BE580978A - - Google Patents

Description

       

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  "Process for the Separation of Mixtures of High Molecular Weight Organic Compounds".



   The present invention relates to new and useful developments in the separation of mixtures of high molecular weight organic compounds; it is a consolidation and a continuation in part of the American claims of the plaintiff, N 293,246 of January 13, 1952, N 379,289 of September 9, 1953 and 9 * 401,092 of December 29, 1953, all of these requests being currently abandoned.



   High molecular weight organic compounds such as fatty acids and esters of natural or synthetic origin are usually obtained in the form of mixtures, the components of which differ from each other by their melting points. Thus, fatty acids and esters are cha -

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 those obtained in the form of mixtures containing constituents / different melting points. It is generally necessary to separate these mixtures into components with different melting points for later use. This separation. hitherto offered certain difficulties, drawbacks and obstacles requiring the use of organic solvents, filtration or hydraulic presses, etc ....



   An object of the present invention is an improved process for the separation of mixtures of high molecular weight organic compounds, such as, for example, di-fatty acid mixtures and mixtures of carboxylic esters, into components exhibiting high molecular weight. different melting points.



   Another object of the present invention includes such separation without making use of organic solvents, hydraulic presses or filtration.



   The foregoing objects and still other objects of the invention will emerge from the following description in conjunction with the accompanying drawings in which:
Figure 1 is a schematic vertical section of one embodiment of an imperforate type centrifuge used in the practice of the invention,
Figure 2 and Figure 3 are vertical sectional views - schematic of other imperforate types of centrifuge baskets which are used in the practice of the invention - (the control, bearing and manifold elements fluid removal that has been omitted).



     In accordance with the invention, a dispersion of the mixture of the high molecular weight organic material is formed in an aqueous solution containing a surfactant material at a temperature at which the mixture contains

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 solid and liquid constituents. The dispersion is then separated by formation of layers into a specifically heavier phase, composed of the aqueous solution of the surfactant material containing suspended particles of the solid constituent, and into a specifically lighter phase composed of the particles. liquid constituents.

   The separation of the dispersion into these two phases is carried out by a centrifugal action, for example in a centrifugal separator of the imperforate type. The liquid constituents of the high molecular weight organic material mixture are straightforward: slowly recovered and the solid constituents can be recovered by separating the aqueous solution from the solid particles suspended therein.



   Raw salières suitable for the implementation of the invention. are mixtures of carboxylic esters and mixtures of fatty acids both of natural or synthetic origin. natural
The carboxylic esters / are mainly di-fatty acid esters, in particular glycerides such as those which are obtained from the fatty matter of plants, terrestrial and marine animals. Examples of the various types of vegetable fats are coconut oil, palm oil, olive oil, soybean oil, linseed oil, wood eight. and rapeseed oil.

   Examples of the various types of fat obtained from land animals are beef fat, pore fat, and bone fat. Examples of the various types of marine animal fats are whale oil, menhaden oil, cod liver oil, and herring oil.



   Among the natural carboxylic asters which contain alcohols other than glycerin as alcoholic constituent, mention may be made, for example, of sperm oil.

 <Desc / Clms Page number 4>

 
 EMI4.1
 W ..: 1ceti which, in addition to 2e glycerides, contains ga2.a.-r¯4: '3 strs wr.:.CIC.-¯. T33 7atcaols alinsties, as well as 23r2 :: S ^ .r'¯ ^ 'n c ..¯. .us des; lycrië2s on ?; ., a ilis: .r simmering desired combination of esters, pc: r ;; X> 3r.:p1.3 c = llcs 4 # 1 are used C3yti..C. 3ssu? 1sst st that D-- ot1r i! 4t: Gt iK113: .c? Nt.



  When the ni-langes of asti = -s c34ti..nent solid constituents and also liqnides to me terD, 3ra.,. = Es doan4 <, it is often important from an industrial point of view to separate the diaper into constituents to different points of, js: lon3, cosme by exempta in the reception of edible oils, the separation of hardened fats, the removal of solid constituents in sleepers and the separation of isomorphic phthalates, etc ...



  The mixtures of fatty acids of natural origin are those obtained from the ela = .ges of carboxylic esters of natural origin mzntioz-néa above. The crystals can be split with water or water vapor, or they can be saponified with caustic alkali, while :: ic1- :: ! s zras can be freed from the resulting sav s with acid aid. Mixtures of fatty acids o - i- 13 s; û h tiqac can be waters which are Jbtf-U3 for example by oxidation of natural 0'- synthetic paraffins and isolation of fatty acids from == 1a-ige of oxidation, or they can be obtained by oxidation of alcohols as is practiced by exermia in the hydrogenation of J.J'.3xyèe of carbon.

   We ? 3 and furthermore obtain the synthetic mixtures by o: r ;, Tdî, tio; of L4 VV which are obtained by adding carbon monoxide t hydrogen to ol.é: f1n ::: s, which leads to j. des .cr; l.3 - "! caa of fatty acids suitable for sa? .¯-atior¯ by the application Process set in accordance with l.'1nvet1on.

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   -directs
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 The fatty mixtures to be treated CJr: fXL: e: Le.'1t to the present invention may preferably c-rten: L-coz-ae main constituents of fatty acids with 8 to 30 and preferably 10 to 25 carbon atoms in their molecule.
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 If the ester mixtures contain fatty acid radicals as carboxy constituents, these radicals can be derived from fatty acids of the same molecular dissension.



   All the materials mentioned above are generally obtained in the form of mixtures containing
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 constituents with different foslon points. These dobbies are of indn8tr: u.e importance and it is generally necessary to separate the mixtures into components with different melting points for subsequent use *.



   The invention is not, however, limited to
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 Specific langea listed above, it is applicable to all xioal mixtures, whatever their origin or whatever their process of obtaining, this being obvious
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 for the professional homie, since the separation is of a physical nature. To obtain the dispersion it is possible to
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 from a summer mixture of years completely liquid organic matter. to a more or less solidified mass.

   In the application of the new process it is necessary that the organic mixture to be separated is present under a condition that the aqueous solution of the surfactant is able to substantially displace the liquid organic substance from the surface of the solid component. .. If the material
 EMI5.7
 The first is a more or less solidified r.éîazrge, it is necessary to subject the mixture to a relatively fine grinding, for example by treatment zecar-iquap notam. 412.l1 t by passing the mixture through sieves, using stirring devices, cylinder presses, emolifica-
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 tears, ball mills, spiked, hammer, dia-, gear uea, disc d,

  $ Impact or other devices

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 I grinding or stripping or spraying 2a devices.



  After this ¯reduction of i..aio :: the solid zsnllituents of the mixture appear below the level of substantially small, distinct particles, that is, individual unbound particles.



   When using substantially molten mixtures of organic material, this is preferably allowed to partially solidify first. He is
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 advantageous to cool the mixture to rma tecnperatare at which the separation is to be carried out. These mixtures can be solidified while they are at re-
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 pos on while qU 'à1B are p1.aB O1I> 3mS 8: I: ".. BLtYe:' elIt. With a view to solidification tranqa * ille) le: n ..: = J.an!; ef: ndl1 can be poured into mold forms from which they are removed after their solidification or solidification by-
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 tial, this mixture then being so = is a reduction in size, in the manner described above.

   he is also
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 possible to pass the suhsta. ^ ¯tielleent iiqnl- des mixtures; that is to say melted, on cooling cylinders
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 In this way, this mixture is formed to solidify while it is substantially at rest on the surface of the cooling cylinder. The conch of the substantially solidified mixture is detached from the cooling cylinder.
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 ment, then it is crushed as described above. He. It is also possible to allow the substantial mixture to cool down in suitable containers while it is
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 is subjected to stirring or agitation.

   For this purpose, for example, a cooled tube of 1. ' outside: - <'"... 2" 15 which the layer of constituents mixed with the solidification path which deposits on the walls of the tube is removed by a scraper or scraper.
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 Solidification can be done 1.entem.ent,

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 that is, in the space of several hours, well it can be done relatively quickly, for example in less than a minute. It can also be carried out in the presence of added substantially liquid organic compounds, such as hydrocarbons, alcohols, esters or carboxylic acids.

   Preferably, substantially liquid organic additive materials are used which are relatively easily removable from the constituents of the organic compounds to be obtained, owing to their physical properties such as solubility or the boiling point. The substantially liquid constituents of the mixture obtained in the mixture are obtained in the mixture. Carrying out the process followed by the invention are especially valuable as additives according to this embodiment of the invention and their addition is particularly advantageous in cases where the mixture to be separated contains relatively few liquid components. The use of the last mentioned additives offers the further advantage that it substantially eliminates the need for separate recovery of the additives.



   The dispersion of the mixture in the aqueous solution of the surfactant material can be effected by adding the ground mixture. to an aqueous solution of the surfactant material or by adding the surfactant material to the mixture before, during or after grinding. The surfactant material can of course in the same way be added at the same time as the ground mixture is dispersed in the aqueous solution. In all cases the end result will be a dispersion of the mixture in an aqueous solution of the surfactant material. In this connection it will be especially noted that the result is an oil-in-water emulsion and not a water-in-oil dispersion.

   In forming this oil-in-water dispersion, the substantially liquid organic constituents of the mixture are displaced from the surface of the substantially solid organic constituents of the mixture forming a dispersion of fine particles in which the constituents.

