonato sódico, metaxilensulfonato y el etilbenceno sulfonato.Preferably the hydrotrope is selected between the group consisting of sodium xylenesulfonate, xylenesulfonate ammonium, metaxylenesulfonate, ethylbenzene sulfonate, urea, cumene sodium sulfonate, cumene ammonium sulfonate, paratoluen acid sulfonic and sodium toluene sulfonate. It is particularly preferred, sodium xylenesulfonate, metaxylenesulfonate and ethylbenzene sulphonate
De acuerdo con una realización preferida del procedimiento de la presente invención, el porcentaje de riqueza de escualeno en la fracción insaponificable tras la etapa b) es de al menos el 75%; mientras que el porcentaje de riqueza de escualeno tras el proceso de destilación molecular es de al menos el 90%, preferentemente más del 95%, y particularmente preferido más del 98%.According to a preferred embodiment of the procedure of the present invention, the percentage of wealth of squalene in the unsaponifiable fraction after stage b) is at minus 75%; while the percentage of squalene wealth after the molecular distillation process is at least 90%, preferably more than 95%, and particularly preferred more than 98%
En el procedimiento de preparación de la presente invención, es preferido el empleo de tiempos de reacción entre 15 y 25 horas, siendo más preferido un tiempo de 19 horas.In the procedure for preparing the In the present invention, the use of reaction times is preferred between 15 and 25 hours, a time of 19 being more preferred hours.
De acuerdo con una realización del procedimiento de la invención, en la etapa de saponificación alcalina se utiliza un exceso de base respecto al índice de saponificación del aceite utilizado. De modo preferido, se emplean aceites con un índice de saponificación de entre 180 y 240 mg base/g grasa. Más preferidos son aceites con un índice de saponificación de entre 190 y 210 mg base/g grasa.According to an embodiment of the procedure of the invention, the alkaline saponification stage is used an excess of base with respect to the oil saponification index used. Preferably, oils with an index of Saponification of between 180 and 240 mg base / g fat. Most preferred they are oils with a saponification index of between 190 and 210 mg base / g fat.
Según otra realización preferida de la invención, se emplea una relación en peso de base/grasa de entre 0,2 y 1, siendo más preferido 0,5. En cuanto a la relación en peso de agua total/grasa, preferentemente dicha relación está comprendida entre 1 y 5, siendo más preferido 1.According to another preferred embodiment of the invention, a base weight / fat ratio of between 0.2 and 1, 0.5 being more preferred. Regarding the weight ratio of total water / fat, preferably said ratio is between 1 and 5, with 1 being more preferred.
En el procedimiento de la presente invención, de modo preferido la saponificación alcalina se lleva a cabo utilizado una base seleccionada entre el grupo formado por NaOH, KOH, Ca(OH)_{2}, Mg(OH)_{2}. Siendo particularmente preferido el uso de KOH.In the process of the present invention, of preferred mode alkaline saponification is carried out used a base selected from the group consisting of NaOH, KOH, Ca (OH) 2, Mg (OH) 2. Being Particularly preferred is the use of KOH.
\global\parskip0.900000\baselineskip\ global \ parskip0.900000 \ baselineskip
De acuerdo con una realización preferida, se añade un ácido para la fluidización de los geles formados durante el proceso de saponificación, que de modo preferido se selecciona entre ácido fosfórico diluido, ácido láctico y ácido cítrico.According to a preferred embodiment, it is add an acid for the fluidization of gels formed during the saponification process, which is preferably selected between dilute phosphoric acid, lactic acid and citric acid.
Según una forma particular de realización del procedimiento de la invención el proceso de saponificación se lleva a cabo a una temperatura de entre 40 y 100ºC. Preferentemente la temperatura está comprendida entre 70 y 90ºC.According to a particular embodiment of the procedure of the invention the saponification process is carried carried out at a temperature between 40 and 100 ° C. Preferably the temperature is between 70 and 90 ° C.
El proceso de la invención puede realizarse de acuerdo con la siguiente descripción general. La numeración indicada hace referencia a la incluida en la Figura 1.The process of the invention can be carried out in According to the following general description. Numbering indicated refers to the one included in Figure 1.
