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(19)

(11) EP 1 137 650 B1


(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:


of the grant of the patent: C07F 9/02 (2006.01) A23D 7/00 (2006.01)
10.03.2010 Bulletin 2010/10 A23J 7/00 (2006.01)

(21) Application number: 98961964.8 (86) International application number:


PCT/US1998/025927
(22) Date of filing: 07.12.1998
(87) International publication number:
WO 2000/034292 (15.06.2000 Gazette 2000/24)

(54) PROCESS FOR PRODUCING DEOILED PHOSPHATIDES


VERFAHREN ZUR HERSTELLUNG VON ENTÖLTEN PHOSPHTIDEN
PROCEDE D’OBTENTION DE PHOSPHATIDES DESHUILES

(84) Designated Contracting States: (74) Representative: MacLean, Martin Robert et al


AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU Mathys & Squire LLP
MC NL PT SE 120 Holborn
London
(43) Date of publication of application: EC1N 2SQ (GB)
04.10.2001 Bulletin 2001/40
(56) References cited:
(73) Proprietor: ARCHER-DANIELS-MIDLAND US-A- 4 093 540 US-A- 4 235 493
COMPANY US-A- 5 453 523 US-A- 5 703 255
Decatur, Illinois 62526 (US)
• PATENT ABSTRACTS OF JAPAN vol. 0112, no.
(72) Inventors: 22 (C-435), 18 July 1987 (1987-07-18) -& JP 62
• HUTTON, Kyle, J. 039594 A (RINOOLE YUSHI KK; others: 01), 20
Latham. IL 62543 (US) February 1987 (1987-02-20)
• GUYMON, John, S. • DATABASE WPIDS LONDON: DERWENT
Forsyth, IL 66535 (US) PUBLICATIONS LTD 90-201661 BRAUN U. ET AL:
’Phosphatide Fractionation -by Ultrafiltration
Using Solvents with Increasing Dielectric
Constant’, XP002903348 & DD 275 461 A
EP 1 137 650 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)


1 EP 1 137 650 B1 2

Description lycerides using non-polar solvents and membrane sep-


aration. Non-polar solvents such as hexanes, chlorinated
Background of the Invention hydrocarbons, ethyl acetate may be separated from mi-
celles with phospholipids which have molecular weights
Field of the Invention 5 less than 50,000 daltons. These micelles act like macro-
molecules and are impermeable to ultra-filtration forming
[0001] The invention relates to deoiled phosphatides; a retentate. They can thus be separated from the triglyc-
food grade or pharmaceutical grade lecithin; and meth- erides which behave as single low molecular weight mol-
ods for producing same. ecules in solution and pass through or permeate the
10 membranes.
Related Art [0007] Phospholipids themselves may also be sepa-
rated from one another in a similar manner using solubility
[0002] The mixture of phosphatides referred to as lec- and ultrafiltration techniques with more polar solvents
ithins is a mixture of naturally occurring fat soluble deriv- such as alcohols.
atives composed of the following structural members: 15 [0008] Phospholipids have been separated from other
glycerol, fatty acids, phosphoric acid, amino alcohols and components of crude vegetable oils. (U.S. Patent No.
carbohydrates. They are found in practically any animal 4,496,489, U.S. Patent No. 4,062,882 and U.S. Patent
and vegetable material. Commercial lecithin refers to this No. 4,533,501). For example, there are several methods
phospholipid mixture which is generally obtained by hy- that exist for refining crude soybean oil (British Patent
drating with water and removing the resultant gums 20 No. 1,509,543, U.S. Patent No. 3,878,232). There is also
formed by centrifugation from neutral triglyceride oil. One a process (British Patent No. 1,509,543) in which a crude
of the primary sources of lecithin is crude soybean oil. hexane extract of the soybean, soybean oil miscella, is
[0003] Other oil bearing seeds such as corn germ and ultra-filtered under pressure through a suitable semiper-
rapeseed yield lecithins, but are of lesser importance meable membrane that allows the passage of a glyceride
commercially. Lecithin produced by drying the gums con- 25 oil solution in hexane, but retains all the phospholipids
tains 25-35% neutral triglycerides and 65-75% phos- together with sugars, sterol glucosides, etc., which form
phatides, and is a plastic or viscous fluid product. This co-micelles with phospholipids in hexane solution. This
65-75% phosphatides is referred to as 65-75% AI (ace- process allows, a separation of phosphorous free lipids
tone insolubles) due to the fact that in general the phos- (e.g., triglycerides) from phospholipids and non-lipids
phatide fraction is insoluble in acetone. It is tested using 30 (e.g., sugars) associated with them. The removal of hex-
AOCS (American Oil Chemists’ Society) Method Ja 4-46. ane from the ultra-filtrate yields an oil free of phosphati-
[0004] In many applications, a solid granular or pow- des, whereas the retentate miscella yields commercial
dered product is desired. Such a product can be made lecithin after hexane is removed.
by removing the neutral triglyceride oil from the lecithin. [0009] DD-A-275461 describes a method for the sep-
The art separates the oil by extracting with acetone ("Lec- 35 aration of phosphatide mixtures in phosphatide class
ithins", B. Szuhaj and G. List, American Oil Chemists preparations by means of ultrafiltration on a membrane.
Society, 1985) and this is referred to as acetone deoiling. [0010] US-A-4 093 540 describes methods for refining
Until now, acetone deoiling has been the only commer- glyceride oil compositions by ultrafiltration.
cially viable process for such preparation. Acetone de- [0011] JP-A-62 039 594 describes the production of
oiling suffers problems, however, in that as a solvent, 40 high-purity powdery lecithin.
acetone has a degree of toxicity. Additionally, residual [0012] None of the methods currently being used result
amounts of acetone can remain in deoiled lecithin at lev- in as pure or desirable a food grade lecithin as the process
els of 5-10 ppm after desolventizing. Furthermore mesityl of the claimed invention because the known methods
oxide, an acetone condensation product, can be present result in lower quality deoiled lecithin that can have an
which imparts a significant off flavor. The acetone deoiled 45 off flavor. Additionally, for currently produced lecithin in-
product must be analyzed routinely to carefully monitor cluding deoiled lecithin chemical bleaching agents much
both acetone and mesityl oxide residuals. as hydrogen peroxide must be used to produce an ac-
[0005] Because of the disadvantages associated with ceptable light colored product. Therefore, the claimed
acetone extraction, alternative methods have been con- process is easier to use for the commercial preparation
sidered for processing of crude lecithin, such as using 50 of deoiled food grade lecithin.
extraction with hydrocarbons (3-4 carbon atoms) under
pressure (1-8 Mpa) with temperatures of from 20-100° Summary of the Invention
C. (U.S. Patent No. 5,597,602). Also the use of high pres-
sure carbon dioxide has been suggested (DE-A 30 11 [0013] The invention concerns the separation and re-
185). 55 fining of phosphatides, in particular soybean phosphati-
[0006] Lipids may be separated from non-lipids and des to an oil-free state without the use of acetone as an
neutral lipids may be separated from polar lipids, espe- extracting agent. It has been found that the claimed in-
cially phospholipids can be separated from neutral trig- vention results in a higher quality lecithin that is made by

