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US2552797A - Solvent fractionation of fatty materials - Google Patents

Solvent fractionation of fatty materials Download PDF

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US2552797A
US2552797A US601374A US60137445A US2552797A US 2552797 A US2552797 A US 2552797A US 601374 A US601374 A US 601374A US 60137445 A US60137445 A US 60137445A US 2552797 A US2552797 A US 2552797A
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propane
fatty
solution
temperature
pressure
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Felix E Lacey
William M Leaders
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JBS USA LLC
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Swift and Co Inc
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B7/00Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils
    • C11B7/0008Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils by differences of solubilities, e.g. by extraction, by separation from a solution by means of anti-solvents
    • C11B7/005Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils by differences of solubilities, e.g. by extraction, by separation from a solution by means of anti-solvents in solvents used at superatmospheric pressures

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  • This invention relates to the treatment of fatty materials to separate desired constituents. More particularly, the invention has to do with the solvent fractionation of fatty materials such as fats, fatty oils and fatty acids to produce puriiied fractions of different solubility.
  • the invention has particular application to the treatment of relatively crude materials to produce fractions thereof improved in color and more adapted for specific commercial uses.
  • Natural fatty materials often contain undesirable color bodies which are necessary to be re moved in the manufacture of commercial products. These color bodies are intensified by normal processes of oxidative deterioration and in many cases render the fatty material unsuited for commercial usage.
  • the color bodies are diii cult to remove and often require expensive factory treatment resulting in low yields.
  • Many fatty materials are composed of relatively high melting point and relatively low melting point mixtures. The loW melting point material is in greater demand than the higher melting point material which is of limited commercial use as now prepared.
  • An object of the present invention is to provide an improved method of removing the color from fatty materials.
  • Another object of the invention is to provide a process for treatment of fatty materials heretofore unavailable for the producti-on of high grade products.
  • Another object of the invention is to remove certain impurities from fatty materials which interfere with subsequent processing operations.
  • a further object of the invention is to provide an improved process of treating fats and fatty oils whereby increased yields of desired products are obtained.
  • a still further object of the invention is to produce from crude fatty materials a higher melting point fraction ⁇ of enhanced value.
  • an object of the invention is to provide a more efficient process for improving color and separating fractions of fatty materials.
  • the fatty materials which may be treated according to the ⁇ present invention comprise all grades of tallow and greases including edible and ine'dible varieties, all types of vegetable and marine oils Whether hydrogenated or unhydrogenated, and fatty acids Vderived from animal, vegetable or marine origin as well as synthetic esters and derivatives of the aforesaid fatty acids.
  • fatty oils Vderived from animal, vegetable or marine origin as well as synthetic esters and derivatives of the aforesaid fatty acids.
  • the material then required acid washing to remove impurities such as emulsifying agents and crystallizing inhibitors.
  • the product was then slowly crystallized by gradual reduction in temperature over an extended period of time.
  • the crystallized product was then separated by pressing into an oil fraction and a solid stearin fraction.
  • the process is complicated, ineicient, ⁇ very laborious, and fails to produce suliiciently Well separated fractions for most effective applications.
  • the yields have been relatively low and the quality of the products is inferior.
  • the present invention contemplates broadlyV the treatment of the raw material with a normally gaseous hydrocarbon solvent to remove undesirable color bodies under relatively high temperature and pressure conditions and the subsequent treatment of the decolorized product under lower temperature and pressure conditions to separate the product into fractions of different solubility and having different degrees of saturation and melting point.
  • the process further contemplates a correlation of the temperature and pressure conditions and a coaction of steps in the decolorization and solvent fractionation operations whereby minimum refrigeration comperatures near the critical point of the hydrocari bon and under sufficient pressure to maintain the hydrocarbon in liquid phase.
  • Infthe decolorizing operation two phases are formed, the heavier phase comprising a solution of ⁇ the color ⁇ .bodies and a lighter phase comprising a Solutionfof the decolorized product.
  • the heavier-solution, ⁇ or foots, is separated and the propane V ⁇ recovered leaving a dark viscous material similar to pitch.
  • the solution of decolorized oil is subjected ⁇ to a depropanizing operation under a reduced pressure. In the depropanizing operation the major portion ,of the 4propane is evaporated and the ⁇ oil chilled Vto a substantially .lower temperature.
  • the .propane rvolati'lized in the depropanizing chilling and recovery operations may Vbe cooled and recompressed to recover the .propane in a liquid form.
  • the .conditions in the decolorizing operation may vary considerably. We Ahave found that tern peratures .of 170 F. to l185 F. are satisfactory and preferably around 175 F.
  • the pressure should be vsuviicient to maintain the hydrocarbon in a liquid phase at the ltemperature specified. Pressures within the range of 400 pounds to 530 pounds are satisfactory, and preferably around 465 pounds per square inc-h absol-ute. 'Ihe Aratio of propane to oil in the decoloriz-ing operation may range from between to 1 to 30 ⁇ to 1 'and preferably .about to 1 by volume.
  • the proportions of the two phases in the decolorizing zone are about of the decolorized solution to 1 of the roots -although these may vary considerably depending on' the temperature conditions. In general -it is desirable from a yield and an eciency standpoint to operate at as low a temperature as possible and yet maintain two phases.
  • the depropanizging operation may be Icarried out under a pressure of about 200 pounds to 300 pounds per square inch preferably about 250 pounds per square inch, and at a temperature of 100 F. to 135 F., preferably about 120 F. Under these conditions sufficient propane is vaporized to reduce the ratio lof propane to oil to around 4 or 5 to l and preferably about 41/2 to l. 'Ihe vaporization of such quantity of propane would often cause undue cooling of the unvaporized solution for example it might be sufficient to reduce the temperature to around 40 F. to 50 F. Such low temperatures are undesirable and accordingly it is advantageous to add heat whereby the Vtempera-ture is maintained at around 115 F. to 130 F. and preferably around 120 F. It is desirable t0.
  • the heat may be supplied by any suitable means such as a direct heat exchange from a steam f or electrical coil, or indirect heating by .an electricalheater 'or steam jacket.