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 Liquid and solid killers are separated from each other in the solution of the surfactant.



   The dispersion in the aqueous solution can be effected by shaking, stirring otherwise intimate contact between the organic mixture and the aqueous solution was ensured.



   In many cases, apparatuses such as homogenizers or emulsifiers of conventional construction should be used for this purpose. It is frequently possible to effect a reduction in size of the organic mixture) as well as, if desired, the addition of the substantially liquid organic materials, together with the dispersion of the aqueous solution mentioned herein of the surfactant into a mixture. single operation.

   Another modification of the process according to the invention comprises incorporating an aqueous solution of surfactants into the mixture substantially. molten organics to be separated and cooling the mixture while it is mechanically working. This mechanical work can for example be carried out in the same way as described above for the cooling of the substantially molten mixtures or for the production of the dispersion. In this way it is possible to obtain the substantially solid organic component of the mixture in an especially fine distribution state.



   Surfactants are intended for. reducing the interfacial tension between high molecular weight organic material and the aqueous medium. Therefore, any known or conventional surfactant material can be used. which is chemically inert to the other constituents in the dispersion. Surfactants are organic compounds which contain hydrophobic and hydrophilic groups in molecules.

   Hydrophilic groups or

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 EMI9.1
 Suitable hydrochloric acid are, for example, multiple free hydroxyl groapes, polyether chains, polyether groups or synthetic semi-esters, and the like. ** Examples of suitable surfactants are Dm alcoylpbé.noJ.po.1.yg1.ycolether, alcoyienifonatey, fatty alcon sulfate, α2coylreazèe-salfonate. Examples of surfactant salt shakers having hydrosolnh11.1 acidic groups are a1.cOy1.benzene-suJ.t'onates, alcohol sulphates, aÎCOyl8UÉfOnates, monoglycerides of fatty acids sU1: tates and soaps, including caapris soaps in particular organic base such as mono-, di- or tr1éthaPo1.a: dne. Surfactants having basic water-soluble groups are known as catalytic compounds.

   Particularly important are the substances of this
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 type which contain quatermirep nitrogen atoms for example dalcoy2pyrid: bii =. Ri. As examples of surfactants having non-saline-forming hydrosoinbilizing groups, mention may be made of the alkylene oxide adducts of high molecular weight compounds having a mobile hydrogen atom, for example polyglycol ethers of Alipmtic alcohols or deatcoylphenolsl, as well as palyaycoiiqaes esters of fatty acids. The surfactants which can be used according to the invention are of course not limited to those described above; we can
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 use any of the conventionally known agents, such as, for example, those described in auvr-sosnrface Active Agents "by A.M, Schwartz and I.W.

   Perry, N "ew-York 2-9493," Encyc1.opaCliA of Surface Active Agents "by J.P. Sisley and P.I.



  Wood ,, N "e.w-York, 1952, Surface Active Agents" by C.B.F. Youp, g-¯and K.x. Coons, Brooklyn, 1945, and A. Chwala "Textilhüfsruittale Vienna 1939, as well as 1.'U.S.P. 2.fi.a? 8.



  When the organic mixture to be separated is m scratched

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 mixture of fatty acids, relatively small amounts of basic-reacting salt shakers can be added to the mixture of fatty acids, resulting in relatively small amounts of fatty acid salts which are obtained. can serve as a surfactant in accordance with the invention. Surfactant materials can also be formed in this way for the treatment of ester mixtures, particularly natural fats which may contain some. amount of free fatty acids.



   The amounts and concentration of the surfactant material to be employed depend in each case on these surfactant properties. In general concentrations of at least 0.05%, and preferably about 0.1 to 5% of surfactant material based on the weight of the aqueous medium will give good results.



   The properties (interfacial activity) of the aqueous surfactant solution can be influenced by the addition of electrolytes which are inert to the other constituents of the dispersion. Electrolytes are frequently present in the form of sodium sulfate or of sodium chloride, in technical surfactants. Further, other salts such as magnesium salts, calcium salts or aluminum salts are suitable as additions. The action of the addition of electrolyte to the solution of the surfactant is, however, not limited to specific descations such as alkali and alkaline earth metals, nor to specific anions such as chlorides, sulphates or nitrates.

   Electrolytes which prevent corrosion of metallic matter, for example nitritas and salts of phosphorus acids which contain less water of constitution, as well as orthophosphoric acid, can also be of importance. than any desired mixture of these electrolytes. The fact that the action of the addition

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 electrolyte is not specific to alkaline or alkaline-earth salts, for example, emerges from the fact that the same effects are obtained in particular by the addition of nickel chloride.



   It will be understood, however, that salts which form substantially insoluble precipitates with the surfactant material will not be used. The amount of aqueous solution of the surfactant material used is preferably kept in the range of about 0.5 to 5 parts by weight of water per part by weight of the high molecular weight organic salt shaker mixture.



   In addition to the wetting action of the aqueous solution of the surfactant material which wets the surface of the individual particles of the organic material and displaces the liquid particles which adhere thereto, the aqueous solution has emulsifying power. The emulsifying power of the aqueous solution should not, however, rise too high since, in this case, the emulsifying effect would be too strong to the point of causing difficulties in the subsequent separation of the particles of liquid and solid organic matter. requiring an: excessive amount of time.

   Thus, if for example the particles to be separated are introduced into a centrifuge, while there is an excessively great power in the dispersion, the centrifugal separation requires an extremely long time and a correspondingly small flow rate will be obtained in the mixture. centrifuge. In some measure the ratio of wetting power to emulsifying power of the aqueous solution of the surfactant material is controlled by the nature and amount of the particular surfactant material chosen; it can also be controlled to some extent by the addition of electrolytes and / or organic solvents.

   However, in accordance with a preferred embodiment of the invention, additional

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 EMI12.1
 ment of the co11J ± of the protectors to the aqueous solution of the = :: tsnsioaetive. We have found Ci:.!;: These protective colloids are particularly effective by favorably adjusting the ratio of moisturizing power - emulsifying power of the acid phase by allowing the concentration of the surfactant material to be maintained at a ui obtaining a: lnsi a emollifying effect is not mTmr. Therefore, with 1- * addition of the protective agent, a reduction in the concentration of the surfactant in the aqueous solution is possible while allowing at the same time an effect
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 mott1Uan.t sufficient $ while nevertheless substantially reducing '8: f. "and emulsifier.



  Leexpressionnoolloldas protectors; is accepted herein and in the claims to designate substances.
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 those metals and organic which are soluble,> 2nacittbles or able to swell in the air, and which are able to increase the viscosity of the aqueous phase. The mineral protective colloids consisted of a: large noathra of mnc1.laginous precipitates or flocts which freqzemmmt of-
 EMI12.4
 die in suspension in colloidal form in 1, * aau / which
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 settling only slowly. Examples of mineral protective colloids are arg: u'3S zonilants, silica m: tcrocr1stalms and other materials which remain in suspension.
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 -7 couo1dale in the water where it is only -ii4 * seated.

   The
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 Completely soluble compounds in 1-> water> coma, for example the salts of phosphoric diacids poers, also contain # ant for i '3rnre: tioiz. The protective gold cs2lodes can be natural to synthetic.



  Glue, gela texts or other proteins) gozme adrac2mt and pectins, alginates, etc ... are exaiaplas of pro.t.?ctaurs darifb xmtnreug colloids. Synthetic organic colloids include polyethers.

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 EMI13.1
 glycoliquss Waxy liquids with high pol. ± molecular, poyacry1aes, ceilulosi glycolates, .ethylcelluloses) etc ... The <es sabsta ,,. cs colloidal properties can be regulated by nos.brn Jà cuts hydrosolubilisants present in los molecules and. by the non-hydrophilic functional groups which are -galbent optionally-
 EMI13.2
 ment present. as examples of :: Dmposés contained in these groups, the copo3.yras of metacrylic acid and the metacrylates as well as the glyealates of ethoxycellulose.

   We: n.ant1onIlsra en oatn lis condensate products f'orma1.dah; 'diques de phenols, de WÍ1 aMiT1 or d'srée, partic: J1.ièrS;: slow when it comes to uncured condensates which contain hydrosolub: l1.1sants groups in J80J.Q.cule, for example sulphuric groups.



  In general protective colloids which contain f1bateJrB groups of salts in nolecnlea are of particular importance. The concentration of protective colloids in the aquause phase can vary within
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 wide limits, concentrations as low as 01.1% being effective, while concentrations as low as 7% by weight are permissible.



   The optimum amount of surfactant material,
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 organic liquids, electra 4es and protective colloids, as well as the finesse of the drafting
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 of size and nature of the treatment, with the aqueous solution of the surfactants, can be easily determined.
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 undermined by pre3.iBCinairas trials.

   By varying the operational cogitions
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 Com :::.:! the nature and the method of cooling, the separation temperature :, the nature and the quantity of the organic compounds
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 ques liquids or: their added mixtures, one pa'at 1 = 'lt2erLeer both the consistency of the zéla; è to separate and the composition of the solid constituents ct liquidas.

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  In some cases it may be necessary to carry out the separation of the organic mixture at temperatures lower than onc, for example for the 1-hibc-r-r-ation of edible oils. In such cases, we must add
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 substances which reduce the Cûn5éa't3Tt point of the aqueous solutim of the surfactant material. Inorganic electrolytes are only suitable to a limited extent for this purpose. It is preferable to use anti-
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 gel. convention.1omme1..s such as polyvalent alcohols or hardly volatile derivatives such as ethylâ2e glycol, glycerin. polyglycery, polyglycols or their esters part1a1.s.

