US3632351A

US3632351A - Method for treating with tannin oleaginous and proteinic material of vegetable origin, and products obtained by said method

Info

Publication number: US3632351A
Application number: US711885A
Authority: US
Inventors: Zelmen Zelter; Jean Delort-Laval; Jean Lassonnery; Jacques Rodeaud
Original assignee: Institut National de la Recherche Agronomique INRA
Current assignee: Institut National de la Recherche Agronomique INRA
Priority date: 1967-03-10
Filing date: 1968-03-11
Publication date: 1972-01-04
Anticipated expiration: 1989-01-04
Also published as: GB1189754A; DE1692003A1; FR1523268A; NL6803398A; OA02759A; NL158841B; BE711923A

Abstract

Treatment of oleaginous and proteinic vegetable substances by adding a tannin-containing substance thereto, submitting the vegetable substance to mechanical pressure and friction forces in the presence of water at a temperature higher than normal ambient temperature while adjusting the amount of water such that it corresponds to a moisture content of about 10-15 percent of the vegetable substance, and separating the oily constituents from the proteinic constituents.

Description

United States Patent [72] Inventors Zelrnen Zelter Paris; Jean Delort-Laval, La Verriere; Jean Lassonnery, Saint Junien; Jacques Rodeaud, Chabanais, all of France [21] AppLNo. 711,885 [22] Filed Mar. 11, 1968 [45] Patented Jan. 4, 1972 [731 Assignees Institut National de la Recherche Agronomique Paris, Prodults Chlmlques et Celluloses Rey Vellzy-Vlllacouhlny, Yvelines, France [32] Priority Mar. 10, 1967 [3 3] France 3 1 1 98223 [54] METHOD FOR TREATING WITl-I TANNIN OLEAGINOUS AND PROTEINIC MATERIAL OF VEGETABLE ORIGIN, AND PRODUCTS 2,354,719 8/1944 Verbeck 3,507,662 4/1970 Leroy et al 99/2 2,288,662 7/1942 Weigel 260/4122 2,533,858 12/1950 Weigel 260/4122 2,618,643 11/1952 Dunning 260/4122 3,437,488 4/1969 I-Iumphreys 99/3 FOREIGN PATENTS 1,453,261 9/1966 France 1,461,364 11/1966 France OTHER REFERENCES Animal Foodstuffs, Harry De Moor, Chemical Abstracts, Vol. 65, 1966, column 20761.

Feeds Resulting From The Reaction Between Nitrogencontaining And Tannin-containing Substances," R. A. Cardenas, Chem. Absts., Vol. 67, 1967, article 2286e.

Protection Of Dietary Proteins From Rumen Bacterial Deamination. Artificial Rumen Studies," Dv l-I. Cox, Chem. Absts., Vol.65, 1964, article 16557h.

C R. Acad. Aug. 24, 1964, pp. 1,592- 1,595.

Primary Examiner-Norman Yudkoff Assistant ExaminerCurtis P. Ribando Attorney-Holman & Stern ABSTRACT: Treatment of oleaginous and proteinic vegetable substances by adding a tannin-containing substance thereto, submitting the vegetable substance to mechanical pressure and friction forces in the presence of water at a temperature higher than normal ambient temperature while adjusting the amount of water such that it corresponds to a moisture content of about 10-15 percent of the vegetable substance, and separating the oily constituents from the proteinic constituents.

METHOD FOR TREATING WITH TANNIN OLEAGINOUS AND PROTEINIC MATERIAL OF VEGETABLE ORIGIN, AND PRODUCTS OBTAINED BY SAID METHOD The present invention relates to vegetable, oleaginous, proteinic substances and, more particularly, to the industrial fields concerned with oils, vegetable fats, oil cakes and other products abstracted from fruit, seeds, and other oleaginous, proteinic vegetable substances.

The invention has for its object a method for improving the raw materials and products of the industrial treatment of oleaginous and proteinic vegetable substances, said method comprising the steps of treating said substances with at least one tannin-containing substance, and then separating the oily and greasy substances contained in the treated vegetable substances. The tannin-containing substances may be mixed with the vegetable substances and the resulting mixture submitted to mechanical pressure and friction stresses in the presence of water, at a temperature higher than the normal ambient temperature.

