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`
`Petition for Inter Partes Review
`Of U.S. Patent 8,278,351
`Exhibit
`ENZYMOTEC - 1032
`
`

`
`oil & soap
`
`play a major physiological role.
`It follows that in analytical work
`the factor of 26 x P, used to cal~
`culatc the purity of egg lecithin,
`should be applied relatively rather
`than literally to commercial veg-
`etable lecithin. An analysis of oil-
`free soybean phosphatide, gave 3.1
`total phosphorus, indicating a high-
`er factor. However, egg lecithin as
`produced is often a mixture and
`not a pure chemical entity and even
`very highly purified egg lecithin
`may exhibit a tendency to become
`in part alcohol insoluble. For con-
`venience the term “Lecithin” here-
`inafter refers to the soya—lecithin of
`commerce unless qualified by the
`context.
`
`Depending upon the raw mate-
`rial and method of manufacture
`the free fatty acid content of leciv
`thin products will vary but, to avoid
`an excessively high figure in any
`case, should not be determined by
`direct
`titration in the usual way.
`The lecithin and other phosphatides
`tend to react with the alkali. Be—
`sides saponifying more readily than
`ordinary oils and fats, lecithin con-
`tains a free acid hydroxyl
`in the
`phosphoric acid group‘; cephaliri
`in particular has somewhat of an
`“organic acid” character and is
`isoelectric at a pH of about 5.
`The free fatty acid should be run
`on the matter extracted by washing
`with an excess of cold acetone.
`Preliminary addition of
`a
`small
`amount of ether
`facilitates
`this
`operation;
`the
`acetone may be
`mixed in warm but the whole mass
`should be chilled to -l5° C.
`Probably the first to envisage the
`possibility of producing vegetable
`lecithin commercially from soy-
`beans and to devise feasible proc~
`esses and equipment was Hermann
`Bollrnann of Hamburg. Bollmann
`concerned himself with solvent
`extraction. After
`the war
`soy-
`beans were handled increasingly
`by the German oil mills and being
`relatively rich in lecithin afforded
`an excellent source for this sub—
`stance. Bollrnann originally used a
`combined solvent of about
`two
`parts alcohol and three parts ben-
`zol or a volatile liquid hydrocarbon
`on the theory that
`the residual
`meal would be more palatable5.
`Also this combined solvent gave a
`larger lecithin yield by loosening or
`breaking the lecithin—protein com-
`bination in the bean. The current
`of solvent moved counter to the
`direction of bean travel and ‘a simi-
`lar counter-current principle was
`employed in steaming the meal to
`remove traces of solvent“.
`
`52
`
`Conway and his associates in this
`country as early as 1923 appre-
`ciated the possibilities of solvent
`extraction including lecithin re-
`covery, and negotiated with Boll-
`mann for licenses under the latter’s
`American patents. A pioneer plant
`was put under construction in Nor-
`folk but
`for various reasons the
`project did not progress to regular
`commercial operation. This cnter~
`prise, however, gave impetus to the
`introduction of soya-lecithin as well
`as stimulated interest in the extrac~
`tion of oil seeds. Since that time
`the domestic supply of soybeans
`has grown tremendously, centering
`in Illinois, and the past five years
`have seen solvent extraction be-
`come a large scale reality. Boll-
`rnann’s methods for separation and
`purification of lecithin as an inte-
`gral part of the extraction process
`are being successfully applied here
`as in Europe. Today, a single sol~
`vent derived from petroleum seems
`to be preferred to Bollmann’s com-
`bined solventl. Soybeans contain
`about 11/2% to 3% of phosphatide
`but not all is removed during ex«
`traction so that
`the meal retains
`about
`l%. VVhile the single sol~
`vent does not afford as large a
`yield the refined lecithins are much
`freer from carbohydrates.
`Before passing through the sol~
`vent the beans are cleaned, dried
`and flaked. The oil and lecithin
`dissolve out and after evaporation
`of the solvent moisture is
`intro-
`duced to hydrate the lecithin. It is
`then possible to effect a good sepa-
`ration with high speed centrifugals.