  • the propane is slowly evaporated kby agradual reduction in the pressure, the pressure being reduced by this operation fromiabou't 250 pounds to around 30 to 75 and preferably around 50 pounds.
  • the reduction in pressure will-cause sufficient propane to be vaporized to reduce the ⁇ ratio of propane ⁇ to-oil to .about 31/2 or 4 to 1.
  • the evaporation of the propane causes a reduction in temperature of the .remaining solution to around 20 .to ⁇ 40.F., preferably between0 F. and +l10,F.
  • This chilling operation must rbe controlled so that the temperature drop is between 1 and 2 per minute, making the total chilling time between 1 and2 hours depending upon the material being treated.
  • a suitable crystal structure for good filtration is formed with a cooling speed of-about 11A" per minute, the optimum ltration Vrang'fe being fobtained with approximately a minute chilling cycle.
  • the chilled solution- may be filtered in .any suitable :type of pressure l'ter, ⁇ preferably a ⁇ continuous rotary filter enclosed withina vapor itype shell.
  • a suitable filter is one shown'in the United States patent to Van Horn No. 2,050,007.
  • a decolorizing tower Referring to the .drawing the fatty charging stock -is introduced under pressure through the line II into the upper portion of a decolorizing tower ,2.
  • the tower 2 is preferably packed ywith a surface contact rmaterial rsuch as Raschig frin'gs not shown.
  • the normally gaseous :hydrocarbon solvent is introduced into the -lower portion of the tower through the line
  • the fatty material being heavier than the propane begins to ⁇ descend through the tower counter-current tothe rising propane solution.
  • the temperature at the top yof the tower is preferably maintained 2 to 10 higher than the temperature at the base of the tower.
  • the temperature conditions maintained in the tower facilitates the continuous separation of color bodies from the rising propane oil solution and enhances the efliciency of the operation from the standpoint of oil yield.
  • Under the temperature and pressure conditions maintained in the tower a separation of phases occurs. face is near the bottom, preferably below the line 3 where the propane is introduced.
  • the heavier phase in the lower portion of the tower is drawn off through the line 4 -controlled by a valve ⁇ 5 to a depropanizer 8.
  • a reduced pressure is maintained in the depropanizer 8 by releasing the pressure through the valve 5. Any propane not spontaneously evaporated by reduction in pressure may be stripped out withsteam.
  • the depropanized oil or foots is withdrawn from the bottom of the depropanizer through the line 9.
  • the propane vapors are withdrawn from the top of the depropanizer through the Vaporline i0.
  • the inter-V al'scsave'r While one depropanizing vessel is shown it is ⁇ preferred to use three depropanizers so as to obtain a three stage depropanization.
  • a suitable manner of operation of the depropanizers is to use 50 pounds in the rst stage, 5 pounds in the second and steam stripping at atmospheric in the final stage.
  • the foots would be drawn off from the final steam stripping stage and the propane vapors would be withdrawn from each stage.
  • the vapors from the first two stages of the depropanization would be pure propane whereas that from the final stage would be a mixture of propane and steam.
  • the propane may be recovered from the vapors and reused in the system.
  • the solution of decolorized oil and propane is withdrawn from the top of the decolorizer through the line l2 to a depropanizer I4.
  • the pressure in the depropanizer I4 is maintained substantially below that in the decolorizer 2 by operation of the reducing valve l5.
  • the reduction in pressure will cause a vaporization of the major portion of the propane and a reduction in temperature of the unvaporized solution.
  • heat is applied thereto. In the drawing such heat is supplied by a steam coil I5 but other means of heating may be used.
  • the propane vapors are withdrawn from the top of the depropanizer through the line I8 for recovery as explained hereinafter.
  • the unvaporized solution is withdrawn from the lower portion of the depropanizer through the line 2D and charged to a surge tank 2
  • acts merely as a reservoir for the chilling vessels 22 and 23.
  • the solution in the surge tank may be charged alternately to Chillers 22 or 23 through the lines 24 or 25 controlled by valves 26 and 2l.
  • a batch of oil is charged from the surge tank into one of the Chillers such as vessel 22.
  • the charge to the chiller is preferably insufcient to completely fill the chiller so as to provide a vapor space.
  • the pressure is gradually released by the valve 23 in the vapor line 30.
  • the reduction in pressure causes vaporization of the propane and a chilling of the oil.
  • the vapor line 33 is closed by valve 28 and the chilled oil is withdrawn from the bottom of the chiller through the liquid line 3
  • the liquid line communicates with a surge tank 33 whereby the oil treated in the chiller may be withdrawn to the surge tank.
  • the function of the surge tank 33 is to supply a steady stream of chilled solution to the rotary lter 35 which operates continuously.
  • the chiller 23 may be charged with another batch of oil from the surge tank 2
  • the chilling operation may be commenced in the vessel 23. This chilling operation is substantially the same as that described in connection with vessel 22 and may take place during the discharge of the chilled yproduct from the vessel 22.
  • Vapors from chiller 23 are passed through vapor line 36 in which is located valve 31 to vapor line 30.
  • the chilled solution in chiller 23 is conducted through a liquid line 43 controlled by valve 42 to the liquid line 3
  • vessels 22 and 23 are alternate batch operations and are Operated in such a manner as to give ade- 6 quate time for the chilling and the formation of crystals.
  • the charging and discharging times required for the loading and unloading of vessels 22 and 23 is small in comparison to the time consumed in the chilling operations so that the two vessels operating alternately maintain a steady supply of chilled solution for the continuous operation of the filter and use up sufcient warm solution from the surge tank 2
  • the vapors from the chillers 22 and 23 collecting in the vapor line 30 are compressed by the -pump 45 and introduced into the vapor line I8.
  • 8 are chilled in a cooler 4S to a suiciently low temperature to cause the vapors to liquefy.
  • the liquid is passed through the line 41 to a propane storage tank 188.
  • the chilled oil from the surge tank 33 is conducted through the line 50 to a filter 35.