The treatment according to the invention may be carried out by using a solid powderous tannin-containing substance, or a concentrated solution of a tannin-containing substance, and particularly by using natural or synthetic tannin-containing extracts; tannin-containing raw vegetable substances may also be used.

The novel treatment may advantageously be carried out at a temperature higher than 50 C., the moisture contents of the mixture constituted by the vegetable and the tannin-containing substances being comprised between and percent.

For the treatment of vegetable substances, such as peanuts, sunflower, colza, cotton, soya, linseed, amounts of about 3 to percent of the tanning extract may be used.

In the treatment of seed such treatment is advantageously carried out after peeling or decortication of the grains.

The tannin-containing substance may be added to oleaginous substances during the oil-making operations, particularly prior to the calendering or pressing operations.

The method according to the invention allows for producing improved vegetable oils and fats, and oil-free vegetable cakes having a higher nutritive value due to the protection of the proteinic substances against bacterial deamination in the rumen.

The invention has also for its object the oils, fats, cakes, and other products extracted from oleaginous proteinic substances by means of the method hereinabove, as well as fruit, seeds, and other vegetable oleaginous proteinic substances treated with a tannin-containing substance, in accordance with the above-mentioned method.

In accordance with known methods, oil cakes are treated with tannincontaining substances with a view to improving their nutritive properties by rendering the proteins insoluble and forming with the latter complex substances which are inaccessible to the bacterial deaminases, but which can be dissociated by the proteolytic enzymes of the digestive tract.

Such tannin treatment of the oil cakes involves no danger for the animal but considerably improves the nutritive properties of the cake, especially where ruminants are concerned, as the latter are particularly subject to bacterial deamination in the rumen.

The tannin-containing substance may be constituted by a raw tanning extract, or by a tanning extract in the form of a powder, a paste, a suspension, a dispersion, or a solution in any convenient solvent.

The amounts of tannin-containing substance to be used will vary according to the amount of tannin which they contain. The type of tannin-containing substance to be used will depend on the nature of the oleaginous seed to be treated and on the proneness of the proteins to be deaminated. The said amounts must be sufiicient for rendering practically insoluble the proteins and prevent the partial or total conversion of the proteins into ammoniac by the action of the micro-organisms in the digestive tract of the animal.

For the treatment of peanut, sunflower and soya the maximum such amount is about 15 percent. For the treatment of colza, said amount is about 12 percent, and for the treatment oflinseed, an amount of only 6 percent will be used.

These amounts are optimum amounts from a technical point of view; they may be reduced on the ground of economical considerations, however, such decrease will result in a decrease of the improvement of the treated product.

The method according to the invention provides not only for improvement of the value of the proteins, but also for improvement of the conditions of its extraction and of the properties of the extracted oils and fats. The tannin-containing substances may be used in the form of powders, pastes, suspensions or solutions; they may also be used in the form of raw tannin substances, provided they contain a sufficient amount of tannin for protecting the protein of the seed and other oleaginous proteinic vegetable substances without altering the nutritive properties of the resulting products such as oil cakes and oils.

The tannin-containing substances may be added during the conventional oil-making operations without any substantial modification of the usual manufacturing conditions, such as crushing, peeling, calendering, dressing, solvent extraction, thermal treatment (toasting), debittering.

In a particularly advantageous embodiment of the instant method, the tannin-containing substance is added prior to the calendering and, where applicable, after peeling or decortication, with a view to preventing losses of tannin-containing substance. The distribution of the tannin-containing substance in the oleaginous substance must be homogenous, and effective contact must be obtained between the tannin-containing substance and the proteinic substances. Calendering and pressing, which are conventional operations in the oil-making industry, provide for effective contact between the tannin-containing substance and the protidic substance, as the considerable mechanical action exerted during these operations involve pressure and friction. Furthermore, the steam usually introduced during the pressing operation results in an increase in moisture and temperature, which contributes to improve the contact between the various constituents of the mixture, and increases the reactivity and affinity between the tannin and the protein.