El aceite (2) junto con la base (4), el hidrótropo(3) y el agua (5), se añaden al reactor (1) y una vez finalizado el proceso de saponificación se separa la fracción saponificable (7) e insaponificable (6). Es en la fracción insaponificable, donde se encuentra la mayor parte del escualeno presente en la muestra de partida. La fracción insaponificable se centrifuga (8) para retirar los restos de jabón (9) que contenga y seguidamente se lava dos veces con ácido fosfórico al 10% (w/w) (11), con objeto de retirar proteínas y sustancias hidrosolubles (13), y una tercera con agua (12) para retirar los restos de ácido fosfórico. Entre lavados consecutivos la muestra se centrifuga nuevamente (14), eliminando así restos acuosos (15). La extracción de esta grasa animal se realiza normalmente por fusión en fase acuosa, lo que aumenta el arrastre de compuestos de carácter no lipídico. El proceso de saponificación, aplicado a aceite de hígado de escualo, conlleva la formación de geles proteicos que engloban grasa neutra. La modificación del pH de estos geles ayuda a la fluidización de la fase gel y liberación de la grasa englobada. Por ello se realizan los lavados de la fracción insaponificable que contiene geles con una disolución de ácido fosfórico, ya que con ello se consigue cambiar el punto isoeléctrico de las proteínas y recuperar la grasa englobada. De este modo se obtiene el insaponificable lavado y sin proteínas que se analiza mediante técnicas cromatográficas (21) con objeto de determinar el porcentaje en peso de escualeno presente en las mismas. Un método de determinación del porcentaje de escualeno es mediante la cromatografía de gases, utilizando la técnica propuesta por la Unión Europea para la determinación conjunta de escualeno y ceras, separando en columna la fracción apolar y utilizando como patrón interno una solución de escualeno (J European Union Comision, Regulation EEC/183/93, Off. J. Eur. Comun. L248 1993). Seguidamente, la fracción insaponificable enriquecida en escualeno se somete a destilación molecular. Previamente se lleva a cabo la decoloración (16) de la misma. El objetivo es eliminar el color debido a compuestos de oxidación y el agua (17). Tras el proceso de destilación molecular a alto vacío (18), es posible obtener fracciones con 99% de riqueza en escualeno, siempre que la muestra de aceite empleado carezca de ácidos grasos libres (19) y (20).The oil (2) together with the base (4), the Hydrotrope (3) and water (5), are added to the reactor (1) and a once the saponification process is finished the fraction is separated saponifiable (7) and unsaponifiable (6). It is in the fraction unsaponifiable, where most of the squalene is found present in the starting sample. The unsaponifiable fraction is centrifuge (8) to remove the remains of soap (9) it contains and then washed twice with 10% phosphoric acid (w / w) (11), in order to remove proteins and water-soluble substances (13), and a third with water (12) to remove the remains of acid phosphoric. Between consecutive washes the sample is centrifuged again (14), thus eliminating aqueous residues (15). The removal of this animal fat is normally performed by phase fusion aqueous, which increases the drag of compounds of non-character lipid The saponification process, applied to liver oil of shark, involves the formation of protein gels that include neutral fat The modification of the pH of these gels helps the fluidization of the gel phase and release of the fat involved. By this is done by washing the unsaponifiable fraction that contains gels with a phosphoric acid solution, since with it is possible to change the isoelectric point of the proteins and recover the fat included. In this way the unsaponifiable washing and without proteins that is analyzed by chromatographic techniques (21) in order to determine the percentage by weight of squalene present in them. A method Determination of the percentage of squalene is by gas chromatography, using the technique proposed by the Union European for the joint determination of squalene and waxes, separating the apolar fraction in a column and using as a standard internal a squalene solution (J European Union Commission, Regulation EEC / 183/93, Off. J. Eur. Common. L248 1993). Next, the unsaponifiable fraction enriched in squalene It undergoes molecular distillation. Previously the discoloration (16) thereof. The goal is to remove the color due to oxidation compounds and water (17). After the process of molecular distillation under high vacuum (18), it is possible to obtain fractions with 99% wealth in squalene, as long as the sample of oil used lacks free fatty acids (19) and (20).