   The separation of the dispersion of the gold mixture
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 ganique in. the aqueous removal can be effected in some cases simply by allowing the dispersion to stand;
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 in lOCCtnnu1 This the upper phase of the liquid portions of the organic mixture forms together with a lower phase containing the aqueous solution with the particles.
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 dispersed solid component of the organic mixture. by decantation of the layers, the products can be recovered very simply.



     In accordance with the preferred embodiment
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 However, the dispersion is separated into layers by centrifugal action. For this purpose we used
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 Imperforated type centrifuges, namely those in which the outer walls of the bowl cen: tr.1.f '± tpDr'- oU- dtt centrifuge basket sant full, unlike the 8AnBea type / perforated contrifuge in which the walls of the cen-tri-% 0% PO <the walls of the centrifuge basket are perforated oc otherwise peaaéab2.es. Therefore, in the imperforate type centrifuge the solid phase is not retained by means of a sieve, screen or filter; the two phases are

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 separated 1 - * = c from each other in the centrifuge due to their density.

   By using the centrifuge, the
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 layering of the dispersion which p-nt5, in certain circumstances going very slowly or not doing everything, can be considerably accelerated.



   The drawings give examples of illustrated embodiments of centrifuge or bowls or baskets
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 Controllers usable in the implementation of the process sulvant 2 'invention for the centrifugal separation of mixtures of organic materials conaae mixtures of fatty acids or mixtures of carboxylic esters; we don't want all-
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 JL. fo1S!]. ter]. ' application of! 1VeaU process to types by-
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 centrifuge tie-bars or centrifuge basket shown therein,
Referring to the schematic representation of the interior of the centrifuge basket like that shown in Figure 1, the centrifuge basket 1 is mounted on a
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 tree 2.

   During the operation of the centr1fugeus e, that is to say during the rotation in the direction of the arrow 2, is first added preferably through the line dJ-a: Umentat: 1on an aqueous solution., tenB1oactive substance, which does not contain a mixture of organic materials such as a mixture of fatty acids, esters or da1.c () o1.s.

   It is advantageous to allow the layer 5 of l3qaida specifically heavier to accumulate (even if the level exceeds): op6 # annular aa opening defined between 1-t ring: z. and the outer wall 4 of the centrifuge basket 1. The substantially contlnue mixture of this solution without organic mixture is set at an addition rate which
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 is the same as that to which this solution is discharged continuously through the withdrawal conduit 8, which ensures the complete immersion in the liquid of the annular space 5a.

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   The supply of the tersioactive aqueous solution containing the mixture of dispersed organic material is then switched on. With the continuous feeding of the dispersion,
 EMI16.1
 the aqueous solution containing solid particles, specifically p1.wr heavy, builds up against the outer basket wallg 1, while the substantially liquid organic materials, specifically lighter, form an inner layer superimposed on the outer basket. specifically pi-os heavy with liquid.

   As the Inner layer of substantially liquid organic matter settles down, an equilibrium is finally established with the outer layer, which can finally take for example the position of layers ¯5 and 6 (figure 1), the internal having accumulated until reaching the inlet of the draw-off duct 9, the acids
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 Greasy schstantiett fmant liquids are then continuously discharged out of the last-mentioned withdrawal duct, while the aqueous dispersion of the particles substantially
 EMI16.3
 tier3.ement solids is continuously discharged through the withdrawal duct 8.

   The ring member z prevents the specifically lighter phase from entering the space above the ring member.



   Figure 3: shows the centrifuge body
 EMI16.4
 12 which is essentially of tubul.a1re construction and which is provided with the feed duct It allows the dispersion to pass into the interior of the centrifuge from its bottom. After introduction of the dispersion: in accordance with the invention through the feed line Ut, this is separated into the specifically heavier phase and into the specifically lighter phase as indicated above. In this case the two phases can for example constitute the two conches indicated in Dotted lines and designated by
 EMI16.5
 the numbers and the.

   In the upper portion of the

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 centrifuge, the two phases are prevented from interfering with each other in their separate discharge from the centrifuge
 EMI17.1
 by the disc we organize a: nu3.aire, 4. The latter is preferably mounted on the tubular member 17 and defines with its outer edge the annular space or opening 12a for the specifically heavier liquid passage in the space above the disc member 14.

   Likewise in this case, it may be advantageous to start the operations by first using an aqueous surfactant solution which does not contain any mixture of organic matter, including
 EMI17.2
 one which may come from a previous separation and containing only the solid particles which are substantially dispersed, by continuous addition of the aqueous surfactant dispersion of the mixture of organic material into the material.
 EMI17.3
 from the centr1.f'ttgeuse to the trojan of the feed line 1, separation into the specifically heavier phase and into the specifically lighter phase occurs,

   which leads to the separation of layers Indicated by the numbers 12
 EMI17.4
 and as indicated above, the layer 1.2 passing contittually through the annular space 12a in the portion above the disc or annular member to and from there into the tubular member 15 to be discharged through the duct 1.9-As the inner layer 13 of liquid specifically lighter (eaccil = -t3e) this is finally discharged continuously through the interior of the tubular member II and through the conduit 18.



   Figure 3 shows urn another variant of cen-
 EMI17.5
 tr1: fugause usable in the implementation of the invention.



  The centrifuge body carries at its upper end an extension of smaller diameter 24 provided with the discharge opening 25. The large centrifuge body
 EMI17.6
 d1amàtre 1Jl is provided at its upper end with 1. ' OD-

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 EMI18.1
 discharge opening 2. The operation of this centrifuge is substantially the same as that depicted in figure 2, the dispersion of organic material being
 EMI18.2
 fed to. 1. ' interior of the centrifuge, -, se by means of the duct dl a1.:Imentat1on go, being separated here into the specifically heavier and lighter layers t 23, which are then discharged separately respectively at = yen of the discharge otzvert.ures, go and 25.

   When using this construction, care must be taken, unlike the constructions illustrated in Figures 1 and 2, that the quantity of dispersion which passes into the centrifuge by means of the supply duct 20 is sufficiently large to ensure an appreciable distance from the centrifuge. 'interface between layers 21 and 22 with respect to the respective openings
 EMI18.3
 3 # and 25. It is also possible and in many advantageous cases, partly for greater efficiency, to use conventional sets of plates or discs in the centrifuge.



   In some cases there. should allow the dispersion to flow into the centrifuge so as to
 EMI18.4
 avoid as much as possible a farte acceleration and / otx a strong turbulence. In most situations, however, this is not necessary.



   For the case where the density of the substantially solid organic constituents of the separated dispersion
 EMI18.5
 According to 1.1nvent1on lies between the density of the aqueous solntiou or the surfactant substances and the density of the substantially liquid organic constituents, it should be expected that, when centrifuging the dispersion, the substantially solid organic constituents pass partly in solution, aqueous and partly in the substantially liquid organic components.

   In this

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 Eventuality the densities of the individual components of the mixture should be expected to cause an intermediate layer composed of a mixture of substantially solid and liquid organic components. Centrifugal separation of an organic mixture in a substantially continuous operation would then become
Impossible because such an intermediate layer would become larger and larger by continuing to feed new quantities of the original dispersion of the organic material mixture, which eventually causes the discharge of a mixture through the individual outlets to the instead of the separated organic constituents.

   Surprisingly, however, such a difficulty is not encountered, so that it is unexpectedly possible to continuously subject a dispersion of a mixture of organic materials to centrifugal action and to continuously obtain substantially complete centrifugal separation. of the entire dispersion into the individual substantially solid and substantially liquid organic constituents. Small amounts of relatively low boiling point solvents which may be contained in the liquid organic constituents after separation can normally be readily removed by heating.

   The substantially solid organic constituents can be recovered from their aqueous solution or dispersion by any suitable means such as, for example, filtration by heating the suspension to temperatures above the melting point of the substantially solid constituents. The aqueous solution of the surfactants can be reused for the preparation of further quantities of dispersions of mixtures of organic materials to be separated in accordance with the invention.



   The properties of the resulting substantially liquid or substantially solid organic constituents

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 EMI20.1
 des, and especially the point of solidification or tiarbidity of the liquid and the melting point of the solid constituents, are a function of the ter.rperat: 1st at which the working and separation of the mixture takes place.

   After separation: addition of the constituents of the mixture It is furthermore possible to repeat the steps of the separation process according to the invention, the solid constituents separated being worked up at a higher temperature and the liquid constituents separated at a higher temperature. low. In this way we
 EMI20.2
 obtains an eternal fractionation of the melting and solidifying powers of the products, and it is possible to recycle the intermediate fractions to the starting material.



   The solvent examples are given to further illustrate the invention and not to limit it. In
 EMI20.3
 In some examples the iodine number is given for identification instead of the solidification point. This measure was adopted because on the one hand the solidification point is a function of the degree of saturation and, on the other hand,
 EMI20.4
 the iodine number indicates the different separation effects more noticeably than does the solidification points.



  MM-UME 1, 'One fatty acid' and tallow (3'acid number 205, saponification number 206, iodine number 59) is pressed at 22% through a disc impact mill using feed ur worm, then press it out. through a cria sieve. The acid is then stirred intensely
 EMI20.5
 at the same temperature with half by weight of an aqueous solution containing 0.5% by weight of sodium salt 1n # of fatty alcoal sulfate with a shear of carbonated carbon in -C Z4 exr weight of sodium chloride and 0% by weight of rfaaS04 ,.