`The operation is continuous. A
`small proportion of oil
`remains
`“bound” to the lecithin, amounting
`to about 30% of the weight of the
`lecithin, and this later serves as a
`carrier.
`sub~
`The lecithin emulsion is
`jected to vacuum distillation to
`drive off the water and this treat:
`ment also improves the taste and
`odors. For certain purposes light
`colored grades are desired and
`bleaching with peroxides, for ex~
`ample hydrogen peroxide, effects a
`substantial reduction in the degree
`of red and yellow coloratiorf’. The
`temperatures applied during proc-
`essing do not prove injurious due
`to the protective presence of the
`oil and moisture. The carrier of
`soya oil
`in the finished lecithin
`guards against change of the active
`substance, which it
`renders soft
`and convenient
`to use.
`
`Purified lecithin, free from oil,
`is waxy and gummy and less solu-
`000002
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`
`march, 1939
`
`this type
`for
`ble. The demand.
`comes chiefly from the pharmaceu~
`tical trade. The production cost is
`high. Less costly but still more
`expensive than the straight
`soya—
`lecithin are those grades which can
`be made by substituting some other
`oil or fat for soya oil as the carrier.
`For use in pure chocolate coatings,
`a purified grade with a cocoabutter
`carrier most
`fully answers trade
`requirements.
`The
`soya—lecithin
`after bleaching is washed with a
`selective solvent, usually acetone, in
`which the oil dissolves but
`the
`lecithin does not. The supernatant
`liquid is drawn off and the specified
`carrier, such as hydrogenated short-
`tening or refined cocoanut whole
`oil, is mixed in. The residual sol«
`vent can then be evaporated”.
`Commercial soya~lecithin can be
`split up into several closely related
`components by treating with alco-
`hol, separating the residue. ins0lu«
`ble at about 60° C. and subjecting
`the solution to fractional crystalli~
`zation by cooling“. So far no im~
`portant commercial advantage or
`superiority has been found for any
`of the phosphatide fractions com—
`pared to the soya-lecithin obtained
`by the above described process
`which would justify the cost of
`separation. V\/hile it has been re—
`ported that highly purified cephalin
`is a more effective anti-oxidant
`than highly purified lecithin”,
`it
`should be borne in mind that we
`are dealing with a natural extract,
`obtained by mechanical rather than
`chemical means.
`Indeed, for most
`purposes
`the natural
`lccithin—oil
`complex seems
`superior
`to the
`separated fractions and to a con-
`siderable extent the process of iso-
`lation may denature or change the
`original potency, even if the com-
`ponents should be later mixed back
`together in the same proportions.
`Nevertheless, future research will
`probably include a more detailed
`study of the individual vegetable
`phosphatides as well as of stable
`lecithin-protein combinations which
`might be used in acid media, as in
`mayonnaise‘3» 1‘.
`1924 Bollmann
`As
`early as
`pointed out that ordinary refining
`and deodorizing methods destroy
`the lecithin naturally present
`in
`oils from seeds and that the addi-
`tion of small fractions of a percent
`of lecithin to refined oils retards
`rancidity”. He observed too that
`in frying the oil did not squirt or
`spatter in the usual way. Lecithin
`is now Widely used in various vege-
`table and animal oils and shorten~
`
`

`
`march, 1939
`
`ings to inhibit oxidation and ran-
`cidity,
`in quantities up to 0.15%.
`Continued use by the trade as well
`as many accelerated tests have
`shown its value as an anti-oxidant,
`and as would be expected the most
`striking results are obtained with
`the more unsaturated oils and fats.
`Beyond 0.15% the improvement is
`not proportionate and in
`some
`cases from 0.05% to 0.1% has been
`adequate“‘- ‘7.
`It is interesting to
`note that in cod liver and halibut
`liver oil preparations vitamin po-
`tency is being prolonged by incor-
`poration of soya-lecithin”.