A lo largo de la descripción y las reivindicaciones la palabra "comprende" y sus variantes no pretenden excluir otras características técnicas, aditivos, componentes o pasos.Throughout the description and the claims the word "comprises" and its variants not they intend to exclude other technical characteristics, additives, components or steps.
Para los expertos en la materia, otros objetos, ventajas y características de la invención se desprenderán en parte de la descripción y en parte de la práctica de la invención. Los siguientes ejemplos y dibujos se proporcionan a modo de ilustración, y no se pretende que sean limitativos de la presente invención.For those skilled in the art, other objects, advantages and features of the invention will be partly detached of the description and in part of the practice of the invention. The following examples and drawings are provided by way of illustration, and are not intended to be limiting of the present invention.
Esquema del proceso de obtención de escualeno a partir de aceites de origen animal de la invención.Scheme of the process of obtaining squalene a from oils of animal origin of the invention.
El equipo experimental utilizado a escala de laboratorio para la realización de la etapa de saponificación consta de un reactor discontinuo tanque agitado que opera en condiciones isotermas. El reactor utilizado es de vidrio, cilíndrico, de 2 L de volumen útil y provisto de tapadera con un sistema de cierre hermético. La tapadera presentaba varios orificios; uno de ellos permitía la extracción de muestras y otro se encontraba conectado a un condensador que minimizaba la pérdida de compuestos por volatilización. El sistema de condensación estaba conectado a un baño termostático Frigiterm Selecta ® por el que circulaba agua a baja temperatura (5-8ºC). La termostatización del reactor se realizó a través de una camisa por la que circulaba glicerina procedente de un baño termostático idéntico al anterior, lo que permitió la calefacción del contenido interno del reactor. La temperatura del proceso se controló con una sonda de temperatura Testo 946.The experimental equipment used at the scale of laboratory for the realization of the saponification stage It consists of a batch tank agitated reactor that operates in Isothermal conditions The reactor used is glass, cylindrical, 2 L of useful volume and provided with cover with a hermetic closure system. The cover had several holes; one of them allowed the extraction of samples and another It was connected to a capacitor that minimized loss of compounds by volatilization. The condensation system was connected to a Frigiterm Selecta ® thermostatic bath where water circulated at low temperature (5-8ºC). The reactor thermostatization was performed through a jacket by the one that circulated glycerin from a thermostatic bath identical to the previous one, which allowed the heating of the content internal reactor. The process temperature was controlled with a Testo 946 temperature probe.
Dado que la agitación es un aspecto clave en las reacciones que transcurren en fase heterogénea, como es el caso de la reacción de saponificación, con objeto de conseguir una adecuada homogeneización del contenido interno del reactor se utilizó un agitador magnético Agimatic-HS Selecta® y un imán revestido de teflón.Since agitation is a key aspect in reactions that take place in a heterogeneous phase, as is the case with the saponification reaction, in order to achieve adequate homogenization of the internal content of the reactor a Agimatic-HS Selecta® magnetic stirrer and a magnet Teflon coated.
El equipo experimental utilizado a escala de planta piloto constaba de un reactor discontinuo de mezcla completa que se encontraba termostatizado, metálico, de 15 L de capacidad y con un orificio en la parte superior, por donde se añadieron los reactivos, y una apertura inferior, por la que se llevó a cabo la extracción de muestras. El reactor contaba con un encamisado conectado a un circuito cerrado por el que circulaba glicerina, para permitir la calefacción del medio de reacción. Dicho sistema calefactor constaba de un depósito de 5 L de capacidad donde se calienta el fluido calefactor, una bomba que permite la circulación de la glicerina y varias sondas de temperatura. La homogeneización del contenido interno del reactor se consiguió mediante un agitador de palas que giraba por acción de un motor. Con objeto de favorecer el mezclado, el reactor presentaba varios tabiques deflectores en su interior.The experimental equipment used at the scale of pilot plant consisted of a batch reactor complete mixing that was thermostated, metallic, 15 L capacity and with a hole at the top, where the reagents, and a lower opening, by which the Extraction of samples. The reactor had a jacket connected to a closed circuit through which glycerin circulated, to allow heating of the reaction medium. Said system heater consisted of a 5 L capacity tank where heats the heating fluid, a pump that allows circulation of glycerin and several temperature probes. Homogenization of the internal content of the reactor was achieved by means of a stirrer of blades that rotated by the action of an engine. In order to favor mixing, the reactor had several baffles in its interior.