2
3 EP 1 137 650 B1 4

a process that can be easily applied to commercial prep- not limited to phosphatidyl choline, phosphatidyl eth-
arations. anolamine, phosphatidyl serine, phosphatidyl inositol,
[0014] The invention is first directed to a method for phosphatidyl glycerol, diphosphatidyl glycerol, N-acyl-
producing deoiled phosphatides, wherein the method phosphatidyl ethanolamine, phosphatidic acid and plas-
does not use acetone and the retentate is decolorized 5 malogen.
following physical separation. [0026] Oil-free refers to lecithin with commercial re-
[0015] The invention is further directed to a method for sidual oil specification of less than 3% oil. Deoiling is the
producing deoiled phosphatides wherein the method process used to remove the oil from the starting material.
comprises a further step of agglomeration. [0027] Lecithin generally refers to a complex, natural-
[0016] The invention is further directed to a method of 10 ly occurring mixture of phosphatides obtained by water-
making phosphatides where a drum desolventizer is washing crud vegetable oil and separating and drying
used. Preferably the drum desolventizer is chrome-plat- the hydrated gums. They generally includes neutral trig-
ed iron or stainless steel. lyceride oil unless otherwise stated such as deoiled or
[0017] The invention is further directed to methods of granular, in which case the neutral oil has been removed.
making phosphatides wherein there is a residual solvent 15 Soybean oil is the largest source of commercial lecithin.
concentration of less than 5 ppm. Other common oils yielding lecithins of lesser importance
[0018] The invention is further directed to a method for are corn, cottonseed, linseed, peanut, canola (rape-
producing deoiled phosphatides, wherein the method seed), safflower and sunflower. Lecithins, ed. Szhuhaj
does not use acetone, there is agglomeration of the phos- and List American Oil Chemists Society, 1985.
phatide and the retentate may not be decolorized follow- 20 [0028] Modified Lecithin refers to but is not limited to
ing physical separation. acetylation, hydroxylation, hydrogenation, hydrolysis
[0019] A preferable embodiment for all the claimed products of lecithin, chlorination, bromination, iodination,
methods is directed to the making of lecithin. A more halogenation, phosphorylation and sulfonation as well as
preferred embodiment is drawn to methods of making any other modification known to those in the art as for
lecithin that is >90 A.I. 25 example found in Lecithins, (eds. Szuhaj and G. List,
[0020] Also disclosed is a food grade or pharmaceuti- pages 203-208, American Oil Chemists Society, 1985,)
cal grade lecithin, preferably characterized by >90 A.I. all of which is incorporated herein by reference. Lecithin
contains a number of chemical functional groups that
Definitions make it suscepible to a variety of chemical reactions.
30 These groups include carbon-carbon double bonds, es-
[0021] In order to provide a clear and consistent un- ters, phosphonate esters, amines and hydroxyl groups.
derstanding of the specification and claims, including the Modification may also result in interesterified lecithin. Ad-
scope to be given such terms, the following definitions ditionally, lecithins may be enzyme modified.
are provided. [0029] Permeate refers to material that passes
[0022] A.I. refers to "acetone insoluble matter" and is 35 through a membrane filter.
used as a measurement of purification. Crude lecithin is [0030] Phosphatides (Phospholipids) refers to but
defined as having an A.I. of 40-90. A.I. can be determined are not limited to mixtures of phosphatidyl choline, phos-
by one of skill in the art by using AOCS (American Oil phatidyl ethanolamine, phosphatidyl serine, phosphati-
Chemists’ Society Method Ja 4-46. dyl inositol, phosphatidic acid, N-acylphosphatidyl eth-
[0023] Bleaching Earth refers to various mined clays. 40 anolamine and other related minor constituents.
These clays undergo commercial processing. Process- [0031] Retentate refers to material that does not pass
ing steps may include, but are not limited to such things through a membrane filter.
as calcining, washing, drying, particle sizing and activa-
tion using various chemical treatments, as well as others Detailed Description of the Invention
performed by the commercial supplier. Bleaching earths 45
may be readily obtained from commercial vendors (e.g. [0032] The present invention relates to deoiled phos-
Süd Chemie, Germany) known to those of skill in the art. phatides; food grade or pharmaceutical grade lecithin;
As an alternative to bleaching earths one could also use and methods for producing same.
chemical means such as carbon, activated carbon, res- [0033] In one embodiment, the present invention re-
ins, chemical methods including but not limited to sodium 50 lates to a method for producing deoiled phosphatides,
hypochloride, peroxides and peracids. the method not using acetone as a solvent and compris-
[0024] Food and Pharmaceutical Grade Lecithin ing:
refers to lecithin having no residual acetone and that is
>90 A.I. a) mixing a crude phosphatide preparation with an
[0025] Fractionated Lecithins refers to lecithins sep- 55 alkane;
arated into subclasses or enriched fractions of lecithins. b) separating triglycerides from phosphatides
The subclasses or enriched fractions may be a mixture through a membrane;
enriched in phospholipids comprising one or more but c) obtaining a retentate following separation;