`Besides counteracting rancidity
`(and retarding hydrolysis”)
`leci-
`thin, because of its colloidal effects,
`can be advantageously used in mix-
`tures of different melting point fat-
`ty oils such as exemplified by com-
`pound shortenings”, or in fats con-
`taining glyceride
`components of
`different melting points
`such as
`coconut oil products or cocoabutter.
`The lecithin, pre-mixed with part
`of the melted oils, should he added
`just prior to chilling. Lecithinated
`shortening exhibits greater physical
`stability, being less subject to “sep-
`aration,” “streaking” and “granu-
`lation.” The fact that the mass of
`plasticizcd
`shortening
`is
`better
`adapted to bind the bubbles of air
`is evidenced indirectly by the foam-
`ing which occurs while testing in
`the Swift Stability Apparatus. On
`the other hand,
`the
`interfacial
`tension relative to water is reduced
`as
`indicated by smaller droplets
`when slices of potatoes are deep
`fried“.
`
`about
`containing
`Shortenings
`0.05% or more of lecithin darken
`very considerably during deep fry-
`ing or on heating to elevated tem-
`peratures“. This may be ascribed
`to carbohydrate and perhaps indi-
`rectly to the phosphoric acid group
`in the lecithin molecule. Strangely
`enough with
`some
`compounds
`tested, but not all, the addition of
`0.01% of
`lecitltdn resulted in a
`slightly lower
`l.ovibond reading
`initially and did not
`increase the
`coloration after heating to 200° C.
`and frying potatoes. The control
`sample emitted a more pungent
`odor and during frying the bubbles
`were larger and less uniform.
`It
`is known, of course,
`that lecithin
`reduces interfacial tension between
`oils and Water”. Evidently the
`composition of the compound and
`the character of its oils and fats
`determines the maximum amount
`of lecithin which can be used where
`deep frying is a factor, so that a
`
`series of tests should be made for
`each formula.
`
`Just as lecithin inhibits granula-
`tion so does it retard crystalliza-
`tion of stearine from refined cot-
`tonseed oil at lower temperatures“.
`An analagous effect has been noted
`in the setting of cocoabutter at
`temperatures where some of
`the
`lower melting point
`fractions re-
`main liquid”. An effort was made
`to utilizevthe action of lecithin on
`surface tension to facilitate the
`pressing of oils, as with cocoabutter
`from chocolate liquor, but this has
`not yet proven significant“.
`Adding 0.5% to 2% of lecithin
`to shortening substantially increases
`the lubricating properties (shorten-
`ing value) and emulsifiability“ 2*.
`Such a shortening would be in-
`tended for bakery use exclusively,
`in bread or cakes or biscuits and
`crackers. The lecithin causes the
`shortening to spread more readily
`throughout the dough and promotes
`uniformity and better moisture re-
`tention as well as increases tender-
`ncss.
`Instead of blending the leci-
`thin directly with the shortening
`it may be first emulsified with water
`and then mixed with the fat but
`this
`should preferably be done
`shortly before use”.
`In any event,
`to assure optimum results the bak-
`ery formula should be kept proper-
`ly balanced.
`Lecithin forms perfectly homo-
`geneous milky emulsions with wa-
`ter which may be diluted almost
`indefinitely. One of the first uses
`for soya-lecithin was in oleomar-
`garine where it replaced more ex-
`pensive egg yolk added to improve
`the
`frying properties“. Up to
`0.30% of lecithin incorporated at
`any stage, usually in the churn,
`counteracts
`spattering
`and
`the
`sticking of milk solids in the frying
`pan and imparts desirable foaming
`and browing effects. At the same
`time there is
`some increase in
`spreadability and shortening value.
`Thus, with lecithin oleomargarine
`is a more universal household fat,
`for kitchen as well as table use.
`Butter, of course, contains a frac-
`tional percentage of lecithin derived
`from the milk“: 32; favorable re-
`sults have been reported with proc-
`ess or
`renovated butter. Olen-
`margarine and butter are emulsions
`containing much more fat
`than
`water. Several examples of
`the
`other type Where water is the con-
`tinuous phase may be given.