\global\parskip1.000000\baselineskip\ global \ parskip1.000000 \ baselineskip
Los reactivos utilizados en los ensayos de saponificación llevados a cabo tanto a escala de laboratorio como en planta piloto para la obtención de escualeno a partir de aceite de hígado de escualo, fueron los siguientes:The reagents used in the tests of saponification carried out both on a laboratory scale and in pilot plant to obtain squalene from oil of spinal liver, were the following:
- --
- disolución de xilensulfonato sódico, de la compañía Huntsman, al 45% (w/w) en peso en agua;sodium xylenesulfonate solution, of the Huntsman company, at 45% (w / w) by weight in water;
- --
- hidróxido potásico (KOH 85%);potassium hydroxide (KOH 85%);
- --
- agua; yWater; Y
- --
- ácido fosfórico 10% w/w.acid 10% phosphoric w / w.
Se introdujeron en el reactor el aceite de hígado de escualo, el xilensulfonato sódico, el KOH y el agua. Se agitó (entre 500 y 1000 rpm) y se calentó durante un tiempo de reacción inferior a 25 horas. Se tomaron muestras a distintos tiempos, se procedió a centrifugar la mezcla de reacción, se lavó consecutivamente con ácido fosfórico diluido y con agua, centrifugándose entre los lavados.Oil was introduced into the reactor shark liver, sodium xylenesulfonate, KOH and water. Be stirred (between 500 and 1000 rpm) and heated for a time of reaction less than 25 hours. Samples were taken at different times, the reaction mixture was centrifuged, washed consecutively with dilute phosphoric acid and with water, spinning between washes.
Tras el análisis cromatográfico de las mismas se obtienen las concentraciones de escualeno que se muestran en la siguiente tabla:After the chromatographic analysis of the same they get the squalene concentrations shown in the following table:
\vskip1.000000\baselineskip\ vskip1.000000 \ baselineskip
\vskip1.000000\baselineskip\ vskip1.000000 \ baselineskip
Las condiciones cromatográficas empleadas son las siguientes:The chromatographic conditions used are the following:
- --
- Fase estacionaria: Columna SPB5 (5% difenil - 95% dimetilpolisiloxano) (25 m 0,25 mm I.D., 0,25 mm espesor de película)Phase stationary: SPB5 column (5% diphenyl - 95% dimethylpolysiloxane) (25 m 0.25 mm I.D., 0.25 mm film thickness)
- --
- Gas portador: Hidrógeno. Flujo: 1 mL/minGas Carrier: Hydrogen. Flow: 1 mL / min
- --
- Programa de temperatura del horno 120ºC durante 4 minutos y rampa de 4ºC/min hasta 310ºC120ºC oven temperature program for 4 minutes and ramp from 4ºC / min to 310ºC
- --
- Inyección "on column" y detector de ionización de llama a 325ºC"On column" injection and detector flame ionization at 325 ° C
\vskip1.000000\baselineskip\ vskip1.000000 \ baselineskip
El aceite de hígado de escualo que se utilizó como materia prima presentaba las características analíticas siguientes:The shark liver oil that was used as raw material it presented the analytical characteristics following:
- --
- Índice de acides (mg KOH/g grasa): 0,58Index of acids (mg KOH / g fat): 0.58
- --
- Índice de saponificaión (mg KOH/g grasa): 200,00Index Saponification (mg KOH / g fat): 200.00
- --
- Riqueza en escualeno (%): 30,00Wealth in squalene (%): 30.00
\vskip1.000000\baselineskip\ vskip1.000000 \ baselineskip
Seguidamente, la fracción insaponificable enriquecida en escualeno se sometió a un proceso de destilación molecular. Previamente se llevó a cabo la decoloración de la misma con tierra no activada (1% en peso) a vacío y a 90ºC.Next, the unsaponifiable fraction Squalane enriched underwent a distillation process molecular. Previously the discoloration of the same was carried out with non-activated soil (1% by weight) under vacuum and at 90 ° C.