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5 EP 1 137 650 B1 6

d) decolorizing the retentate with bleaching earth. preferably, less than 1 ppm, or less than 0.1 ppm).
e) evaporating the alkane from the retentate. [0042] Preferably the above described methods use a
drum desolventizer to remove the alkane. More prefera-
[0034] Preferably, the above-described method fur- bly the drum desolventizer is chrome-plated cast iron or
ther comprises the step of granulating in a powder ag- 5 stainless steel.
glomerator. [0043] Preferably, the crude phosphatide used in the
[0035] In another embodiment, the present invention above-described methods is from a vegetable selected
relates to a method for producing deoiled phosphatides, from the group consisting of soybean, corn, cotton-seed,
the method not using acetone as a solvent and compris- linseed, peanut, canola, rapeseed, safflower and sun-
ing: 10 flower.
[0044] Preferably, the crude lecithin used in the above-
a) mixing a crude phosphatide preparation with an described methods is from a vegetable selected from the
alkane; group consisting of soybean, corn, cotton-seed, linseed,
b) separating triglycerides from phosphatides peanut, canola, rapeseed, safflower and sunflower.
through a membrane; 15 [0045] Preferably, the mixed tocopherols used in the
c) obtaining a retentate following separation; above-described methods are added after bleaching and
d) evaporating the alkane from the retentate; and before evaporating the alkane from the retentate.
e) granulating in a powder agglomeration. [0046] Membrane separation technology is increas-
ingly used in the refining of edible oils. Such technology
[0036] In a further embodiment, the present invention 20 allows for the physical separation of phosphatides or lec-
relates to a method for producing food grade or pharma- ithin from other products in the crude starting material.
ceutical grade deoiled lecithin, the method not using ac- The application of this technology and the membranes
etone as a solvent and comprising: used in this technology are known to one of skill in the
art and have been described in several publications. For
a) mixing crude lecithin with an alkane; 25 example, see Japanese Application No. Showa
b) separating triglycerides from phosphatides 63-308882, December 8, 1988, laid open June 15, 1990:
through a membrane; Kosseoglu, et al., JAQCS 67:315-322 (1990): Iwama,
c) obtaining a retentate following separation; Proceedings of World Conf. Biotechnol. Fats and Oils
d) decolorizing the retentate with bleaching earth. Ind. 88.00,00 244-50 (1988). The choice of the specific
e) evaporating the alkane from the retentate. 30 membrane to use will obviously depend upon the solvent
system being used to separate the components of inter-
[0037] Preferably, the above-described method fur- est. The main criteria for selection of the membrane is
ther comprises the step of granulating in a powder ag- that it is resistant to the solvent being used and also al-
glomerator. lows the unwanted materials to pass through, thereby
[0038] In another embodiment, the step involving de- 35 leaving the desired phospholipids on the retentate side.
coloring with bleaching earth is replaced (either before [0047] The employment of a membrane (preferably,
evaporating or at an appropriate point in the method) with resistant to the solvent being used) is the principle means
alternative decolorizing agents such as carbon, activated of physically separating the triglyceride from the phos-
carbon, resins or chemical means included but not limited phatides in a solvent based system where crude lecithin
to use of peroxided sodium hypochorite or peracids. 40 comprising a range of 40-90 A.I. phosphatides is mixed
[0039] In another embodiment, the present invention with commercial solvent (preferably, in a 1:1 mass ratio).
relates to a method for producing a food grade or phar- [0048] Many membrane types can be used effectively
maceutical grade of deoiled lecithin, the method not using over a wide range of molecular weight cutoff. These in-
acetone as a solvent and comprising: clude polysufones, polyamide, cellulose, polypropylene,
45 polyvinylidine fluoride (PVDF), membranes on aluminum
a) mixing crude lecithin with an alkane; and other commercially available filters.
b) separating triglycerides from phosphatides [0049] Preferably, the membrane has a molecular
through a membrane; weight cutoff of 50,000 daltons or less. More preferably
c) obtaining a retentate following separation; the membrane has a molecular weight cutoff of 10,000
d) evaporating the alkane from the retentate; and 50 daltons.
e) granulating in a powder agglomeration. [0050] Also preferably, the membrane is compatible
with the solvents described herein.
[0040] Preferably, the phosphatide or lecithin obtained [0051] Further preferably, the membrane used in the
by the above-described methods is virtually oil free and above-described methods is a polyvinylidine fluoride
is > 90 acetone insoluble matter (A.I.) (more preferably, 55 (PVDF) membrane.
> 97 A.I., > 99 A.I. or > 99.9 A.I.). [0052] Preferably, the alkane used in the above-de-
[0041] Preferably, the above-described methods have scribed methods is an alkane with 3-8 carbons. More
a residual solvent concentration of less than 5 ppm (more preferably, the alkane used in the above-described meth-