`In a
`3% emulsion of oleo resin of cap-
`sicum 0.50% of lecithin was satis-
`factorily used as the emulsifying
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`
`oil & soap
`
`agent, while with a 50% Castor oil
`or cod liver oil emulsion 4% to 5%
`of lecithin was used in a prepara-
`tion stable for months.
`
`Cake fillings and icings compris-
`ing‘ shortening and water cream
`up to larger volume when lecithin
`is used. The moisture is more
`finely divided and uniformly dis-
`tributed and the texture apprecia-
`bly smoother“. Likewise the sur-
`face of icings finishes with a more
`attractive
`lustre.
`“Lecithinated”
`fats for pan or slab greasing are
`more spreadable and go further.
`Another instance of lecithin util-
`ity where fats must be emulsified in
`the presence of moisture may be
`seen in the manufacture of con-
`fectionery, especially chewing can-
`dies, such as cararnels. Ordinarily
`the added fat floats on top during
`the cook and the candy itself tends
`to be greasy to the touch, the film
`of fat being readily oxidizablc. A
`fractional percentage of
`lecithin
`causes the fat to disappear and mix
`throughout the batch during cook-
`ing and improves the handling and
`keeping properties of the caramel.
`Moreover, the caramel cuts better
`and cleaner due to the greater lub-
`ricating value of the fat“. Leci-
`thin can be used to similar advan-
`tage in boiled icings, such as butter-
`scotch.
`
`Having an affinity for both oil
`and water and being adsorbed at
`interfaces,
`lecithin promotes
`the
`rapid and complete wetting by oils
`or fats of a wide variety of solid
`particles. This property, plus the
`fact that the oil will form a thin-
`ner continuous film, makes lecithin
`a time,
`labor and material saver.
`Thus, where plastic cocoanut butter
`or shortening is to be mixed with
`sugar to form a wafer filling, leci-
`thin permits a higher solids content
`while maintaining the necessary
`workability; the mass has a better
`body and the fat
`is less likely to
`bleed from the sugar. So too in
`coatings where oil or
`fat
`is
`the
`liquid
`phase
`lecithin
`facilitates
`grinding and uniform dispersion
`and improves the flow and covering
`properties“. The first 010% shows
`the greatest effect and with in-
`creasing additions
`the viscosity
`curve flattens out, depending on the
`physical properties of the solid and
`the proportion of
`free liquid.
`It
`may be noted that when mixed
`with oils as with water,
`lecithin
`gives a colloidal solution. However,
`while lecithin will
`form a stable
`emulsion or dispersion with water
`in any proportion, only relatively
`53
`
`

`
`oil & soap —~
`
`small amounts can be dissolved in
`oils and fats.
`Its solubility is, of
`course, greater at high tempera-
`tures. The addition of lecithin does
`not reduce the viscosity of a fatty
`oil per se, the tendency is rather the
`reverse.
`
`Lecithin finds many miscellane-
`ous applications With oil and fat
`products. A small percentage in-
`corporated in citrus oils and other
`oil soluble flavors acts as a fixative,
`reducing flavor losses due to volatil-
`ization, and at the same time as-
`sures better
`flavor
`distribution,
`particularly in the presence of
`moisture“. Cosmetics,
`0 including
`shaving creams, made with lecithin
`possesses enhanced softening and
`penetrating value”: 35. Liquid soaps
`so treated are milder and more
`thorough in cleansing action”, 4°.
`Peculiarly enough lecithin. which
`forms milky emulsions with water,
`gives a clear solution with liquid
`soap. Still other uses in conjunc-
`tion with oily materials are in the
`drumming or fat liquoring of leath-
`ers“ and in the sizing of textile
`niaterials“. The addition of about
`15% benzyl alcohol to the lecithin
`has been found helpful in making
`
`Water emulsions without undue stir
`ring“.