El sistema de destilación empleado constó de una unidad de destilación de Recorrido Corto/Destilación Molecular KDL 5 de UIC GMBH, cuyas características son:The distillation system used consisted of a KDL Short Path / Molecular Distillation distillation unit 5 of UIC GMBH, whose characteristics are:
- --
- Caudal máx: 2 kg/hFlow max: 2 kg / h
- --
- Temperatura del evaporador máx: 300ºCMax evaporator temperature: 300ºC
- --
- Superficie del evaporador: 4,8 dm^{2}Evaporator surface: 4.8 dm 2
- --
- Superficie del condensador: 6,5 dm^{2}Condenser surface: 6.5 dm 2
- --
- Presión de trabajo: <0,5 mbarWorking pressure: <0.5 mbar
- --
- Suministro eléctrico: 230 V, 50-60 Hz. Potencial total: 12 kw.Power supply: 230 V, 50-60 Hz. Total potential: 12 kw.
\vskip1.000000\baselineskip\ vskip1.000000 \ baselineskip
Se llevaron a cabo dos procedimientos de destilación con idéntico resultado:Two procedures of distillation with identical result:
- --
- Destilación directa de la muestraDirect distillation of the sample
- --
- Destilación fraccionada secuencialFractional distillation sequential
\vskip1.000000\baselineskip\ vskip1.000000 \ baselineskip
Tras el proceso de destilación se obtuvieron fracciones con 99% de riqueza en escualeno.After the distillation process they were obtained fractions with 99% wealth in squalene.
Claims (18)
- a)to)
- saponificación alcalina de la materia prima:alkaline saponification of matter cousin:
- b)b)
- separación física de la fracción saponificable e insaponificable; yphysical separation of the fraction saponifiable and unsaponifiable; Y
- c)C)
- destilación molecular a alto vacío.molecular distillation at high empty.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES200700462A ES2304102B1 (en) | 2007-02-22 | 2007-02-22 | PROCEDURE FOR OBTAINING SCALES. |
| PCT/ES2008/000082 WO2008102032A1 (en) | 2007-02-22 | 2008-02-14 | Method for obtaining squalene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES200700462A ES2304102B1 (en) | 2007-02-22 | 2007-02-22 | PROCEDURE FOR OBTAINING SCALES. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| ES2304102A1 true ES2304102A1 (en) | 2008-09-01 |
| ES2304102B1 ES2304102B1 (en) | 2009-07-06 |
Family
ID=39708037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES200700462A Expired - Fee Related ES2304102B1 (en) | 2007-02-22 | 2007-02-22 | PROCEDURE FOR OBTAINING SCALES. |
Country Status (2)
| Country | Link |
|---|---|
| ES (1) | ES2304102B1 (en) |
| WO (1) | WO2008102032A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381274B (en) * | 2008-10-16 | 2012-05-30 | 中国农业大学 | Method for removing dissolvent residual from lycopene oleoresin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES8602102A1 (en) * | 1985-01-25 | 1985-11-16 | Derivan Sa | Squalene and squalane recovery |
| ES2002428A6 (en) * | 1986-10-21 | 1988-08-01 | Hispano Quimica | Hexa:methyl tetracosane prepn. |
| JPH06116171A (en) * | 1992-10-06 | 1994-04-26 | Nippon Fine Chem Co Ltd | Method for purifying natural squalene |
| CN1376471A (en) * | 2002-03-22 | 2002-10-30 | 海南加华海产生物制药有限公司 | Soft capsule 'Shaganling' |
-
2007
- 2007-02-22 ES ES200700462A patent/ES2304102B1/en not_active Expired - Fee Related
-
2008
- 2008-02-14 WO PCT/ES2008/000082 patent/WO2008102032A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES8602102A1 (en) * | 1985-01-25 | 1985-11-16 | Derivan Sa | Squalene and squalane recovery |