   The resulting dispersion of diacid particles

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 EMI21.1
 Substantially solid and liquid fat in the aqueous solution is then separated by centrifugation in a centrifuge.
 EMI21.2
 trifngeuse coatinne operation of the 1mpêrf'oré type provided with withdrawal conduits for two specifically different constituents, and having a diameter of about 30 cm. The centrifuge operated at about 3000 taurs per minute. Centrifugal separation produces oleic acid.
 EMI21.3
 (8d iodine number on one part, and a suspension of stearic acid in aqueous sJ1utàom on the other part. On heating at 80 ° C., the suspension of stearic acid gives a layer of sos .. and stearic acid. liquid (index ('ioda 10,) ine 1'on soutîre.



  a liquid substat1eJ.J. mixture composed of 80% by weight of tallow fatty acid (solidification point
 EMI21.4
 29.8OC) and 2Kl% in. weight of material oJ.é1qne obtained as described in eexample 1, is subjected to cooling substantially cont: flm from 40 ° C to 10 C, thus obtaining a pulp or fat relatively. liquid penalty.

   For this purpose an externally cooled tube is used in 1que1. rotating radials continuously loosen solidifying gm-e acid constituents from the inner surface of the cooling tube. A good dispersion of this fat is obtained, quaed oefigite with the same amount by weight of an aqueous solution at + 1o C which contains 0.5% by weight of BOd1tm se1 of a fatty alcohol s \ l1: tate with a length of carbon chain in Cj-Cu 3% by weight of r, 3.torura of socH: t! # and 0.5% by weight of by ess2tr3itgëage of this dispersion at ma # at temperature in a centrifuge of the type t: nper:

  ror4, provided with sout1rage conduits, cam is given in particular as an example in the schematic representation of Figure i, we obtain a. oleic acid with an index of 6. ' iodine 83.2 and

 <Desc / Clms Page number 22>

 a solidification point of 8.2 ° C. (the oleic acid used in the examples denotes a product consisting predominantly of 1-oleic acid, but which contains, as appropriate, other unsaturated fatty acids). The centrifugation further results in an aqueous suspension of stearic acid which, after its separation, is heated to about 52 ° C. and then cooled while stirring to 46-47 ° C. over the course of about one hour.

   This dispersion is again subjected at the same temperature to centrifugation in a centrifuge of the imperforate type with withdrawing ducts, thus obtaining a fatty acid having an iodine number of 27.1 on the one hand, and an aqueous suspension of stearic acid, on the other hand, from which by (heating at 80 C there separates a stearic acid having an iodine number of 5.1 and a solidification point of 53.1 C.



   The oleic acid material obtained in the separation process at 10 ° C is mixed with the same amount by weight of aqueous solution of which the stearic acid was. removed and the mixture is cooled with stirring to a temperature of -3 C. After that the resulting aqueous dispersion of fatty acid is centrifuged in a centrifuge of the type described above having an imperforate basket, the centrifuge being in operation. at the same temperature as that to which the mixture was cooled. By this means the oleic acid material can be separated again into two components having solidification points of +20.8 C and -5.3 ° C, respectively.



  EXAMPLE 3. -
A substantially liquid tallow fatty acid (solidification point 38.2 C) together with an equal amount by weight of an aqueous solution containing 0.1% by weight of the sodium salt of a fatty alcohol sulfate with a

 <Desc / Clms Page number 23>

 
 EMI23.1
 chain length of Cg-CU "0.3% by weight sodium chloride: and 0.1% by weight codiom sulfate, is cooled while stirring from a temperature of 40 C to 20 C.

   The resulting dispersion is subjected to centrifugation in
 EMI23.2
 a laperforated type centrifuge, an example of which was given above, the basket of the centrifuge consisting of a
 EMI23.3
 elongated cylinder (diameter z5 cm, number of revolutions per minute 1000): centrifuging results in a liquid constituent comprising rscbstantie2lement. mainly oleic acidic material (iodine number 79); the substantially solid particles suspended in the aqueous solution are separated from the aqueous phase by heating to about 80 ° C. (solidification point 50.1 ° C.).
 EMI23.4
 



  : E: XEMPt & 4.-
A substantially hardened whale oil fatty acid (acid number 198), saponification number 203 ioda number 42, solidification point 39.0 C) is ground. between rapidly moving knives at a temperature
 EMI23.5
 from about 0 C until a pulpy or fatty consistency is obtained, the resulting product then being vigorously stirred with the same amount by weight of aqueous solution having substantially the same composition as indicated. in example 2.

   The resulting dispersion is then subjected to centrifugation in the
 EMI23.6
 same type of centrifuge 1mperlorée indicated above, this one being however provided in this case with a set of dis-
 EMI23.7
 conventional ques (centrifuge diameter 11 cur., number of revolutions per minute 10.000). The fatty acid snbsta :: rt1e11.ElnSnt. solid recovered from aqueous solution after centrifugal separation has an iodine number of 16.2 and a
 EMI23.8
 so: l1d1f'lcat, ion of 4S, 3 C.

 <Desc / Clms Page number 24>

 
 EMI24.1
 



  EXSrw # J: rE 5.A fatty acid of partially hardened sperxaceti oil (acid number z saponification number 211, iodine number 6t! Solidification point. 45,; OC) is treated at +10 C with an aqueous solution having the composition described in Example 2, the treatment being carried out as indicated in Example 2, after which the resulting dispersion is separated By centrifugation using a centrifuge of the type
 EMI24.2
 lmperford as for example specified in Example 1 and provided with withdrawal conduits.

   The separated substantially liquid constituents have an iodine number of 71 and
 EMI24.3
 The solidification point of 14> 50Cl while the substantially solid constituents have an iodine number of 28 and a solidification point of 44.2 C.



  EXAMPLE 6. -
 EMI24.4
 th fatty acid prepared to synthesizece: t, obtained by oxidation, according to Fischer-Tropsch -Catsch (Index
 EMI24.5
 of acid 2t?, saponification index. 226, iodine number 21, solidification point 39.6 C) is heated to approx. 50 C.



  After addition of about: 5% by weight of methanol, the heated fatty acid mixture is cooled while stirring: Slowly at a temperature of +20 C, together with 5 times the amount by weight of the fatty acid of an aqueous solution containing
 EMI24.6
 1 ive by weight of soniss salt of a technical a1.coy1.benz Ème-stJ1.f'ona te containing 30% salt. The dispersion thus obtained is then subjected to centrifugation in a centrifuge of the plate type or disc type of the waterproof basket.
 EMI24.7
 drilled (diameter 11 cm, number of revolutions per minute 1o, 00p) after which one obtains a substantially liquid fatty acid, on the one hand, and a substantially liquid fatty acid suspension
 EMI24.8
 solid in aqueous solution, antepart.

   After separation of methanol. residual fatty acid substantially liquid

 <Desc / Clms Page number 25>

 has the following characteristics: acid number
 EMI25.1
 2ei, saponification number - .38, iodine number 35, solidification point 26.3 OC. The fatty acids substantially separated from aqueous salt by extraction and have the following characteristics: acid number 198, saponification number 199, number
 EMI25.2
 iodine 10.8, solidification point 52 2 C.



  EXAMPLE 7.- oil
A fatty / fish acid (Acid number 196,
 EMI25.3
 saponification number: 196, iodine number 216 solidification point 27.9 C) is heated to a temperature of 30 C and then it is cooled to a temperature of +6 C while stirring Coajo1ntOOlSIlt with the double quantity by weight of mre aqueous solution containing 5% by weight of au polygly-
 EMI25.4
 coléther tens1oactit 'and 10% by weight of magnesium sulfate.

   The dispersion obtained in this way provides after
 EMI25.5
 separation in a centrifuge of the 1m type: per: drilled (as described in Example 3) a substantially liquid fatty acid (acid number 191, saponification number 195, index
 EMI25.6
 of iodine M3, solidification point -0290C) and naked seispeusion of fatty acids snhstantieUe41e ::: t solids in the solution being aqueous, the fatty acids / separated from it by heating,
 EMI25.7
 (characteristics of the solid snbstaat1en fatty acid obtained: acid number 201, saponification number 205, Iodine number 69, solidification point 40.8 C).



  EXAMPLE 8. -
A fatty acid of cottonseed oil (iodine index
 EMI25.8
 87t solidification point +334 C) is reacted in the space of 10 hours while stirring from an initial temperature of about 40 C to. a temperature of +3 C together with an equal amount by weight of an aqueous solution containing 0,, S% by weight of se1 of m: a '? él.s1tm: d "a

 <Desc / Clms Page number 26>

 C9-C11 chain-length fatty alcohol sulfate and 5% by weight MgSO4.

   The resulting dispersion of substantially solid and substantially
 EMI26.1
 liquids.: then pass. in a conventional emulsifier, the tesperatore in this case amounting to about + 7 ° C, temperature at which the dispersion is subjected to centrifugation.
 EMI26.2
 g7st, pa,: have an imperforate type centrifuge provided with draw-off c #s as shown in Example 1. The separated substantially liquid components have an iodine number of 117 and a solidification point of -0 , 9 C.