  • the surge tank is preferably elevated somewhat above the lter 35 so that the oil feeds through the line 5U by gravity. Separation in filter 35 takes place under a positive pressure of propane gas, the solution passing through the rotary drum.
  • the crystalline material is collected on the drum and subjected to a wash of cold propane to further reduce the liquid portion absorbed on the crystal surfaces.
  • the crystal cake is removed from the rotary drum by a scraping mechanism which causes the crystalline material to fall into a trough where the temperature is increased suiliciently to cause a solution of the crystal fat in the propane present.
  • the solution is then conducted out of the lter through line 5
  • the liquid portion separated on the filter is combined with the wash solution and the mixture conducted through line 55 to a solvent recovery system 58, wherein the solvent is stripped out and solvent as vapors passed through the vapor line 59.
  • the oil is withdrawn through the line 60.
  • a sample of brown grease was decolorized in 30 volumes of propane at a temperature of about 175 F. and under a pressure of about 475 pounds in a tower. A temperature gradient of about 3 F. between the top and bottom of the tower was maintained. The lighter deoolorized liquid phase was withdrawn from the top of the tower and was introduced into a depropanizer with a reduction in pressure to about 250 pounds. The reduction in pressure caused suflicient propane to volatilize to reduce the propane to oil ratio to about l1/2 to 1 by volume. In the latter operation additional heat was supplied by a low pressure steam coil to maintain the temperature of the product at about 118 F.
  • the product was then introduced into a chiller wherein the pressure was gradually reduced to 40 pounds per square inch over a period of about minutes.
  • the gradual reduction in pressure was accomplished by boiling oi about 1/2 volume of propane producing a temperature of about 10 F. and leaving a nal ratio of propane to oil of about 4 to 1.
  • the product was removed from the chiller, ltered, and the oil and stearin fractions stripped of their propane content.
  • the yield of oil obtained in the ltrate was 81.2% and the yield of stearin removed as press cake was 18.8%, based on the decolorized material charged. to the lter.
  • the yield in the decolorizing tower was 97% overhead and 3% bottoms or foots.
  • the stearin cake from the lter had an iodine number .of 27.7, Aandthe filtrate from the filter had an iodine number of 78.0 and a pour point o f 40 vF.
  • the titer of the stearin was 50.1 C.
  • hydrolyzed white grease fatty acids which were too dark to read on the F.
  • A. C. color system were subjected to a propane decolorizing operation ina column using 30 volume propane to 1 ,of oil.
  • the temperature was about 174 F. with a 3 F. temperature gradient and the pres- V.Sure was about 475 pounds per square inch.
  • A. C. was 97.3%.
  • the bottoms or foots fraction was black and viscous and contained about total fatty acids.
  • the decolorized overhead fraction from the tower was subjected to a depropanizing operation whereby the propane to oil ratio was reduced to about 4 to 1 at a temperature .of .about 120 F.. and at a pressure of about 26.5 pounds. Heat was supplied in the depropanizing operation by an electrical heating coil. The material was then chilled by gradually reducing the pressure to about 45 pounds per square inch. The temperature was reduced to about 12 F. with an accompanying reduction of the propane ratio to about 3.6 to 1 of oil. The material was ltered and the products stripped of propane. The resulting red oil fraction had an iodine number of 991/2, a titer of about '3 C. and a color not darker than 3 F. A. C'.
  • the stearin or stearic acid removed from the filter had an iodine number of 3.4 and a melting point of 124 F.
  • the yield of red oil was 60.6% and of stearic acid was 39.4% on the basis of the overhead decolorized product.
  • Soybean fatty acids obtained by the acidulation and hydrolyzing of soybean rening foots may be subjected to a decolorizing operation as above described and the product subjected to a subsequent chillng and filtration at a propane ratio of 5 to 1 and temperature of about -20 F. to 30 F.
  • An ⁇ overhead fraction with an iodine number of about 90 and a liquid filtrate fraction with an iodine number of around 165 are obtained.
  • Sperm oil may be decolorized in a manner similar to that described above and the propane to oil ratio reduced from 20 to 1 to about 3.5 to 1 in the depropanizing operation. A slow release of an additional 1/ volume of propane will chill the solution from 120 F. to a temperature of 10 F. suitable for filtering. A yield of about 92.9% of sperm oil with a maximum pour point of 40 F. and 7.1% of spermaceti with an iodine number of 15.2 and a melting point of 108 F. are obtained.
  • fatty material which as used in the claims is intended to mean fats, fatty oils, and fatty acids, or mixtures thereof, and methyl esters of said fats and fatty oils.
  • fat as used in the claims is intended te mean solid fats or fattir oils of animal, vegetable, or marine origin.
  • the present invention has the advantage of decolorizing and fractionating products in one continuous operation without the necessity of changing solvents. Also the energy required to compress the normal gaseous hydrocarbon into the liquid state for the decolorizing operation is more advantageously utilized in this process by the subsequent refrigeration-operation in the fractionation step. For example, on account of the relatively high temperature conditions in the decolorizing operation, a large amount of energy is required to maintain the propane in the liquid phase. This excess energy is advantageously utilized for chilling the decolorized product and to crystaliize the higher melting point fractions in the subsequent fractionation operations. Moreover, in the process of the presentl invention the solvent is more eiciently used and may be recovered with a. minimum amount of equipment and power facilities.
  • a process for treating fatty materials which comprises subjecting a solution of the fatty material in a normally gaseous hydrocarbon solvent to elevated temperature and pressure conditions whereby two liquid phases are formed, the lighter of said phases containing relatively light color fatty material and the heavier of said phases containing relatively dark color materials, separating the phases, vaporizing at least a .portion of the normally gaseous hydrocarbon in the lighter phase by reducing the pressure While controlling the heat content of the remainder of the solution so that the temperature thereof does not fall below about to 135 F., chilling the solution of light color fatty material sufficient to precipitate a higher melting point fraction and separating said highe1l melting point fraction from the lower melting point fractions.