| ES2002428A6 (en) * | 1986-10-21 | 1988-08-01 | Hispano Quimica | Hexa:methyl tetracosane prepn. |
| JPH06116171A (en) * | 1992-10-06 | 1994-04-26 | Nippon Fine Chem Co Ltd | Method for purifying natural squalene |
| CN1376471A (en) * | 2002-03-22 | 2002-10-30 | 海南加华海产生物制药有限公司 | Soft capsule 'Shaganling' |
Non-Patent Citations (2)
| Title |
|---|
| [en linea] [recuperado el 13.06.2008] Recuperado de: EPO WPI Database & CN 1376471 A (JIAHUA MARINE PRODUCT AND BIOL) 30.10.2002, (resumen) * |
| [en linea] [recuperado el 23.06.2008] Recuperado de: EPO WPI Database & JP 06116171 A (NIPPON FINE CHEMICAL CO) 26.04.1994, (resumen) * |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2304102B1 (en) | 2009-07-06 |
| WO2008102032A1 (en) | 2008-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU602326B2 (en) | Extraction of lipids from animal material by use of supercritical co2 | |
| CN106267902B (en) | The extraction and distribution that the pressure of molecule improves | |
| ES2364768B2 (en) | PROCEDURE FOR THE EXTRACTION OF FATTY ACIDS FROM ALGAE BIOMASS. | |
| JP2021516712A (en) | Purification of triacylglyceride oil | |
| KR102031995B1 (en) | Use of at least one coproduct from the vegetable-oil refining industry for obtaining a purified total unsaponifiable vegetable oil product | |
| ES2304102B1 (en) | PROCEDURE FOR OBTAINING SCALES. | |
| Rathnakumar et al. | Improvements in the extraction of milk phospholipids from beta-serum using ultrasound prior to tertiary amine extraction | |
| ES2308924B1 (en) | PROCEDURE FOR OBTAINING SCALES. | |
| US3869482A (en) | Method of producing highly purified phosphatides | |
| JPS61257191A (en) | Production of polyalcohol fatty acid ester | |
| Aldaw et al. | Isolation and ultra-purification of oleic acid extracted from olive oil using urea crystallization | |
| Irsigler et al. | Studies on Tissue Thromboplastin II. Species Specificity* | |
| Deshpande et al. | Shata-dhauta-ghrita–A case study | |
| CN100559957C (en) | The separation method of phosvitin in the birds, beasts and eggs | |
| RU2002119578A (en) | A method for the treatment of infectious diseases | |
| Chatgilialoglu et al. | Biomimetic models of radical stress and related biomarkers | |
| JP5041790B2 (en) | Process for producing phosphatidylserine having polyunsaturated fatty acid as a constituent | |
| JP2016535160A (en) | Concentration of triterpene esters | |
| Tsanev et al. | Nucleic acid content in mouse epidermis separated from dermis by different methods | |
| Hashim | Hemolytic activity of Cicer arietinum l. Extracts by two extraction techniques | |
| WO2023043323A1 (en) | Method of extraction from animal material, and extracts therefrom | |
| CN111330514A (en) | Preparation method of oleosin | |
| Munakata et al. | Study on the porcine tubular basement membrane | |
| Edah et al. | Sustainable Deacidification of Crude Soybean Oil by Thermally Activated Arrinrasho Nanoclay | |
| Xu et al. | Fate of minor free amino acids and phospholipids in crude tallow during steam splitting |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EC2A | Search report published |
Date of ref document: 20080901 Kind code of ref document: A1 |
|
| PC2A | Transfer of patent | ||
| FD2A | Announcement of lapse in spain |
Effective date: 20180912 |