   Substantially solid fatty acids suspended in solution. aqueous solution are heated together with the aqueous solution to a temperature of about-52 C, the mixture then being cooled over about 2 hours while stirring at about 48 C, after which the resulting dispersion
 EMI26.3
 is subjected to centrifugation at the last mentioned temperature in a centrifuge of the imperforate type equipped with withdrawal conduits.

   In addition to the constituents of this latter dispersion which were substantially liquid at the
 EMI26.4
 last mentioned temperature (solidification point 47.1 ° C.) a suspension of substantially solid fatty acids is obtained in the aqueous solution, from which is separated by heating at about 80 ° C. a fatty acid having an iodine number of 28 and a solidification point of 5l, 6 C.
 EMI26.5
 



  EXE: KPLE 9. A rapeseed halle fatty acid (solidification point 18.6oc) is dispersed in the same manner and in use is the same aqueous solution of surfactants as given in Example 8. temperature after cooling in this case is however 0 C, with a rise in temperature
 EMI26.6
 erase after passage in 17 emul.s: if'icator at -r4 C.

   Centrifugation of the dispersion is carried out in a centrif'tlget1S e

 <Desc / Clms Page number 27>

 of the imperforate basket type, provided with withdrawal conduits at the last mentioned temperature, which gives a substantially liquid component having a solidification point of -1.5 C, and a substantially aqueous dispersion of fatty acids solids which are separated from the aqueous medium by heating to about 80 ° C. in the form of a liquid layer. The solid fatty acids that make up this layer have a solidification point: of 32 C.



    @
In a tallow fatty acid having a solidification point of 39.8 C and an iodine number of 52.3, dispersed with vigorous stirring: 1% by weight of a technical wetting agent consisting of a 28% solution sodium salt of: fatty alcohol sulphate with a chain length of C10 This mixture is cooled continuously to about 18 C in a cooling tube fitted with scrapers, until a sasse pulpy consistency. The mass is then stirred with parts:

  .es equal by weight of a 3% aqueous solution of magnesium sulfate. The result is a dispersion in which there are sieved particles of liquid and solid fatty acid separated from each other.



   The dispersion is then separated in an imperforate centrifuge with two continuously operating chambers, fitted with a separation disc. The lighter phase which is separated consists of liquid fatty acids and the heavier phase of the aqueous solution contains solid fatty acid particles suspended therein. The liquid fatty acid has an iodine number of 84.6 and the solid fatty acids obtained after melting have an iodine number of 17.3.

   The liquid fatty acid: solid fatty acid ratio is 52:

 <Desc / Clms Page number 28>

 
48.EXAMPLE 11.-
One kg of lard,: iodine value 50, solidification point 32.2 C, is stirred for a few utes
 EMI28.1
 at 20 C with the n # me amount of donkey wetting agent solution containing 0.5 μl of the sodium salt of an aliphatic alcohol sulfata with CJ chain length: .a-C14, bzz by weight dellta,> SO4 until the formation of a dîapersion :, This dispersion is passed through a filter sieve in rete-
 EMI28.2
 deny the non-dispersed portims of fat which may still be present, then centrifuged into tubes.

   After the centrifuging It separates 4: #, 2 kg of liquid fat (iodine value 6: solidification point +4,? OC) under light left foraM. The heavy bottom layer contains the so1.ut1on. of moun.1ant age. in which the fatty acids are in suspension, mainly in the upper part of this layer. By heating the solution a-
 EMI28.3
 queuse 11 .. separates 0.56 kg of solid fat than 1. ' it is removed (iodine number 37, solidification point 37, 3 C). EXAMPLE 12. -
 EMI28.4
 20 kg of the lard filled in is squeezed into the shaft and, at the same time, stirred v1gonrensecrent. 3. 2S C and passes it through a sieve in 50 kg of one soletim of wetting agent containing 3% of a tec1Jrlqt1s dsa2coylbenzene-su1.::tonate paste containing 30% salt and 2% 2aC ..

   The homogeous dispersion which forms, orsql1) is separated in a continuous skimming centrifuge, gives about 10 kg of a liquid fat (iodine number 63), from one part and an aqueous suspension of fat. solids (iodine number 34), on the other hand. The molten solid substances (approximately @ kg) which are deposited by heating the aqueous suspension are washed several times with water at 500 ° C. in order to remove all retained traces of contaminating agent as well as the liquid substances.

   About a kg of fat remains in the centrifuge as a dispersion,

 <Desc / Clms Page number 29>

 The centrifuge works in such a way
 EMI29.1
 that neither one occurs; farte acceleration nor turbulence of the ester dispersion: Introduced. This is achieved by lo-trûdaisant the dispersion in the center of a hollow conical fortage body rotating in the centrifuge., S s the internal surface of which the dispersion is conducted from the center of
 EMI29.2
 centrifuge towards its periphery and is thus continuously accelerated to peripheral speed.

   EXAMPLE 13. -
 EMI29.3
 08 kg of the saindoox mentioned in Example 11 and 0.2 kg of the liquid substances obtained in Example 1a are: melted together, cooled to 20 C over several hours, the mixture acquiring the consistency of thick paste, stirred for a short time with a
 EMI29.4
 equal amount of one! solution of oioolllant containing Os, 4% magnesium salt. of an aliphatic alcohol sulfate with a long chain in% -% as well as 6% of ligSO41, and one .1ntrodu1t in tl1beS '# ntrff'ugeurs.

   The separation of the dispersion at. Liquid in a discontinuously operating centrifuge gives 0.57 kg of liquid substance with an iodine number of 62, and 0.42 kg of solid substances with an iodine number of 41.



  EXAMPLE 14. -
 EMI29.5
 10 kg of spermacéti hall without spermacéti (: index of Ioda? Of melting point 3-? Or-) which was solidified after several hours of agitation at 0 ° C in a thick paste, still runny, and the issoie quantity of a solution of soft agent11.1an: t. consisting of 1CO g of 50% technical sodium salt of a. sulphate of aliphatic alcohol with lons, -,: r in chains in -C: t.4t 500 g of 16g04 2000 g of ethylene glycol and 7400 g of water are stirred for 1 minute at 0 C;

   the il paine liquida dispersion produced is then centrifuged in

 <Desc / Clms Page number 30>

   a solid-wall centrifuge operating in contins, at the same temperature. Separation takes place into liquid portions (4.5 kg, iodine number 80, melting point -3 C) and into an aqueous suspension containing the solid portions of spermaceti oil (approximately 4.3 kg, ode number 59, melting point 27 C). Part of the aqueous suspension
 EMI30.1
 ast heated to 100r- while stirring over 1 hour, then centrifuged again. The liquid portions that now separate have an iodine number of 70 and a blanket point of 8.5 C.

   The solid portions which still remain in the aqueous phase and which can be separated by heating the cage, have an iodine number of 35 and a melting point of 36 C.
 EMI30.2
 The dispersion is introduced into the centrifuge through a pipe placed so that the dispersion emerges in the vicinity of the centrifuge wall in a direction approximately, tangential to it and in the direction of rotation of the centrifuge with a speed approximately equal to the peripheral speed
 EMI30.3
 centrifugerase. In this way, strong acceleration and tnrbulence are avoided.



  EXAMPLE 15. - A mixture of 1 kg of spermaceti oil
 EMI30.4
 mentioned in 1'exeI: 1p: le 14 and on 1/2 kg of a wetting agent solution which contains 1% of sodium salt of us. Alcohol sulphate allphatic chain length in Sa4 'as well as dare to N'aOD4 and 5% N1C1.aast cooled while stirring slowly for several hours at 20 C to +2 C. The dispersion obtained is then separated in a centrifuge tubular at 0 C in two components.

   One of the constituents consists of 13S portions of spermaceti oil liquid at 0 C (0.63 kg, iodine number 77), while the other contains, suspended in the wetting agent solution, the portions

 <Desc / Clms Page number 31>

 solid spermaceti oil at 0 C, which can be separated by heating (0.33 kg, iodine number 57).



  EXAMPLE 16. -
Olive oil (iodine index 82, melting point +7 C) which has been solidified by standing for several days at 0 C, is crushed at 0 C by rapid cutting followed by pressing through a horsehair sieve to obtain a pasty consistency. 500 g thereof are stirred with the same amount of a wetting agent solution containing 1.0% of a technical sodium salt to 50% of a sulfate. C12-C14 chain-length aliphatic alcohol at 0 C; a flowable dispersion is thus obtained which is separated by centrifugation in a tabular centrifuge.

   The liquid portions which separate as a top layer (about 260 g) have an iodine number of 89 and a melting point of -14 C, while the solid portions suspended in the a- solution. gent wetting (about 320 g), which can be separated by heating, have an iodine number of 74 and a melting point of +10 C.



  EXAMPLE 17. The olive oil mentioned in Example 16 is cooled over 12 hours from +20 C to -5 C mixed with twice its quantity of a wetting agent solution containing 2% of a 50% technical sodium salt of an alcohol excess. C12-C14 chain-length aliphatic, 27, MgSO4, 82% water and 14% glycerin, then it is centrifuged in a tubular centrifuge. In this case the temperature is raised to +5 C.

   The liquid portions which separate as a top layer have an io-index of 87 and a melting point of -4 ° C, while the solid portions suspended in the solution of wetting agent have an iodine number of 79 and a melting point of +9 C.