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7 EP 1 137 650 B1 8

ods is selected from the group consisting of hexane, hep- ventizing step is performed at a temperature such that
tane, pentane, propane, isooctane, butane, isohexane darkening of the lecithin does not occur. A fluid bed dryer
and cyclohexane. Alternatively supercritical CO2 alone is used and insures solvent residuals of less than 5 ppm.
or with modifiers (e.g. other solvents) may be used as From this dryer, flakes are conveyed to storage bins prior
well. 5 to granulation and/or grinding. The product is generally
[0053] The separation yields a permeate consisting of agglomerated to granules of two mesh sizes. These may
triglycerides and hexanes. The solvent is evaporated and be formed with the use of any of the following equipment:
the resulting oil is of higher quality when compared to the tumble agglomerators, extrudeers, disk pellitizers, flow
oil recovered in the acetone extraction process. This is through mixing agglomerators, fluid bed agglomerators
due to lack of an off odor or of the mesityl oxide noted 10 and powder agglomerators. Other agglomerators known
above. In addition commercial hexane is used in the ex- to those of skill in the art could also be used. A powder
traction of crude oil from oil bearing seeds and seed by- agglomeration is used to make two of the sizes of gran-
products. Thus by using hexane for both processes (i.e. ules. A Shugii flexomix is currently preferred. A powdered
preparation of the oil-free phosphatide and the oil per- form of the product can be easily ground directly from
meate,) the additional separate solvent system for ace- 15 the flakes.
tone is not needed resulting in a cost savings. The reten- [0060] In a further embodiment, the present invention
tate consists of virtually oil free (>90 A.I.) phosphatides relates to deoiled phosphatide made by any of the above-
including an enhanced fraction of phosphatidyl choline described methods.
when compared to the acetone derived product. The re- [0061] In another embodiment, the present invention
tentate can be 35-40% phospholipid in 60-65% hexane. 20 relates to a food-grade or pharmaceutical grade lecithin
[0054] Because color bodies which are commercially made by any of the above-described methods. The food-
objectionable remain with the phospholipid fraction dur- grade lecithin may either be used either for animal feed
ing preparation of the phosphatides, a decolorization step or for human consumption.
is used. [0062] Also disclosed is food grade or pharmaceutical
[0055] This optional step also removes other impurities 25 grade lecithin that has no residual acetone, is virtually
which can lead to premature oxidation. This step com- oil-free and is characterized by >90 acetone insoluble
prises the use of bleaching earth. Chlorophylls and xan- matter (A.I.) (more preferably, > 97 A.I., > 99 A.I. or >
thophylls and other prooxidants are absorbed, bleached 99.9 A.I.).
or removed in this process. The earth is added to a vessel [0063] None of the information provided above or in
containing a 35-40% deoiled concentrate in hexane. A 30 the examples below should be construed in any way to
typical rate of addition is 5-8% earth on a phospholipid limit the scope of the claims.
mass basis. The color bodies physically adsorb to the
clay. The clay is then separated from the deoiled con- Example 1
centrate via dead end filtration.
[0056] If antioxidants are added to provide increased 35 [0064] To obtain a deoiled lecithin preparation, crude
stability for the deoiled product, this point in the process- lecithin was mixed with commercial hexane. The triglyc-
ing is a convenient opportunity to add them while the erides were separated from the phosphatides through a
phosphatides are still in solution prior to evaporation of PVDF membrane (e.g. from Advanced Membrane Tech-
the solvent. Accordingly, antioxidants are preferably add- nologies, Cal.) having a molecular weight cutoff of
ed before evaporating the hexane from the solvent. Pre- 40 10,000-50,000 daltons. The retentate consisted of virtu-
ferred antioxidants are mixed tocopherols, however, oth- ally oil free (>90 A.T.) phosphatides and was 35-40 %
ers would be known to those of skill in the art. phospholipid in 60-65 % hexanes.
[0057] Desolventizing removes the hexanes from the [0065] The preparation was decolorized with bleach-
purified oil-free phospholipids. Many different means can ing earth. The degree of decolorization will depend upon
be used to desolventize the product. These include but 45 the wants and needs of those of skill in the art. The
are not limited to spray dryers, fluid bed driers with or bleaching earth was added to a vessel containing a
without vibration, drum driers, belt driers, tumble driers, 35-40% deoiled concentrate in hexane. A typical rate of
all of these can be either batch or continuous. addition was 5-8% earth on a phospholipid mass basis.
[0058] Of key importance to the process is the use of Tocopherols and/or antioxidants can be added at this
drum desolventizers. The desolventizing drums can be 50 point. Preferably mixed tocopherols are added.
chrome-plated cast iron or stainless steel. Low pressure [0066] Of importance to the process is desolventizing.
steam is added as the heat source. The refined deoiled Desolventizing drums were chrome-plated cast iron or
concentrate is added to the nip of the rolls and as the stainless steel. Low pressure steam was added as the
hexane evaporates, the phospholipids adhere to the rolls. heat source. The refined deoiled concentrate was added
[0059] A doctor knife scrapes the product from each 55 to the nip of the rolls and as the hexane evaporates, the
drum. The solvent vapor is captured and condensed for phospholipids adhered to the rolls.
reuse. The deoiled flakes are conveyed to the subse- [0067] The desolventizing step was performed at a
quent drying step for final hexane removal. This desol- temperature such that darkening of the lecithin did not