  • a process for refining and fractionating fatty materials which comprises forming a solution of the fatty material in a. normally gaseous hydrocarbon solvent, raising the temperature of the solution to around to 185 F. to form a lighter refined liquid .phase and a heavier liquid phase containing impurities while maintaining pressures sufficiently high to retain the normally gaseous hydrocarbon in the liquid phase, separating the phases, reducing the pressure in the lighter phase sufficiently to Vaporize at least a portion of the normally gaseous hydrocarbon thereby cooling the unvaporized portion to around 100 to 135 F., chilling said unvaporized portion to around 20 to +40 F. to crystallize a higher melting point fraction, and separating the crystals from the refined product.
  • a process for refining and fractionating fats which comprises mixing with the fat about 20 to 30 Volumes of a liquefied normally gaseous hydrocarbon, subjecting the resulting solution. 'to temperatures sufficiently high to cause the separation of a phase containing impurities while under pressures sufficiently high to maintain said hydrocarbon substantially liquefied, separating said phase, vaporizing a portion of the liquefied normally gaseous hydrocarbon from the remain ing solution until about 4 to 5 Volumes of hydrocarbon remain while controlling the heat in said solution so that it is not chilled below about 100 F., continuing said chilling sufficient to cause the crystallization of a fraction of the fat and separating said crystallized fraction from the re mainder of the fat.
  • a process for refining and destearinizing fats which comprises subjecting the fatty material in the presence of liquefied propane to temperatures near the critical point of the propane whereby two liquid phases are formed, one of said phases containing decolorized fatty material and the other phase containing foots, separating the foots, reducing the pressure in the decolorized phase to around 200 to 300 pounds thereby Vaporizing the propane and cooling the solution while controlling the temperature whereby the temperature does not fall below about 1000 F., chilling said solution by further reducing the pressure to about 30 to 75 pounds to cause the stearin to crystallize and filtering the solution to separate the stearin.
  • a process for refining and fractionating fatty acids which comprises forming a solution of the fatty acids in about 15 to 30 volumes propane, subjecting said solution While under pressure sufliciently high to maintain the propane in the liquid phase to temperatures of about 170 to 185 F. at which the product separates into tWo phases, one of said phases containing refined fatty acids and the otherl phase containing irnpurities, separating the phases, chilling the refined fatty acid phase by utilizing the heat of vaporization of the propane to temperatures sufficiently low to crystallize high melting point fatty acids, said chilling taking place in two stages, the temperature in the rst stage being reduced to about 100 to 135 F.. and in the second stage to about 20 to +40 F., and filtering said crystallized fatty acids from the solution.
  • a process for refining and fractionating fatty materials which comprises subjecting a solution of the fatty material in a normally gaseous hydrocarbon solvent to temperature and pressure conditions to cause a separation of a heavier liquid phase containing impurities and a lighter liquid phase containing decolorized fatty material, separating said phases, reducing the pressure to Vaporize a portion of said hydrocarbon from the lighter liquid phase while supplying heat to avoid cooling below about 100 lF., chilling the decolorized fatty material by vaporizing a further quantity of the normally gaseous hydrocarbon to a temperature suiciently low to crystallize the higher melting constituents of said fatty material and then filtering the mixture to separate said higher melting point constituents.

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Description

May 15, 1951 F. E. LACEY ETAL l 2,552,797
soLvENT FRACTIONATION oF FATTY MATERIALS Filed June 25, 1945 cH LLER NA? mh BY ffl/@ Arroz/#Ey Patented May 15, 1951 SOLVENT FRACTIONATION OF FATTY MATERIALS Felix E. Lacey and William M. Leaders, Chicago, Ill., assignors, by mesne assignments, to Swift & Company, a corporation of Illinois Application June 25, 1945, Serial No. 601,374
6 Claims.
This invention relates to the treatment of fatty materials to separate desired constituents. More particularly, the invention has to do with the solvent fractionation of fatty materials such as fats, fatty oils and fatty acids to produce puriiied fractions of different solubility. The invention has particular application to the treatment of relatively crude materials to produce fractions thereof improved in color and more adapted for specific commercial uses.
Natural fatty materials often contain undesirable color bodies which are necessary to be re moved in the manufacture of commercial products. These color bodies are intensified by normal processes of oxidative deterioration and in many cases render the fatty material unsuited for commercial usage. The color bodies are diii cult to remove and often require expensive factory treatment resulting in low yields. Many fatty materials are composed of relatively high melting point and relatively low melting point mixtures. The loW melting point material is in greater demand than the higher melting point material which is of limited commercial use as now prepared.
An object of the present invention is to provide an improved method of removing the color from fatty materials.
Another object of the invention is to provide a process for treatment of fatty materials heretofore unavailable for the producti-on of high grade products.
Another object of the invention is to remove certain impurities from fatty materials which interfere with subsequent processing operations.
A further object of the invention is to provide an improved process of treating fats and fatty oils whereby increased yields of desired products are obtained.
A still further object of the invention is to produce from crude fatty materials a higher melting point fraction `of enhanced value.
Also an object of the invention is to provide a more efficient process for improving color and separating fractions of fatty materials.
The fatty materials which may be treated according to the `present invention comprise all grades of tallow and greases including edible and ine'dible varieties, all types of vegetable and marine oils Whether hydrogenated or unhydrogenated, and fatty acids Vderived from animal, vegetable or marine origin as well as synthetic esters and derivatives of the aforesaid fatty acids. Heretofore in the manufacture of fatty oils from greases a selection of raw material was made (Cl. Bll-4.28.5)
to provide sumciently high quality of products. The material then required acid washing to remove impurities such as emulsifying agents and crystallizing inhibitors. The product was then slowly crystallized by gradual reduction in temperature over an extended period of time. The crystallized product was then separated by pressing into an oil fraction and a solid stearin fraction. The process is complicated, ineicient,` very laborious, and fails to produce suliiciently Well separated fractions for most effective applications. The yields have been relatively low and the quality of the products is inferior. y f
Sperm oils have been treated heretofore in much the same manner as greascs. The same disadvantages are in general inherent in the process of the treatment of marine oils as in the treatment of greases. In the prior methods of manufacturing fatty acids such as red oil and stearic acid raw ma-A terials Which are usually quite dark in color are often used. The resulting crude fatty acids are distilled to recover a light color distillate and to separate the color bodies as bottoms. The distilled fatty acids are then subjected to repeated crystallization and pressing to separate the saturated from the unsaturated fatty acids. In such an operation there are high losses in the distillation step due to polymerization sometimes amounting to as much as 12%. Also the seeding or crystallizing and pressing operations are expensive, require a large amount of equipment and require much hand labor. In the `treatment of foots resulting from the rening of vegetable oils such as cotton and soybean oil it has been customary heretofore to acidulate and distill the resulting released fatty acids. The losses in this operation are very high often running to as much as 25% to 35%. 'These products have been suitable only for use requiring a relatively cheap source of raw material.