 <Desc / Clms Page number 32>

 
 EMI32.1
 EXE1 # 'LE 18.- 500 g of lard are stirred (iodine value 47)
 EMI32.2
 for half an hour at 23 C with: The same amount of aqueous solution containing 5% of a. emulsifier n: tOitroglyc6ride tec1mique (eovirocE 14% soap, 4% free fatty acid., 6 p of saD, the remainder being glycerides of fatty acids consisting for 2/3 of:

   monoglycerides and for 1/3 in dig1ycerides). The dispersion formed is then treated according to
 EMI32.3
 in Example 11, which gives 165 g of liquid substances (iodine number 61) and 330 g of solid substances (iodine number 43).



  EXAMPLE 19.-
 EMI32.4
 500 g of u2x est4rlfication of noXYacat.iqu.9 acid and spermaceti ethnil alcohol, product which can be used tta: m # fabric softener (.od-code 44, solidification point llt6OC) are cooled in a 1/2 hour while stirring at +2 C with the same amount of an aqueous solution containing 0.75% dodecyl-benzyl chloride
 EMI32.5
 diétby1.-szmon 0.75% technical sodium alginate and 10% MgSO4, the resulting dispersion then being vented into tubes.

   The separation gives as upper layer 245 g of liquid esters (iodine value 54, solidification point +1.3 C) and, after heating the aqueous layer
 EMI32.6
 which contains solid esters in the state of suspension, 250 g of solid esters with an iodine value of 34 and a solidification point of 18.1 C. are obtained.
 EMI32.7
 EXAMPLE 3 & .. '.



   Two kg of coconut oil, having an iodine number of 9.3, are intimately mixed at a temperature of 20 C,
 EMI32.8
 ..have a melting point of P-5-C and a solidification point of at., 1.OC, with two kg of an aqueous solution containing p by weight of 50% sadistic sulfate. fatty alcohol

 <Desc / Clms Page number 33>

 
 EMI33.1
 having a chain length between C12 and 4 'which contains an additional 5% KgSC. Mixing is carried out with vigorous stirring. The mixture is sieved twice through a spread to give a barely liquid dispersion. that we centri-
 EMI33.2
 fuge. Following centrifngoffl there is a slight peaks liquid fatty phase and a heavier phase consisting of the aqueous phase containing the solid constituents.

   Both
 EMI33.3
 constituent are ohterms in pure form by heating and washing. The liquid constituents have an iodine number of 11.5 and a solidification point of 17 9 C while the solid constituents have an iodine number of 5.3, a solidification point of 25.7 C. , and a melting point of
 EMI33.4
 29 C. The liquid: solids ratio is - is an excellent 70:30. Separate solid fatty constituents / coconut butter substitute.



    EXAMPLE 21.-
We treat x kg of hardened coconut oil, having
 EMI33.5
 tn iodine number of 0 and a solidification point of '2: 1.2OC with a solution of wetting agent at 3O C of the 1st described in 1-'example 20 and centrifugal arT in 1T. the centrifuge dn type of laboratory. Approximately 1.1 kg of the liquid fatty constituents separate, with a solidification point of 18 C.



  A part of the remaining dispersion of the solid fatty constituents (solidification point 31.1 C) in the aqueous wetting agent solution is heated while stirring at 30 C,
 EMI33.6
 or stir for 2/2 hour and centrifuge non-calf in glasses preheated in the centrifuge. A further separation is linked with 15% liquid fatty constituents which separate (referring to the solid fatty constituents separated at 20 ° C). Solidification of constituents
 EMI33.7
 liquids in the separation at 30 C is at 28.3 C and that of the solid constituents is at 32.9 to.

 <Desc / Clms Page number 34>

 



  EXAMPLE 22. -
Unrefined palm oil is continuously cooled in a scraper cooler from 45 to
C. The scraper cooler consists of a 16 liter capacity tube cooled externally and provided with rotating scrapers which move in the vicinity of the wall.



  Palm oil is pumped through this tube at a rate of 50 liters per hour and leaves the cooler as a liquid paint mixture of liquid fatty constituents with crystals of solid fatty constituents finely embedded therein. scattered. The partially solidified fat is then dispersed in an aqueous wetting agent solution in six agitation vessels connected together by overflows in series. In the first stirring vessel the fat is continuously mixed to form a dispersion with half its amount by weight (25 liters per hour) of an aqueous solution having a temperature of 25 C which contains 2% of a technical sodium salt of a C10 fatty alcohol sulfate (0.3% of active substances) as well as 3% of magnesium sulfate.

   In the next three stirring vessels, the dispersion formed in the first stirring vessel is diluted by the addition of a 3% solution of magnesium sulfate. The amount added is 12.5 liters per hour, which is distributed roughly evenly across the three stirring vessels. The dispersion is thus diluted to a fat: aqueous solution amount ratio of 1: 0.75. The following two stirring vessels serve to homogenize the dispersion by stirring. The dispersion thus formed at a temperature of 25 ° C. passes through a centrifuge with a solid envelope and it is here continuously separated into an aqueous phase containing the solid fatty constituents and a liquid fatty phase.

   The quantitative ratio of solid constituents: fluids is approximately 20:80. The raw material and the fractions have the

 <Desc / Clms Page number 35>

 following features:
 EMI35.1
 ird.sagnn.acid. înd.fade P.F. in
 EMI35.2
 
<tb>
<tb> C
<tb>
 
 EMI35.3
 raw material a, 0 199 50.6 3 ?, constituting a solids 1: 8 198 3ex? 48.5
 EMI35.4
 
<tb>
<tb> constituents <SEP> liquids <SEP> 2.1 <SEP> 203 <SEP> 53.6 <SEP> 20.0
<tb>
 
The suspension of the solid fatty constituents in the aqueous phase is then heated over the course of one hour with stirring. at 39 ° C. The solid fatty constituents are partially liquefied at this temperature and separated in a solid shell centrifuge at 7:. lighter phase state.

   The heavy phase consists of the aqueous solution comprising solid fat particles suspended therein. By melting, the solid constituents are separated from the aqueous solution and the fractions are washed with water. The ratio of the amounts of solid to liquid constituents is about 25:75.



  The materials have the following characteristics:
 EMI35.5
 Ind. Ind.aap4m acid. lnd.lada .... en ¯¯¯¯¯¯¯ ¯¯¯¯¯¯ - ilc raw material z, 8 1s9 39.7 48.5 solid constituents i, 6 the 33.5 49.5 liquid constituents 18,197,511.7 - 4l5.5
 EMI35.6
 EXEKILE23.-
In order to remove small amounts of a high melting point component of palm oil, the first portion. of Example 22 is repeated for a palm oil having an iodine number of 47.6 and a melting point
 EMI35.7
 of 4 C. In the scraper cooler on. cools the palm tree from 4S * C to 3. C. The temperature of the dispersion in the first stirring vessel is 3.

   C and rises to a temperature of 370C when entering the centrifuge The following products are obtained: A solid fatty constituent having an iodine number of 22.1 and a melting point of 56 C, and a liquid fatty constituent

 <Desc / Clms Page number 36>

 
 EMI36.1
 having an: iodine number of 49.2 and a melting point of 9.

   The quantitative ratio of solid: liquid constituents is 6.4: 93.6. EXAMPLE 24.-
 EMI36.2
 One kg of palm oil having an ioda number of z and a melting point of 410C is cooled while stirring in the space of one hour at 45 to 35 C, then it is further stirred for a further period. hour at 35 C. Then stirred
 EMI36.3
 halle for 15 minutes at the same temperature with 100 g of solstian aqueusa onions containing 3% zag sulphate :::. 8i: u as well as 5% sodium sulphate tec1m1qu of fatty alcohol 50% having uc chain length of <; .- C.lB.

   Aoentrifugation of the resulting dispersion leads to an upper phase containing the liquid constituents of palm oil which, after washing with water, have an iodine number of 50 and
 EMI36.4
 a melting point of 34.5 "C) and a lower aqueous phase in which the solid constituents are dispersed. After melting and separation from water, the constituents are
 EMI36.5
 Killer-solids have an iodine number of 305 and a melting point of 53 C. The liquid-solid component ratio is 88:12.



  EXAMPLE 25.-
Raw coconut fat, having a
 EMI36.6
 temperature of 3 ° C. is cooled to 21 ° C. in the apparatus described in Example 22 with a. hourly output of 30 kg. The cooled fatty mixture is stirred: with half of its quantity
 EMI36.7
 by weight of an aqueous solatfora which contains 0.6% by weight of C10 fatty alcohol sodium sulphate and 4% by weight MgSO4 in the first of six stirring vessels arranged in series. The resulting dispersion passes from the agitating vessels.
 EMI36.8
 tation in a ctr1f ':: tge :: tse of the In.perfaré type and it separates corrtfnne1.1.e ;;: t2nt in and in the dispersion of fat

 <Desc / Clms Page number 37>

 
 EMI37.1
 solid in the aqueous phase at a temperature of 2 & c.

   The separate
 EMI37.2
 The aqueous phase is then heated to 50 ° C., so that the solid fatty constituents are completely liquefied and they are separated from the aqueous phase in disk centerfugsase. The content ratio of the high and low melting point constituents obtained is 28:72. The aqueous solution to the wetting agent is added after adding one tenth of a percent by weight of wetting agent for future separation.