5
9 EP 1 137 650 B1 10

occur. A fluid bed dryer was used and insured solvent b) separating triglycerides from phosphatides
residuals of less than 5 ppm. From this dryer, flakes were through a membrane;
conveyed to storage bins prior to granulation and grind- c) obtaining a retentate containing phospholip-
ing. Granulation was performed in a Shugii agglomerator. ids following separation;
[0068] The finished particles had a U.S. Sieve Size (G 5 d) decolorizing said retentate with bleaching
cut) of -10 to +20; F cut of -20 to +40, while a finished earth.
powder product had a U.S. Sieve Size of -40. e) evaporating alkane from said retentate.
[0069] The invention concerns a method of making de-
oiled phosphatides, particularly lecithin and to the phos- 5. The method of claim 4 further comprising the step
phatide or lecithin that is obtained by the process. 10 of granulating in a powder agglomerator.
[0070] All references mentioned herein are incorporat-
ed by reference into the disclosure. 6. A method for producing a food grade or pharmaceu-
[0071] Having now fully described the invention by way tical grade of deoiled lecithin, said method not using
of illustration and example for purposes of clarity and acetone as a solvent and comprising:
understanding, it will be apparent to those of ordinary 15
skill in the art that certain changes and modifications may a) mixing crude lecithin with an alkane;
be made in the disclosed embodiments and such modi- b) separating triglycerides from phosphatides
fications are intended to be within the scope of the through a membrane;
present invention. c) obtaining a retentate containing phospholip-
20 ids following separation;
d) evaporating alkane from said retentate; and
Claims e) granulating in a powder agglomeration.

1. A method for producing deoiled phosphatides, said 7. The method of any one of claims 1-6, wherein said
method not using acetone as a solvent and compris- 25 phosphatide or lecithin obtained by the method is
ing: virtually oil free and is > 90 acetone insoluble matter
(A.I.).
a) mixing a crude phosphatide preparation with
an alkane; 8. The method of claim 7, wherein said phosphatide or
b) separating triglycerides from phosphatides 30 lecithin obtained is > 97 A.I.
through a membrane;
c) obtaining a retentate containing phospholip- 9. The method of any one of claims 1-6, wherein there
ids following separation; is a residual solvent concentration of less than 5 ppm.
d) decolorizing said retentate with bleaching
earth. 35 10. The method of any one of claims 1-6, wherein said
e) evaporating the alkane from said retentate. alkane is selected from the group consisting of al-
kanes with 3-8 carbons, hexane, heptane, pentane,
2. The method of claim 1 further comprising the step propane, isooctane, butane and cyclohexane.
of granulating in a powder agglomerator.
40 11. The method of any one of claims 1-3 wherein said
3. A method for producing deoiled phosphatides, said crude phosphatide is from a vegetable selected from
method not using acetone as a solvent and compris- the group consisting of soybean, corn, cotton-seed,
ing: linseed, peanut, canola, rapeseed, safflower and
sunflower.
a) mixing a crude phosphatide preparation with 45
an alkane; 12. The method of any one of claims 4-6 wherein said
b) separating triglycerides from phosphatides crude lecithin is from a vegetable selected from the
through a membrane; group consisting of soybean, corn, cotton-seed, lin-
c) obtaining a retentate containing phospholip- seed, peanut, canola, rapeseed, safflower and sun-
ids following separation; 50 flower.
d) evaporating alkane from said retentate; and
e) granulating in a powder agglomeration. 13. The method of any one of claims 1-6 wherein mixed
tocopherols are added before evaporating the al-
4. A method for producing food grade or pharmaceuti- kane from the retentate.
cal grade deoiled lecithin, said method not using ac- 55
etone as a solvent and comprising: 14. The method of any one of claims 1-6, wherein said
membrane is a polyvinylidine fluoride (PVDF) mem-
a) mixing crude lecithin with an alkane; brane.

6
11 EP 1 137 650 B1 12

15. The method of claim 14, wherein said membrane a) das Mischen einer rohen Phosphatidzuberei-
has a molecular weight cutoff of 50,000 or less. tung mit einem Alkan;
b) das Abtrennen von Triglyceriden von Phos-
16. The method of any one of claims 1-6, wherein step phatiden durch eine Membran;
"a", is replaced with supercritical CO2 or CO2 with 5 c) das Erhalten eines Retentats, welches Phos-
solvents to separate phosphatides from oil. pholipide enthält, nach der Abtrennung;
d) das Entfärben des Retentats mit Bleicherde;
17. The method of any one of claims 1-6, wherein toco- e) das Abdampfen des Alkans von dem Reten-
pherols are added before evaporating the alkanes. tat.
10
18. The method of any one of claims 1-6, wherein a 2. Verfahren nach Anspruch 1, ferner umfassend den
chrome-plated or stainless steel desolventizing Schritt des Granulierens in einer Pulveragglomerie-
drum is used to remove the alkane. rungsvorrichtung.