`Hardly ten years have elapsed
`since lecithin became available com-
`mercially and was introduced to
`industry.
`In that period a variety
`of uses have been developed and
`factories built in the United States
`which are currently producing all
`that can be sold, with considerable
`capacity to spare. As consumption
`has mounted,
`the price trend has
`been downward to about 1/E2, of the
`1929 level. This is simply an ex-
`pression of the normal relationship
`between the cost of producing and
`selling as the numerator and the
`tonnage as the denominator. Many
`patents on methods of manufac-
`ture and use have encouraged mis-
`sionary work in this field and made
`possible enlisting the interest and
`capital necessary for research and
`for plant equipment. The recovery
`of lecithin has increased the value
`of fami products and provided a
`new and useful material; its future
`depends more on expanding exist-
`ing markets and discovering new
`uses than on solving manufacturing
`or technological problems.
`1. Rewald -~ Pharm. Zeitung, No. 88, 1928.
`2. MacI.ean -- Lecithin
`and Allied Sub-
`stances. p. 6.
`
`march, 1939
`
`32:???‘-‘E1333
`
`Leycnc —— Jour. Biol. Chem. p. 759, Jan.
`1923.
`Mathews —— Physiological Chemistry, p.
`108.
`.
`. Patent No. 1464557.
`. Patent No. 1371546.
`. Patent No. 2024398.
`. Patent No. 1776720.
`. Patent No. 1893393-
`. Patent No. 1895424.
`.
`. Patent No. 1667767.
`Olcott Bi Lfattill -- Oil 8: Soap 13 (4)
`D. 100,
`.1936.
`Olsen -- Incl. & Eng. Chcm.. Vol. 27.
`p. 1222, Oct. 1935.
`Whitaker — jour. Dairy Science, Vol.
`XIII. No. 1.
`U. S. Patent No. M75529.
`Royce -— Soap, p. 25, Sept. 1951.
`Evans -— incl. 8: Eng. Chem., 1:. 329, Mar.
`1935.
`Holmes ——— Ind. 8: Eng. Chem., p. 133,
`Jan. 1936.
`Truslcr -—- Oil 6: Fat Ind., April 1931.
`U. S. Patent No. 1831728.
`Oil 8: Soap,
`13. 261, Oct. 1936.
`U. 5. Patent No. 1982186.
`Drug 8: Cosmetic Ind., May 1932.
`U. S. Patent No. 2050328.
`Manf. Confectloncr, Nov.
`1929:
`U. S. Patent No. 1903597.
`Bakers Review, April 1931.
`Siebel Tech. Review. Jan. 1931.
`U. 8. Patent No. 1936713
`German Patent No. 142397.
`Hmrall, Purdue Univ., Bul. 401.
`Fleming — Anal. Ecl., Ind. 8:. Eng. Chem.,
`Vol. 4, p. 362, Oct. 15. 1932.
`Glabau — Bakers Weekly, Nov. 29, 1930.
`U. S. Patent No. 1859240.
`U. S. Patent No. 1781672
`U. S. Patent No. 2019494.
`Augustin — Amer. Perfumer, Sept. 1932.
`MacDo,u_gall — Proc. Am. Philo. Soc.,
`D. 55, Vol. LXVIT.
`Soap. p. 55, June 1935-
`Seifensieder — Zeit., Nr. 51, Dec. 1933.
`U. S. Patent No. 1779012.
`U. 3. Patent No. 1946332.
`U. S. Patent No. 1934005.
`
`
`
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`
`40.
`41.
`42.
`43.
`
`IVimer/':z’72g Co olers
`
`A MODERN OIL
`REFINERY
`
`T4211». Farm and filling equipment
`
`A. E. Staley 8: Company
`Decatur,
`Illinois
`
`Bleac/zing P765395
`
`Exterior Oil Refinery:
`000004
`(cid:19)(cid:19)(cid:19)(cid:19)(cid:19)(cid:23)
`
`Ce»v£rr'fuge.t