   The separate products have the following characteristics:
 EMI37.3
 .aa1de f d.8a àn <, iodine P. in ¯¯¯¯¯¯ ¯¯¯¯¯¯¯ -C
 EMI37.4
 
<tb>
<tb> fat <SEP> from <SEP> nuts <SEP>
<tb>
 
 EMI37.5
 starting coconut = 9,260 95 23 const1t.aOL1des 5.3 256 2.9 a9 finding. l.1qn1des l't, 3 2ëL 1à, 19
 EMI37.6
 KWZK 86.- Crude palm kernel fat & oil is always kept separate to the same extent. The outlet temperature of the reiro leaves the scraper and the inlet temperature of the dispersion to the centrifuge is 35 ° C. All other conditions are equal to + 25. The liquid solids component ratio is 30: z.

   The product before and after separation: know the characteristics
 EMI37.7
 :! ad.ac1de Insapoin md.1ode P.F. in bd, aeid mEsapom and, iodine OC palm kernel fat 10, & am 1425 26 solid eonstitoants 7fl 246 6.0 30 colistit. 1.1qu1c1es l2z3 252 18.2 ai
 EMI37.8
 The solid constituents obtained according to Examples 25 and 26 are washed with .a1.Ca1..i to remove all. free acid and, therefore, the melting points are
 EMI37.9
 brought to 30 and 3 (C respectively. The products thus pri-

 <Desc / Clms Page number 38>

 They have a melting range of only 1 C and their expansion curves on melting show pronounced maxima at 29-30 C and 33-34 C respectively.

   The characteristics therefore come very close to coconut butter, and are therefore an excellent substitute for it.



    EXAMPLE 27.-
Completely melted crude palm kernel oil fat having an acid number of 18, a saponification number of 244 and an iodine number of 15.2 is cooled in a scraper cooler such as the one. used in Example 22, 50 liters capacity, with an hourly flow rate of 55 kg. The first portion of the cooler is cooled with water to a temperature of while the second half is cooled with aean to a temperature of 25 C. The outlet temperature of palm kernel oil fat is 24. , 8 C.

   The cooled fatty mixture is then worked with 25 kg per hour of an aqueous solution at 25 ° C. which contains 0.3% by weight of NaOH and 4% by weight of Na4SO4 in the first of the six stirring vessels connected in series. The free fatty acid present in crude palm kernel fat forms an alkaline, soap which acts as a surfactant and disperses the fat in solution. watery.

   In the second of the five stirring vessels the mixture is diluted in stages with 5.5 kg per hour in each stage of a 3% solution of Na2SO4- After passing through the sixth stirring vessel, the dispersion: formed which at a temperature of 25 ° C. passes through an imperforate centrifuge in which a separation of the liquid fatty constituents takes place in the suspension of the solid fatty constituents in the aqueous phase. After heating to a temperature of about 60 ° C, 12%, based on the initially processed crude palm kernel oil fat, solid constituents separate.

   These solid constituents after al- refining

 <Desc / Clms Page number 39>

 cuddly have a flowing melting point of 33.5 C and a clear melting point of 33.7 C.



  EXAMPLE 28.-
Deacidified cottonseed oil is cooled with an equal amount of an aqueous solution which contains 0.7% by weight of a 30% by weight technical fatty alcohol sodium sulfate, having a chain length of C10, and 4% by weight of magnesium sulfate. The mixture is stirred and cooled over 1/2 hour from 20 to 5 ° C. The dispersion formed is left to stand for 20 hours at this temperature without stirring. During this time the higher melting point constituents crystallize out of the cottonseed halle in the dispersion; then the mixture is separated after stirring for a short time at a temperature of 6 ° C in an imperframe centrifuge.

   The aqueous solution with the higher melting point solid glycerides suspended therein separates out as a heavy phase. The lighter phase of cottonseed oil is obtained with a yield of env: tron 86% which, after removing traces of moisture, remains completely clear after standing for 5% hours in water. ice water, indicating extremely high resistance to cold.



  EXAMPLE 29.-
Melted cottonseed oil fatty acid, Iodine Index 95, is cooled continuously in a kneading machine at +15 C. The fatty acid paste thus obtained is stirred for 5 minutes with an identical amount of an aqueous solution to. the same temperature containing 0.5; a technical sodium sulfate 50% aliphatic alcohol chain length C12-C14, 5% MgSO4, and the resulting dispersion is loaded into centrifuge tubes, then it

 <Desc / Clms Page number 40>

 is centrifuged. After centrifugation for 5 minutes 2 layers formed, the lower layer consists of. the aqueous phase with the solid fatty acid portions in. suspension in it, while the top layer consists of liquid fatty acid.

   We repeat the example with various
 EMI40.1
 amounts of salt added to the aqueous solution. The volume of liquid fatty acid separates out is a measure of the effect of the addition of alginate. We can see it from the following table
 EMI40.2
 concentration of aLflnate% by weight of acids
 EMI40.3
 
<tb>
<tb> in <SEP> the <SEP> aqueous <SEP> solution <SEP> fatty <SEP> liquids <SEP> separated
<tb>
 
 EMI40.4
 of surfactant substances per weight
 EMI40.5
 
<tb>
<tb> tives <SEP> en <SEP>% <SEP> en.

   <SEP> weight, <SEP> of <SEP> the <SEP> dispersion <SEP> total
<tb> 0.0 <SEP> 1
<tb> 0.25 <SEP> 8
<tb> 0.5 <SEP> 12
<tb> 1.0 <SEP> 15
<tb>
 EXAMPLE 30.-
 EMI40.6
 100 g of tallow fatty acid, iodine value 55 which has been ground at 22C to a pasty consistency in a cutter at high speed, are stirred for 10 minutes at the same temperature with the quantity of marl. an aqueous solution of a wetting agent containing 0.2% sodium salt of a single
 EMI40.7
 sulfuric ester of technical aliphatic alcohol at 50, the cuban length of which is Cig-f ± <z of JIgSO4 and 0.5% of sodium alginate, after which the dispersion obtained is vantroduite dan ,,, central tubes. 2geurs and it is centrifuged.



  64 g of liquid fatty acids separated, iodine number 79, in the form of a soperative layer, while the lower aqueous layer contains 33 g of solid fatty acids which are separated by fusion, iodine number 8, 2. A parallel test carried out with the wetting agent solution without the addition of alginate, leads to. solid fatty acids with an iodine number of 20.

 <Desc / Clms Page number 41>

 



    EXAMPLE 31.-
500 g of a mixture of animal fatty acids, iodine number 61, acid number 204, joint-
 EMI41.1
 ment with twice the amount of a natural agent solution containing 0.2% of a 50% sodium tachric salt of a half-ester! 3tIJ ..! "uric aliphatic a.cao1 throughout chain in C12 -C is and 5% Kgso4l> within 3 hours with stirring, from 40 to 20 C, after which the dispersion produced is separated in a centrifuge as described in Example 30.



   The solid portions which separate have an iodine number of 25.8. In parallel runs in which 1% of different protective colloids are additionally added to each of the wetting agent solutions, the separated solid parts have the following iodine numbers
 EMI41.2
 
<tb>
<tb> colloid <SEP> protective <SEP> Index <SEP> of <SEP> iodine <SEP> of
<tb> the <SEP> solid <SEP> portion
<tb> without <SEP> addition <SEP> 25.8
<tb>
 
 EMI41.3
 alginate techaJ-qoe le, 6 tragacanth techniqne il po1 range, ymé tacry1.a te d '8! IIIIlOII: 1tmt zou 8
 EMI41.4
 
<tb>
<tb> <SEP> cellulose <SEP> sodium <SEP> glycolate <SEP> technical <SEP> 15.3
<tb>
 
 EMI41.5
 EXAMPLE 3ulh- 1 kg of the mixture of fatty acids described in Example 30 is cooled while stirring at 40 to 20 ° C., forming a di-fatty acid paste, which is still fluid;

   it is then stirred with the same quantity of a wetting agent solution containing 0.2% air 50% technical sadistic salt of a half-sulfuric ester of fatty alcohol of chain length in
 EMI41.6
 -C1.4 1'fgSOi as well as 1% sodium cellulose dreglycolate technical. Os separates the dispersion in a centr1: fl1- geuse of the tabular type.

   The liquid portions of fatty acid separate, iodine number 85, they are separated and the solution

 <Desc / Clms Page number 42>

 The lower water is heated so that the solid portions therein in suspension, iodine number 18.3, can be melted and separated. Then 0.2% of the above sodium aliphatic alcohol sulfate is dissolved in the remaining aqueous phase, which is free of fatty acid, and the wetting agent solution is used as described above for further separation of the acid. fresh fatty acid.



  The solid portions obtained after separation have an iodine number of 19.6. A parallel run with a fresh solution of wetting agent of the same concentration, but without the addition of cellulose glycolate, gives solid portions having an iodine number of 24.2.



  EXAMPLE 33. -
The mixture of fatty acids described in Example 30 is melted and cooled continuously to 20 ° C., forming a fluid pasty mass in a scraper cooler. 100 kg of this mixture are stirred in 60 kg of a wetting agent solution which contains 1% of an approximately 30% technical sodium alkyl-benzene-sulfonate having a chain length of 10 to 16 carbon atoms, 2% NaCl and 2% ammonium polymetacrylate. After that the dispersion produced is further diluted with 140 kg of a 2% sodium chloride solution, and then it is stirred for 10 minutes.