19. The method of any one of claims 1-6, wherein the 15 3. Verfahren zur Herstellung von entölten Phosphati-
phosphatide or lecithin is a modified lecithin. den, wobei das Verfahren kein Aceton als Lösungs-
mittel verwendet und umfasst:
20. The method of claim 19 wherein the modified lecithin
is selected from the group comprising acetylated lec- a) das Mischen einer rohen Phosphatidzuberei-
ithin, hydroxylated lecithin, hydrogenated lecithin, 20 tung mit einem Alkan;
hydrolysis products of lecithin, chlorinated lecithin, b) das Abtrennen von Triglyceriden von Phos-
brominated lecithin phosphorylated lecithin, halo- phatiden durch eine Membran;
genated lecithin, sulfonated lecithin, iodinated leci- c) das Erhalten eines Retentats, welches Phos-
thin, interesterfied lecithin and enzyme modified lec- pholipide enthält, nach der Abtrennung;
ithin. 25 d) das Abdampfen des Alkans von dem Reten-
tat; und
21. The method of any one of claims 1, 2, 4 or 5 wherein e) das Granulieren in einer Pulveragglomerie-
the decolorizing step is replaced by bleaching with rungsvorrichtung.
a decolorizer selected from the group consisting of
carbon, activated carbon, resins and peroxides. 30 4. Verfahren zur Herstellung von entöltem Lecithin mit
Lebensmittelqualität oder pharmazeutischer Quali-
22. The method of any one of claims 1-6, wherein the tät, wobei das Verfahren kein Aceton als Lösungs-
phosphatide or lecithin is in the form of crude oil mis- mittel verwendet und umfasst:
cella extracted from oil seeds and oil bearing plant
materials. 35 a) das Mischen von rohem Lecithin mit einem
Alkan;
23. The method of any one of claims 1-6, wherein the b) das Abtrennen von Triglyceriden von Phos-
phosphatide or lecithin is derived from an animal phatiden durch eine Membran;
source. c) das Erhalten eines Retentats, welches Phos-
40 pholipide enthält, nach der Abtrennung;
24. The method of any one of claims 1-6, wherein the d) das Entfärben des Retentats mit Bleicherde;
phosphatide or the lecithin is a fractioned lecithin. e) das Abdampfen des Alkans von dem Reten-
tat.
25. The method of claim 24 wherein the fractionated lec-
ithin is selected from the group consisting of phos- 45 5. Verfahren nach Anspruch 4, ferner umfassend den
phatidyl choline, phosphatidyl ethanolamine, phos- Schritt des Granulierens in einer Pulveragglomerie-
phatidyl serine, phosphatidyl inositol, phosphatidyl rungsvorrichtung.
glycerol, diphosphatidyl glycerol, N-acylphosphati-
dyl ethanolamine, phosphatidic acid and plasmalo- 6. Verfahren zur Herstellung einer Lebensmittelqualität
gen 50 oder pharmazeutischen Qualität von entöltem Leci-
thin, wobei das Verfahren kein Aceton als Lösungs-
mittel verwendet und umfasst:
Patentansprüche
a) das Mischen von rohem Lecithin mit einem
1. Verfahren zur Herstellung von entölten Phosphati- 55 Alkan;
den, wobei das Verfahren kein Aceton als Lösungs- b) das Abtrennen von Triglyceriden von Phos-
mittel verwendet und umfasst: phatiden durch eine Membran;
c) das Erhalten eines Retentats, welches Phos-

7
13 EP 1 137 650 B1 14

pholipide enthält, nach der Abtrennung; geben werden.


d) das Abdampfen des Alkans von dem Reten-
tat; und 18. Verfahren nach einem der Ansprüche 1 bis 6, wobei
e) das Granulieren in einer Pulveragglomerie- eine verchromte oder Edelstahl-Trommel zur Entfer-
rungsvorrichtung. 5 nung von Lösungsmittel zur Entfernung des Alkans
verwendet wird.
7. Verfahren nach einem der Ansprüche 1 bis 6, wobei
das Phosphatid oder Lecithin, welches durch das 19. Verfahren nach einem der Ansprüche 1 bis 6, wobei
Verfahren erhalten wird, praktisch frei von Öl ist und das Phosphatid oder Lecithin ein modifiziertes Leci-
> 90 Acetonunlösliches Material (A.I.) aufweist. 10 thin ist.