The present invention contemplates broadlyV the treatment of the raw material with a normally gaseous hydrocarbon solvent to remove undesirable color bodies under relatively high temperature and pressure conditions and the subsequent treatment of the decolorized product under lower temperature and pressure conditions to separate the product into fractions of different solubility and having different degrees of saturation and melting point. The process further contemplates a correlation of the temperature and pressure conditions and a coaction of steps in the decolorization and solvent fractionation operations whereby minimum refrigeration comperatures near the critical point of the hydrocari bon and under sufficient pressure to maintain the hydrocarbon in liquid phase. Infthe decolorizing operation two phases are formed, the heavier phase comprising a solution of `the color `.bodies and a lighter phase comprising a Solutionfof the decolorized product. The heavier-solution, `or foots, is separated and the propane V`recovered leaving a dark viscous material similar to pitch. The solution of decolorized oil is subjected `to a depropanizing operation under a reduced pressure. In the depropanizing operation the major portion ,of the 4propane is evaporated and the `oil chilled Vto a substantially .lower temperature. The
Y remainder of .the solution containing unvaporized propane is subjected to additional vaporization under a further reduced pressure. In .the latter vaporizgation operation -the oil is chilled to -a suiciently low temperature to crystallize the high melting point constituents, suficient propane remaining in the product to enable the mixture to be i"ltered.4 The chilled product is then filtered to remove the crystalline portion from the solution of oiland propane. The higher melting point fraction and the .oil fraction are subjected to solvent .recovery operations to recover the propane.
The .propane rvolati'lized in the depropanizing chilling and recovery operations may Vbe cooled and recompressed to recover the .propane in a liquid form.
The .conditions in the decolorizing operation may vary considerably. We Ahave found that tern peratures .of 170 F. to l185 F. are satisfactory and preferably around 175 F. The pressure should be vsuviicient to maintain the hydrocarbon in a liquid phase at the ltemperature specified. Pressures within the range of 400 pounds to 530 pounds are satisfactory, and preferably around 465 pounds per square inc-h absol-ute. 'Ihe Aratio of propane to oil in the decoloriz-ing operation may range from between to 1 to 30 `to 1 'and preferably .about to 1 by volume. Grdinari-ly the proportions of the two phases in the decolorizing zone are about of the decolorized solution to 1 of the roots -although these may vary considerably depending on' the temperature conditions. In general -it is desirable from a yield and an eciency standpoint to operate at as low a temperature as possible and yet maintain two phases.
The depropanizging operation may be Icarried out under a pressure of about 200 pounds to 300 pounds per square inch preferably about 250 pounds per square inch, and at a temperature of 100 F. to 135 F., preferably about 120 F. Under these conditions sufficient propane is vaporized to reduce the ratio lof propane to oil to around 4 or 5 to l and preferably about 41/2 to l. 'Ihe vaporization of such quantity of propane would often cause undue cooling of the unvaporized solution for example it might be sufficient to reduce the temperature to around 40 F. to 50 F. Such low temperatures are undesirable and accordingly it is advantageous to add heat whereby the Vtempera-ture is maintained at around 115 F. to 130 F. and preferably around 120 F. It is desirable t0.
maintain such temperature in the first stage of depropanization so that the further cooling and crystallization of the higher melting point fats can be brought about subsequently under controlled conditions which favor the growth of more readily filtered solids. Another adyantage of maintaining such temperature -in the .first stage of -depropanization is the `fact that the pressure of the Vapor formed is sufficient to permit lique- :faction by a simple condensing operation which eliminates a great deal of mechanical compresision. 'The heat may be supplied by any suitable means such as a direct heat exchange from a steam f or electrical coil, or indirect heating by .an electricalheater 'or steam jacket.
In thecchilling operation the propane is slowly evaporated kby agradual reduction in the pressure, the pressure being reduced by this operation fromiabou't 250 pounds to around 30 to 75 and preferably around 50 pounds. The reduction in pressure :will-cause sufficient propane to be vaporized to reduce the `ratio of propane `to-oil to .about 31/2 or 4 to 1. vThe evaporation of the propane causes a reduction in temperature of the .remaining solution to around 20 .to {40.F., preferably between0 F. and +l10,F. This chilling operation must rbe controlled so that the temperature drop is between 1 and 2 per minute, making the total chilling time between 1 and2 hours depending upon the material being treated. A suitable crystal structure for good filtration is formed with a cooling speed of-about 11A" per minute, the optimum ltration Vrang'fe being fobtained with approximately a minute chilling cycle. The chilled solution-may be filtered in .any suitable :type of pressure l'ter, `preferably a `continuous rotary filter enclosed withina vapor itype shell. A suitable filter is one shown'in the United States patent to Van Horn No. 2,050,007.
The vinvention `will be ,more clearly understood from fthe following description read `in connection with :the accompanying drawing.