   The barely liquid mixture thus obtained can be separated continuously in an imperforated centrifuge of the type with separating discs, 150 kg of dispersion giving 28 kg of liquid fatty acids, iodine number 84, on the one hand, and a suspension of solid fatty acids in the aqueous phase, on the other hand. On heating the aqueous phase, 20.5 kg of solid fatty acids separate out as an upper liquid layer, which can be removed. Iodine number of solid fatty acids: 14.9.



   Well. that the invention: has been described in detail

 <Desc / Clms Page number 43>

 With reference to certain specific embodiments, various changes and modifications will be apparent to those skilled in the art which are within the spirit of the invention and are within the scope of the appended claims.



   When using the process of the invention for the production of coconut butter type fats, the starting fats should contain a relatively high content of C12 fatty acids. The content of C12 fatty acid radicals should be at least 30 and preferably 40 to 55% by weight relative to the total fatty acid radicals present in the starting glycerides. Fats which have such a composition are the fats of palm seeds. Therefore cocoa fat, palm kernel oil and babassu halle offer Special Importance as raw materials.

   These fats are processed in such a way that the lower melting point fats are separated and the content of C12 fatty acid radicals is enriched. The higher melting point component is suitable as a substitute for cocoa butter. The starting fats are preferably processed in the raw state and the solid constituents are refined.



   In the hibernation of edible oils, oils are used as raw materials which become cloudy when cooled to 0 ° C. for more than 3 hours, preferably for 5 to 20 hours. In accordance with the invention the higher melting point constituents are removed from these oils to such an extent that the oils do not become cloudy when tested as described. Hibernated oils must be cold tested according to the official Coll-53 method of the American Oil Chemist Society.


    

Claims (1)

EMI44.1 EVE DIe A T l 0 s.- --------------------------- 1.- Process for separating mixtures of organisms selected from the group consisting in 1.3.:!-;es of fatty acids and naiads of carboxylic esters of the compounds, rims having different melting points, characterized in. which forms a dispersion of a te-1 '; mixture of a sufficient quantity of an aqueous solution of a surfactant material which is substantially inert to EMI44.2 constituents of this mixture ponr ma1nte: cite continuous aqueous phase at a temperature at which the nE-mixture contains both solid and liquid constituents, in that the dispersion is then subjected to a centrifugal action in a zone impermeable to liquids , confined externally, separating the dispersion, aqueous into a specific phase- EMI44.3 substantially liquid coenstituents of the mixture and in a specifically heavier phase of aqueous content with the substantially solid constituents EMI44.4 of the mixture in suspension in this JXd1.ielI, and in that at least a portion of at least one of these phases is removed separately. 2. A method according to claim 1, charac- EMI44.5 terized or that the surfactant has at least one organic hydrophobic radical and one group byc1roBOJ.l1: U1sa .. "'1t in its molecule. 3. A method according to claim 2, characterized in that the surfactant material is present in an amount of at least 0.05% by weight of its aqueous solution) and in that the aqueous solution is present in this dispersing ion in an amount of 0.5 to 5 parts by weight per part EMI44.6 by weight #. # - ####### '....- r of the organic mixture. 4. A method according to claim 1, characterized in that the dispersion further contains a solvent. <Desc / Clms Page number 45> low boiling liquid organic. 5. A process according to claim 1, characterized in that the dispersion is forced by intimately contacting the aqueous solution of a surfactant material with this mixture under a condition of substantially complete melting, and in that. then the resulting intimate mixture is cooled to the separation temperature, 6. A solvent process according to claim 1, charac- terized in that the aqueous dispersion contains. besides an electrolyte. 7. A method according to claim 1, characterized in that the aqueous dispersion further contains a protective colloid. 8. A method according to claim 7, characterized. in that: the protective colloid is present in an amount of up to 7% by weight. 9. A process according to claim 1, characterized in that the aqueous solution of the surfactant material containing the separated solid constituents of the organic mixture is separated from the latter and in that the aqueous solution is reused for the preparation of 'a new dispersion, 10. A method according to claim 1, characterized in that at least one of the separated phases is again subjected to centrifugal inaction in the form of this dispersion, at a temperature which for the liquid component of this mixture is lower and which, for the solid constituent dispersed of this mixture, is higher than the temperature at which the centrifugal separation is carried out in the preceding centrifugation process. It * - A method according to claim 1, characterized in that the separate aqueous solution containing the dispersed substantially solid component of the organic mixture <Desc / Clms Page number 46> at least one additional phase separation is subjected to a temperature for the dispersion and for the separation above the temperature of the previous separation 12. A process according to claim 1, characterized in that the aqueous dispersion contains an agent for lowering the freezing point of the aqueous medium. 13. A method according to claim 1, charac- terized in. that the mixture is ground prior to the formation of the dispersion. 14.- Process. According to claim 1, characterized in that the mixture contains free fatty acid and in that the surfactant material is formed in site by the addition of: a reaction material: alkaline. 15. A process according to claim 1, characterized in that the surfactant material is a member selected from the group consisting of alkylphenol-polyglycolethers, alkylsulfonates, fatty alkylsulfates and alkylbenzene sulfonates. 16. A process according to claim 1, characterized in that the surfactant material is initially added to the organic mixture prior to the formation of this dispersion. 17.- A process for the separation of fatty acids from a. mixture thereof, characterized in that this mixture is subjected, while it is substantially dispersed in a continuous phase aqueous solution of a surfactant substantially inert to fatty acids, to a centrifugal action confined externally to a temperature for dispersion at which a portion of the fatty acids is in a substantially solid condition and the remainder in a substantially liquid condition, in that this substantially centrifugal action is continued <Desc / Clms Page number 47> at this temperature, thus forming a first layer comprising the solution, aqueous and, in the state dispersed therein, the substantially solid fatty acids, and a second layer comprising substantially the liquid fatty acids, and in which separate = -en is removed, at least one portion of at least one of these layers. 18.- A process for the separation of fatty acids from a mixture thereof, characterized in that a dispersion of this mixture is fed substantially continuously in an aqueous solution in continuous phase of a substantially inert surfactant material. towards fatty acids, at a temperature for dispersion at which a portion of these fatty acids is in a substantially solid condition and the remainder in a substantially liquid condition, in a centrifugal zone confined externally in ,,: section thereof, in that this dispersion is subjected in a substantially continuous manner, while being substantially at this temperature, to centrifugal action in this zone, thus forming: in this zone a first layer comprising the aqueous solution and , dispersed therein, the substantially solid fatty acids, and a second layer comprising the substantially liquid acids, and in that material from each of these layers is substantially continuously removed in sections. layers away from the section; of dispersion feed zone, the feed of the dispersion and the removal of the layer material being adjusted so that these layers are maintained in a substantially continuous manner within that zone. 19.- A process for separating mixtures of carboxylic esters, characterized in that one forms a dispersion of this mixture in a sufficient quantity of a solution. <Desc / Clms Page number 48> aqueous surface-active material to maintain a continuous aqueous phase at a temperature at which the mixture contains solid and liquid esters, and in that the solid ester and the liquid ester are separately recovered. 20.- Process for the separation of carboxylic esters from a mixture thereof, characterized in that this mixture is subjected, while it is substantially dispersed in a continuous phase aqueous solution of surfactant material substantially inert to these carboxylic esters, to centrifugal action confined externally to a temperature for dispersion at which a portion of these carboxylic esters is in a substantially solid condition and the remainder in a substantially liquid condition! in that this centrifugal action is continued at substantially this temperature, thereby forming a first layer comprising the aqueous solution and dispersed therein the substantially solid carboxylic esters, and a second layer comprising the substantially liquid carboxylic esters, and in that a portion of at least one of these layers is separately removed. 21. A process for the separation of carboxylic esters from a mixture thereof characterized in that 1-'on is fed. A substantially continuous dispersion of this mixture in a continuous phase aqueous solution of a surfactant material, substantially inert to these carboxylic esters, at a temperature for the dispersion at which a portion of the carboxylic esters is in a substantially solid condition and the remaining in a substantially: Liquid, in a centrifugal zone confined externally in a section thereof, <Desc / Clms Page number 49> in that this dispersion is subjected in a substantially continuous manner, while it is substantially at this temperature, to centrifugal action in this zone, thus forming therein a first layer comprising the aqueous solution and dispersed therein the substantially solid carboxylic esters, and a second layer comprising the substantially liquid carboxylic esters, and in which material is substantially continuously removed from each of these layers in distant layer sections. the section of the dispersion feed zone, this supply of dispersion and the removal of the layer material being controlled so that these layers are maintained substantially continuously in this zone. 22, - Process for preparing butter substitutes. of cocoa, characterized in that a dispersion of a fat having a relatively high quantity content is formed. sufficient number of C1-3 fatty acid radicals. in an aqueous solution containing a surfactant material to maintain a continuous aqueous phase at a temperature at which the fat contains solid and liquid components, in that the dispersion is separated, by forming layers, into. a specifically lighter phase of substantially liquid constituents of the mixture and a specifically heavier phase of substantially solid constituents of aqueous medium with the substantially solid constituents of the mixture suspended therein, which are separately removed from the mixture. minus a portion of the heavier phase and in recovering the distinct solid constituents thereof in the form of a cocoa butter substitute. 23.- Process according to claim 1, characterized in that the surfactant material has at least one organic hydrophobic radical and one water-solubilizing group in its molecule, and in that it is present in one <Desc / Clms Page number 50> amount of about 0.1 - 5% by weight of its aqueous solution.