8. Verfahren nach Anspruch 7, wobei das Phosphatid 20. Verfahren nach Anspruch 19, wobei das modifizierte
oder Lecithin, welches erhalten wird, > 97 A.I. auf- Lecithin aus der Gruppe ausgewählt ist, welche ace-
weist. tyliertes Lecithin, hydroxyliertes Lecithin, hydriertes
15 Lecithin, Hydrolyseprodukte von Lecithin, chlorier-
9. Verfahren nach einem der Ansprüche 1 bis 6, wobei tes Lecithin, bromiertes Lecithin, phosphoryliertes
eine Lösungsmittelrestkonzentration von niedriger Lecithin, halogeniertes Lecithin, sulfoniertes Leci-
als 5 ppm vorhanden ist. thin, iodiertes Lecithin, umgeestertes Lecithin und
Enzym-modifiziertes Lecithin umfasst.
10. Verfahren nach einem der Ansprüche 1 bis 6, wobei 20
das Alkan aus der Gruppe ausgewählt ist, welche 21. Verfahren nach einem der Ansprüche 1, 2, 4 oder 5,
aus Alkanen mit 3 bis 8 Kohlenstoffen, Hexan, Hep- wobei der Entfärbungsschritt ersetzt wird durch Blei-
tan, Pentan, Propan, Isooctan, Butan und Cyclohe- chen mit einem Entfärbungsmittel, welches aus der
xan besteht. Gruppe ausgewählt ist, die aus Kohlenstoff, Aktiv-
25 kohle, Harzen und Peroxiden besteht.
11. Verfahren nach einem der Ansprüche 1 bis 3, wobei
das rohe Phosphatid von einem Pflanzenmaterial 22. Verfahren nach einem der Ansprüche 1 bis 6, wobei
stammt, welches aus der Gruppe ausgewählt ist, die das Phosphatid oder Lecithin in der Form von roher
aus Sojabohne, Getreide, Baumwollsamen, Leinsa- Ölmiszella, extrahiert aus Ölsamen und Öl-enthal-
men, Erdnuss, Canola, Raps, Färberdistel (Saflor) 30 tenden Pflanzenmaterialien, vorliegt.
und Sonnenblume besteht.
23. Verfahren nach einem der Ansprüche 1 bis 6, wobei
12. Verfahren nach einem der Ansprüche 4 bis 6, wobei das Phosphatid oder Lecithin von einer Tierquelle
das rohe Lecithin von einem Pflanzenmaterial abgeleitet ist.
stammt, welches aus der Gruppe ausgewählt ist, die 35
aus Sojabohne, Getreide, Baumwollsamen, Leinsa- 24. Verfahren nach einem der Ansprüche 1 bis 6, wobei
men, Erdnuss, Canola, Raps, Färberdistel (Saflor) das Phosphatid oder das Lecithin ein fraktioniertes
und Sonnenblume besteht. Lecithin ist.

13. Verfahren nach einem der Ansprüche 1 bis 6, wobei 40 25. Verfahren nach Anspruch 24, wobei das fraktionierte
vor dem Abdampfen des Alkans von dem Retentat Lecithin aus der Gruppe ausgewählt ist, welche aus
Tocopherolgemische zugegeben werden. Phosphatidylcholin, Phosphatidylethanolamin,
Phosphatidylserin, Phosphatidylinositol, Phosphati-
14. Verfahren nach einem der Ansprüche 1 bis 6, wobei dylglycerol, Diphosphatidylglycerol, N-Acylphos-
die Membran eine Polyvinylidinfluorid (PVDF)-Mem- 45 phatidylethanolamin, Phosphatidsäure und Plasma-
bran ist. logen besteht.

15. Verfahren nach Anspruch 14, wobei die Membran


einen Molekulargewichtsgrenzwert von 50.000 oder Revendications
niedriger aufweist. 50
1. Procédé de production de phosphatides déshuilés,
16. Verfahren nach einem der Ansprüche 1 bis 6, wobei ledit procédé n’utilisant pas d’acétone comme sol-
Schritt "a" mit überkritischem CO2 oder CO2 mit Lö- vant et comprenant :
sungsmitteln ersetzt wird, um Phosphatide von Öl
abzutrennen. 55 a) le mélange d’une préparation de phosphatide
brute avec un alcane ;
17. Verfahren nach einem der Ansprüche 1 bis 6, wobei b) la séparation des triglycérides d’avec les
vor dem Abdampfen der Alkane Tocopherole zuge- phosphatides à travers une membrane ;

8
15 EP 1 137 650 B1 16

c) l’obtention d’un rétentat contenant des phos- 1-6 dans lequel le phosphatide ou la lécithine obtenu
pholipides après la séparation ; (e) par le procédé est presque totalement exempt(e)
d) la décoloration dudit rétentat avec une terre d’huile et est contient plus de 90 % de matière inso-
de blanchiment ; luble dans l’acétone (A.I).
e) l’évaporation de l’alcane dudit rétentat. 5
8. Procédé selon la revendication 7, dans lequel ledit
2. Procédé selon la revendication 1, comprenant en phosphatide ou la lécithine obtenu(e) contient plus
outre l’étape de granulation dans un agglomérateur de 97 % d’A.I.
de poudre.
10 9. Procédé selon l’une quelconque des revendications
3. Procédé de production de phosphatides déshuilés, 1-6, dans lequel il existe une concentration de sol-
ledit procédé n’utilisant pas d’acétone comme sol- vant résiduelle inférieure à 5 ppm.
vant et comprenant :
10. Procédé selon l’une quelconque des revendications
a) le mélange d’une préparation de phosphatide 15 1-6, dans lequel ledit alcane est choisi dans le groupe
brute avec un alcane ; constitué d’alcanes avec 3-8 atomes de carbone,
b) la séparation des triglycérides d’avec les d’hexane, d’heptane, de pentane, de propane,
phosphatides à travers une membrane ; d’isooctane, de butane et de cyclohexane.
c) l’obtention d’un rétentat contenant des phos-
pholipides après séparation ; 20 11. Procédé selon l’une quelconque des revendications
d) l’évaporation de l’alcane dudit rétentat ; et 1-3, dans lequel ledit phosphatide brut provient d’un
e) la granulation dans un agglomérateur de pou- végétal choisi dans le groupe constitué de soja,
dre. maïs, graine de coton, graine de lin, arachide, cano-
la, colza, carthame et tournesol.
4. Procédé de production d’une lécithine déshuilée de 25
qualité alimentaire ou pharmaceutique, ledit procédé 12. Procédé selon l’une quelconque des revendications
n’utilisant pas d’acétone comme solvant et 4-6, dans lequel ladite lécithine brute provient d’un
comprenant : végétal choisi dans le groupe constitué de soja,
maïs, graine de coton, graine de lin, arachide, cano-
a) le mélange d’une lécithine brute avec un 30 la, colza, carthame et tournesol.
alcane ;
b) la séparation des triglycérides d’avec les 13. Procédé selon l’une quelconque des revendications
phosphatides à travers une membrane ; 1-6, dans lequel des tocophérols mélangés sont
c) l’obtention d’un rétentat contenant des phos- ajoutés avant évaporation de l’alcane du rétentat.
pholipides après séparation ; 35
d) la décoloration dudit rétentat avec une terre 14. Procédé selon l’une quelconque des revendications
de blanchiment ; 1-6, dans lequel ladite membrane est une membrane
e) l’évaporation de l’alcane dudit rétentat. de poly(fluorure de vinylidine) (PVDF).