Referring to the .drawing the fatty charging stock -is introduced under pressure through the line II into the upper portion of a decolorizing tower ,2. rThe tower 2 is preferably packed ywith a surface contact rmaterial rsuch as Raschig frin'gs not shown. The normally gaseous :hydrocarbon solvent is introduced into the -lower portion of the tower through the line The fatty material being heavier than the propane begins to `descend through the tower counter-current tothe rising propane solution. The temperature at the top yof the tower is preferably maintained 2 to 10 higher than the temperature at the base of the tower. The temperature conditions maintained in the tower facilitates the continuous separation of color bodies from the rising propane oil solution and enhances the efliciency of the operation from the standpoint of oil yield. Under the temperature and pressure conditions maintained in the tower a separation of phases occurs. face is near the bottom, preferably below the line 3 where the propane is introduced. The heavier phase in the lower portion of the tower is drawn off through the line 4 -controlled by a valve `5 to a depropanizer 8. A reduced pressure is maintained in the depropanizer 8 by releasing the pressure through the valve 5. Any propane not spontaneously evaporated by reduction in pressure may be stripped out withsteam. The depropanized oil or foots is withdrawn from the bottom of the depropanizer through the line 9. The propane vapors are withdrawn from the top of the depropanizer through the Vaporline i0.
The inter-V al'scsave'r While one depropanizing vessel is shown it is `preferred to use three depropanizers so as to obtain a three stage depropanization. A suitable manner of operation of the depropanizers is to use 50 pounds in the rst stage, 5 pounds in the second and steam stripping at atmospheric in the final stage. When three stages of depropanization are used the foots would be drawn off from the final steam stripping stage and the propane vapors would be withdrawn from each stage. The vapors from the first two stages of the depropanization Would be pure propane whereas that from the final stage would be a mixture of propane and steam. The propane may be recovered from the vapors and reused in the system.
The solution of decolorized oil and propane is withdrawn from the top of the decolorizer through the line l2 to a depropanizer I4. The pressure in the depropanizer I4 is maintained substantially below that in the decolorizer 2 by operation of the reducing valve l5. The reduction in pressure will cause a vaporization of the major portion of the propane and a reduction in temperature of the unvaporized solution. In order to avoid excessive cooling of the solution in the depropanizer heat is applied thereto. In the drawing such heat is supplied by a steam coil I5 but other means of heating may be used. The propane vapors are withdrawn from the top of the depropanizer through the line I8 for recovery as explained hereinafter. The unvaporized solution is withdrawn from the lower portion of the depropanizer through the line 2D and charged to a surge tank 2|. The surge tank 2| acts merely as a reservoir for the chilling vessels 22 and 23. The solution in the surge tank may be charged alternately to Chillers 22 or 23 through the lines 24 or 25 controlled by valves 26 and 2l.
In one method of operation a batch of oil is charged from the surge tank into one of the Chillers such as vessel 22. The charge to the chiller is preferably insufcient to completely fill the chiller so as to provide a vapor space. After the vessel is charged the pressure is gradually released by the valve 23 in the vapor line 30. The reduction in pressure causes vaporization of the propane and a chilling of the oil. When sufcient vaporization and chilling has occurred the vapor line 33 is closed by valve 28 and the chilled oil is withdrawn from the bottom of the chiller through the liquid line 3| controlled by valve 32. The liquid line communicates with a surge tank 33 whereby the oil treated in the chiller may be withdrawn to the surge tank. The function of the surge tank 33 is to supply a steady stream of chilled solution to the rotary lter 35 which operates continuously. During the operation of the chiller 22 the chiller 23 may be charged with another batch of oil from the surge tank 2|. When the charge in chiller 22 is Sufliciently chilled and the valve 28 is closed the chilling operation may be commenced in the vessel 23. This chilling operation is substantially the same as that described in connection with vessel 22 and may take place during the discharge of the chilled yproduct from the vessel 22. Vapors from chiller 23 are passed through vapor line 36 in which is located valve 31 to vapor line 30. The chilled solution in chiller 23 is conducted through a liquid line 43 controlled by valve 42 to the liquid line 3|.
It will be observed that the operations of vessels 22 and 23 are alternate batch operations and are Operated in such a manner as to give ade- 6 quate time for the chilling and the formation of crystals. The charging and discharging times required for the loading and unloading of vessels 22 and 23 is small in comparison to the time consumed in the chilling operations so that the two vessels operating alternately maintain a steady supply of chilled solution for the continuous operation of the filter and use up sufcient warm solution from the surge tank 2|' to allow continuous operation prior to the batch chilling. The vapors from the chillers 22 and 23 collecting in the vapor line 30 are compressed by the -pump 45 and introduced into the vapor line I8.
The combined vapors in the line |8 are chilled in a cooler 4S to a suiciently low temperature to cause the vapors to liquefy. The liquid is passed through the line 41 to a propane storage tank 188.
The chilled oil from the surge tank 33 is conducted through the line 50 to a filter 35. The surge tank is preferably elevated somewhat above the lter 35 so that the oil feeds through the line 5U by gravity. Separation in filter 35 takes place under a positive pressure of propane gas, the solution passing through the rotary drum. The crystalline material is collected on the drum and subjected to a wash of cold propane to further reduce the liquid portion absorbed on the crystal surfaces. The crystal cake is removed from the rotary drum by a scraping mechanism which causes the crystalline material to fall into a trough where the temperature is increased suiliciently to cause a solution of the crystal fat in the propane present. The solution is then conducted out of the lter through line 5| to a solvent recovery system wherein the solvent is stripped of the fat, the solvent being withdrawn through the line 53 and the fat through the line 54. The liquid portion separated on the filter is combined with the wash solution and the mixture conducted through line 55 to a solvent recovery system 58, wherein the solvent is stripped out and solvent as vapors passed through the vapor line 59. The oil is withdrawn through the line 60.
As an example of the operation of the invention, a sample of brown grease was decolorized in 30 volumes of propane at a temperature of about 175 F. and under a pressure of about 475 pounds in a tower. A temperature gradient of about 3 F. between the top and bottom of the tower was maintained. The lighter deoolorized liquid phase was withdrawn from the top of the tower and was introduced into a depropanizer with a reduction in pressure to about 250 pounds. The reduction in pressure caused suflicient propane to volatilize to reduce the propane to oil ratio to about l1/2 to 1 by volume. In the latter operation additional heat was supplied by a low pressure steam coil to maintain the temperature of the product at about 118 F. The product was then introduced into a chiller wherein the pressure was gradually reduced to 40 pounds per square inch over a period of about minutes. The gradual reduction in pressure was accomplished by boiling oi about 1/2 volume of propane producing a temperature of about 10 F. and leaving a nal ratio of propane to oil of about 4 to 1. The product was removed from the chiller, ltered, and the oil and stearin fractions stripped of their propane content. The yield of oil obtained in the ltrate was 81.2% and the yield of stearin removed as press cake was 18.8%, based on the decolorized material charged. to the lter. The yield in the decolorizing tower was 97% overhead and 3% bottoms or foots. The
-7 original .brown grease charged to the decolorizer .nadia color too .dark .to read by the F. A. C. .SYS- tem .(Fat Analysis Committee). The overhead from the decolorizer 'had a color of 2.9 red in a `inch Lovibond column. The 3% foots obtained were .of the consistency and color of ordinary pitch. This pitch contained 591/2% moisture and Volatile matter, 131/2% tota] fatty acids, 1.3% nitrogen and 0.32% phosphorus, the remainder `being insoluble matter. The original brown grease had an iodine number (Wijz) of 68.0. The stearin cake from the lter had an iodine number .of 27.7, Aandthe filtrate from the filter had an iodine number of 78.0 and a pour point o f 40 vF. The titer of the stearin was 50.1 C.
As another example of the operation of the invention, hydrolyzed white grease fatty acids which were too dark to read on the F. A. C. color system were subjected to a propane decolorizing operation ina column using 30 volume propane to 1 ,of oil. The temperature was about 174 F. with a 3 F. temperature gradient and the pres- V.Sure was about 475 pounds per square inch. The yield off decolorized fatty acids with a color not darker than 1 F. A. C. was 97.3%. The bottoms or foots fraction was black and viscous and contained about total fatty acids. The decolorized overhead fraction from the tower was subjected to a depropanizing operation whereby the propane to oil ratio was reduced to about 4 to 1 at a temperature .of .about 120 F.. and at a pressure of about 26.5 pounds. Heat Was supplied in the depropanizing operation by an electrical heating coil. The material was then chilled by gradually reducing the pressure to about 45 pounds per square inch. The temperature was reduced to about 12 F. with an accompanying reduction of the propane ratio to about 3.6 to 1 of oil. The material was ltered and the products stripped of propane. The resulting red oil fraction had an iodine number of 991/2, a titer of about '3 C. and a color not darker than 3 F. A. C'. The stearin or stearic acid removed from the filter had an iodine number of 3.4 and a melting point of 124 F. The yield of red oil was 60.6% and of stearic acid was 39.4% on the basis of the overhead decolorized product.
Soybean fatty acids obtained by the acidulation and hydrolyzing of soybean rening foots may be subjected to a decolorizing operation as above described and the product subjected to a subsequent chillng and filtration at a propane ratio of 5 to 1 and temperature of about -20 F. to 30 F. An `overhead fraction with an iodine number of about 90 and a liquid filtrate fraction with an iodine number of around 165 are obtained.
Sperm oil may be decolorized in a manner similar to that described above and the propane to oil ratio reduced from 20 to 1 to about 3.5 to 1 in the depropanizing operation. A slow release of an additional 1/ volume of propane will chill the solution from 120 F. to a temperature of 10 F. suitable for filtering. A yield of about 92.9% of sperm oil with a maximum pour point of 40 F. and 7.1% of spermaceti with an iodine number of 15.2 and a melting point of 108 F. are obtained.
Other materials which may be treated substan* tially as described above include edible tallow, lard, cottonseed oil, coconut oil, soybean oil, sardine oil, whale oil of the glyceride variety, dark inedible tallows, yellow grease, white grease, hydrogenated fish oils, and the methyl esters and fatty acids of such products. The latter materials as Well as those mentioned .in the above examples are .included Within the meaning of the term fatty material which as used in the claims is intended to mean fats, fatty oils, and fatty acids, or mixtures thereof, and methyl esters of said fats and fatty oils. The term fat as used in the claims is intended te mean solid fats or fattir oils of animal, vegetable, or marine origin.
While we have described the invention in connection With the use of propane as solvent other normally gaseous hydrocarbons such as ethane, propylene, iso and normal butanes and mixtures thereof may be used.
The present invention has the advantage of decolorizing and fractionating products in one continuous operation without the necessity of changing solvents. Also the energy required to compress the normal gaseous hydrocarbon into the liquid state for the decolorizing operation is more advantageously utilized in this process by the subsequent refrigeration-operation in the fractionation step. For example, on account of the relatively high temperature conditions in the decolorizing operation, a large amount of energy is required to maintain the propane in the liquid phase. This excess energy is advantageously utilized for chilling the decolorized product and to crystaliize the higher melting point fractions in the subsequent fractionation operations. Moreover, in the process of the presentl invention the solvent is more eiciently used and may be recovered with a. minimum amount of equipment and power facilities.
Obviously, many modifications and variations of the invention hereinbefore set forth may be made Without departing from the spirit and scope thereof, and, therefore, only such limitations should be imposed as are indicated in the appended claims.
We claim:
1. A process for treating fatty materials which comprises subjecting a solution of the fatty material in a normally gaseous hydrocarbon solvent to elevated temperature and pressure conditions whereby two liquid phases are formed, the lighter of said phases containing relatively light color fatty material and the heavier of said phases containing relatively dark color materials, separating the phases, vaporizing at least a .portion of the normally gaseous hydrocarbon in the lighter phase by reducing the pressure While controlling the heat content of the remainder of the solution so that the temperature thereof does not fall below about to 135 F., chilling the solution of light color fatty material sufficient to precipitate a higher melting point fraction and separating said highe1l melting point fraction from the lower melting point fractions.
2. A process for refining and fractionating fatty materials which comprises forming a solution of the fatty material in a. normally gaseous hydrocarbon solvent, raising the temperature of the solution to around to 185 F. to form a lighter refined liquid .phase and a heavier liquid phase containing impurities while maintaining pressures sufficiently high to retain the normally gaseous hydrocarbon in the liquid phase, separating the phases, reducing the pressure in the lighter phase sufficiently to Vaporize at least a portion of the normally gaseous hydrocarbon thereby cooling the unvaporized portion to around 100 to 135 F., chilling said unvaporized portion to around 20 to +40 F. to crystallize a higher melting point fraction, and separating the crystals from the refined product.