5. Procédé selon la revendication 4, comprenant en 40 15. Procédé selon la revendication 14, dans lequel ladite
outre l’étape de granulation dans un agglomérateur membrane a une masse moléculaire de 50 000 ou
de poudre. moins.

6. Procédé de production d’une lécithine déshuilée de 16. Procédé selon l’une quelconque des revendications
qualité alimentaire ou pharmaceutique, ledit procédé 45 1-6, dans lequel l’étape « a » est remplacée par un
n’utilisant pas l’acétone comme solvant et traitement avec du CO2 supercritique ou avec du
comprenant : CO2 avec solvants pour séparer les phosphatides
de l’huile.
a) le mélange de lécithine brute avec un alcane ;
b) la séparation de triglycérides d’avec les phos- 50 17. Procédé selon l’une quelconque des revendications
phatides à travers une membrane ; 1-6, dans lequel des tocophérols sont ajoutés avant
c) l’obtention d’un rétentat contenant des phos- évaporation des alcanes.
pholipides après la séparation ;
d) l’évaporation de l’alcane dudit rétentat ; et 18. Procédé selon l’une quelconque des revendications
e) la granulation dans un agglomérateur de pou- 55 1-6, dans lequel un tambour de désolvantation en
dre. acier inoxydable ou plaqué de chrome est utilisé pour
enlever l’alcane.
7. Procédé selon l’une quelconque des revendications

9
17 EP 1 137 650 B1 18

19. Procédé selon l’une quelconque des revendications


1-6, dans lequel le phosphatide ou la lécithine est
une lécithine modifiée.

20. Procédé selon la revendication 19, dans lequel la 5


lécithine modifiée est choisie dans le groupe com-
prenant de la lécithine acétylée, de la lécithine hy-
droxylée, de la lécithine hydrogénée, des produits
d’hydrolyse de lécithine, de la lécithine chlorée, de
la lécithine bromée, de la lécithine phosphorylée, de 10
la lécithine halogénée, de la lécithine sulfonée, de
la lécithine iodée, de la lécithine inter-estérifiée et de
la lécithine modifiée par enzyme.

21. Procédé selon l’une quelconque des revendications 15


1, 2, 4 ou 5, dans lequel l’étape de décoloration est
remplacée par un blanchiment avec un agent déco-
lorant choisi dans le groupe constitué de carbone,
de charbon actif, de résines et de peroxydes.
20
22. Procédé selon l’une quelconque des revendications
1-6, dans lequel le phosphatide ou la lécithine est
sous la forme de micelles d’huile brute extraite de
graines d’oléagineux et de matériaux végétaux con-
tenant de l’huile. 25

23. Procédé selon l’une quelconque des revendications


1-6, dans lequel le phosphatide ou la lécithine est
dérivé(e) d’une source animale.
30
24. Procédé selon l’une quelconque des revendications
1-6, dans lequel le phosphatide ou la lécithine est
une lécithine fractionnée.

25. Procédé selon la revendication 24, dans lequel la 35


lécithine fractionnée est choisie dans le groupe cons-
titué de phosphatidyl choline, de phosphatidyl étha-
nolamine, de phosphatidyl sérine, de phosphatidyl
inositol, de phosphatidyl glycérol, de diphosphatidyl
glycérol, de N-acylphosphatidyl éthanolamine, d’aci- 40
de phosphatidique et de plasmalogène.

45

50

55

10
EP 1 137 650 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• US 5597602 A [0005] • US 3878232 A [0008]


• DE 3011185 A [0005] • DD 275461 A [0009]
• US 4496489 A [0008] • US 4093540 A [0010]
• US 4062882 A [0008] • JP 62039594 A [0011]
• US 4533501 A [0008] • JP SHOWA63308882 B [0046]
• GB 1509543 A [0008]

Non-patent literature cited in the description

• B. Szuhaj ; G. List. Lecithins. American Oil Chemists • Kosseoglu et al. JAQCS, 1990, vol. 67, 315-322
Society, 1985 [0004] [0046]
• Lecithins. American Oil Chemists Society, 1985 • Iwama. Proceedings of World Conf. Biotechnol. Fats
[0027] and Oils Ind., 1988, vol. 88.00,00, 244-50 [0046]
• Lecithins. American Oil Chemists Society, 1985,
203-208 [0028]

11