3. A process for refining and fractionating fats, which comprises mixing with the fat about 20 to 30 Volumes of a liquefied normally gaseous hydrocarbon, subjecting the resulting solution. 'to temperatures sufficiently high to cause the separation of a phase containing impurities while under pressures sufficiently high to maintain said hydrocarbon substantially liquefied, separating said phase, vaporizing a portion of the liquefied normally gaseous hydrocarbon from the remain ing solution until about 4 to 5 Volumes of hydrocarbon remain while controlling the heat in said solution so that it is not chilled below about 100 F., continuing said chilling sufficient to cause the crystallization of a fraction of the fat and separating said crystallized fraction from the re mainder of the fat.
4. A process for refining and destearinizing fats which comprises subjecting the fatty material in the presence of liquefied propane to temperatures near the critical point of the propane whereby two liquid phases are formed, one of said phases containing decolorized fatty material and the other phase containing foots, separating the foots, reducing the pressure in the decolorized phase to around 200 to 300 pounds thereby Vaporizing the propane and cooling the solution while controlling the temperature whereby the temperature does not fall below about 1000 F., chilling said solution by further reducing the pressure to about 30 to 75 pounds to cause the stearin to crystallize and filtering the solution to separate the stearin.
5. A process for refining and fractionating fatty acids which comprises forming a solution of the fatty acids in about 15 to 30 volumes propane, subjecting said solution While under pressure sufliciently high to maintain the propane in the liquid phase to temperatures of about 170 to 185 F. at which the product separates into tWo phases, one of said phases containing refined fatty acids and the otherl phase containing irnpurities, separating the phases, chilling the refined fatty acid phase by utilizing the heat of vaporization of the propane to temperatures sufficiently low to crystallize high melting point fatty acids, said chilling taking place in two stages, the temperature in the rst stage being reduced to about 100 to 135 F.. and in the second stage to about 20 to +40 F., and filtering said crystallized fatty acids from the solution.
6. A process for refining and fractionating fatty materials which comprises subjecting a solution of the fatty material in a normally gaseous hydrocarbon solvent to temperature and pressure conditions to cause a separation of a heavier liquid phase containing impurities and a lighter liquid phase containing decolorized fatty material, separating said phases, reducing the pressure to Vaporize a portion of said hydrocarbon from the lighter liquid phase while supplying heat to avoid cooling below about 100 lF., chilling the decolorized fatty material by vaporizing a further quantity of the normally gaseous hydrocarbon to a temperature suiciently low to crystallize the higher melting constituents of said fatty material and then filtering the mixture to separate said higher melting point constituents.
FELIX E. LACEY. WILLIAM M.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,974,542 Parkhurst Sept. 25, 1934 2,118,454 Schaafsma May 24, 1938 2,281,865 Van Dyck May 5, 1942 2,288,441 Ewing June 30, 1942

Claims (1)

  1. 6. A PROCESS FOR REFINING AND FRACTIONATING FATTY MATERIALS WHICH COMPRISES SUBJECTING A SOLUTION OF THE FATTY MATERIAL IN A NORMALLY GASEOUS HYDROCARBON SOLVENT TO TEMPERATURE AND PRESSURE CONDITIONS TO CAUSE A SEPARATION OF A HEAVIER LIQUID PHASE CONTAINING IMPURITIES AND A LIGHTER LIQUID PHASE CONTAINING DECOLORIZED FATTY MATERIAL, SEPARATING SAID PHASES, REDUCING THE PRESSURE TO VAPORIZE A PORTION OF SAID HYDROCARBON FROM THE LIGHTER LIQUID PHASE WHILE SUPPLYING HEAT TO AVOID COOLING BELOW ABOUT 100* F., CHILLING THE DECOLORIZED FATTY MATERIAL BY VAPORIZING A FURTHER QUANTITY OF THE NORMALLY GASEOUS HYDROCARBON TO A TEMPERATRE SUFFICIENTLY LOW TO CRYSTALLIZE THE HIGHER MELTING CONSITUENTS OF SAID FATTY MATERIAL AND THEN FILTERING THE MIXTURE TO SEPARATE SAID HIGHER MELTING POINT CONSISTUENTS.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1000225B (en) * 1954-02-01 1957-01-03 Dr Hans P Kaufmann Process for the fractional extraction of lipoids from natural raw materials
US2848550A (en) * 1956-02-03 1958-08-19 Gen Dynamics Corp Code call circuit
US4048203A (en) * 1976-12-06 1977-09-13 Thomas Philip Purification of lutein-fatty acid esters from plant materials

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1974542A (en) * 1932-04-04 1934-09-25 Standard Oil Co Destearinizing fatty oils
US2118454A (en) * 1935-03-30 1938-05-24 Shell Dev Process for separating high molecular mixtures of the ester type
US2281865A (en) * 1935-03-22 1942-05-05 Shell Dev Process for separating high molecular mixtures
US2288441A (en) * 1939-05-19 1942-06-30 Frederick J Ewing Process for refining animal and vegetable oils

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1974542A (en) * 1932-04-04 1934-09-25 Standard Oil Co Destearinizing fatty oils
US2281865A (en) * 1935-03-22 1942-05-05 Shell Dev Process for separating high molecular mixtures
US2118454A (en) * 1935-03-30 1938-05-24 Shell Dev Process for separating high molecular mixtures of the ester type
US2288441A (en) * 1939-05-19 1942-06-30 Frederick J Ewing Process for refining animal and vegetable oils

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1000225B (en) * 1954-02-01 1957-01-03 Dr Hans P Kaufmann Process for the fractional extraction of lipoids from natural raw materials
US2848550A (en) * 1956-02-03 1958-08-19 Gen Dynamics Corp Code call circuit
US4048203A (en) * 1976-12-06 1977-09-13 Thomas Philip Purification of lutein-fatty acid esters from plant materials

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