The conventional operations carried out in the oil-making process, and which vary in accordance with the nature of the oleaginous material to be treated and in accordance with the traditional working method of any particular plant, are sufficient to ensure the efficiency of the method according to the invention, as evidenced by the tannintreatment of the proteins of oil-free oilcakes.

The following examples illustrate the present invention; however, they are not to be construed as involving any limitation of the scope of the present invention as defined herein.

EXAMPLE 1 A bulk quantity of peanut grains is decorticated and divided into 2 parts. The first part which serves as reference material is crushed into fragments of the size of a rice grain and then treated into the conventional manner by calendering without adding any additional substance, and then solvent extraction.

One hundred parts of peanut grains of the above-mentioned second part, containing 95 percent of dry matter and 35 percent of protidic oilcake are crushed on serrated cylinders.

Eight parts of tanning extract of chestnut wood in the form of a fine powder are added in as homogenous a manner as possible. This can be effected, for instance, by uniformly sprinkling on a conveyor belt, or by mixing in a mixer. The homogenous mixture is heated to C. and its moisture contents is brought to about 10-12 percent by steam injection prior to forwarding said mixture to a flake-producing calendering and pressing station.

The tannin-treated material coming from the calendering and pressing station is allowed to rest for about 12 hours so as to enhance the swelling of the proteins and the fixing of the tannin on their molecules. This material is then submitted to the usual operations of extraction by means of a solvent (hexane, essence B, etc.), and elimination of volatile substances.

Furthermore, the oil is submitted to convenient conventional treatment such as degumming, decoloration, filtration and the like.

EXAMPLE 2 In this modified embodiment the mixture of peanut and tanning extract is not treated by means of a flake-producing calendering and pressing device, but laminated by means of smooth cylinders, which produces chips having a diameter of 3 to 4 cm. and a thickness of about 0.1 mm. These chips are shaped into bands while steam is injected so as to heat the material to about 70 to 80 C. and to bring its moisture contents to about to 12 percent. The extraction process is then effected as indicated in example l, using the above-mentioned bands.

EXAMPLE 3 In another modified embodiment the tanning extract is added by atomization of a hot concentrated solution in a horizontal mixer. On account of the amount of water thus introduced in the material the subsequent operation of mechanical treating and extraction are effected in a dehydrating atmosphere so that the oleaginous substance reaches the extracting station with a convenient moisture contents.

TEST OF THE EFFICIENCY OF THE TREATMENT, USING ARTIFlClAL RUMENS The oil-free oilcake obtained from the reference grains which have not been treated with tannin and the oilcake treated in accordance with the present invention are introduced into artificial rumens and contacted for 15 hours with the contents of the rumen of living sheep. in this manner the phenomena of bacterial deamination of the proteins which take place in vivo in the rumen of the animal are reproduced approximately, in vitro.

It is observed that the proteins of the nontreated oilcake are rendered soluble in an amount of 65 percent in the artificial rumen, while 61.2 percent of their total nitrogen contents are converted into ammoniac.

As opposed hereto the proteins of the tannin-treated oilcake are rendered soluble only in an amount of 6.4 percent, while only 4.8 percent of their total nitrogen contents is converted into ammoniac.

The complex proteins of the oilcake treated according to the invention are entirely liberated by the proteolytic enzymes (pepsine trypsine) of the digestive tract. The quantity of total nitrogen digested in vitro by these enzymes represents 98.9 percent of the proteins of the tannin-treated oilcake, as compared to the corresponding value of 98.3 percent of the proteins of the nontreated oilcake.

The degradation of the cellulose of coarse fodder under the action of the micro-organisms in the rumen does not undergo any modification by the tannin treatment of the seed in accordance with the invention. Thus, the cellulose of wheat straw introduced in the artificial rumen is degradated in an amount of 3 l .9 percent in the presence of tannin-treated oilcake as compared to 32.8 percent in the presence of nontreated oilcake. In the absence of any oilcake this degradation takes place only in an amount of 26.7 percent. The properties of the oilcake obtained by the method according to the invention are in conformity with those of the tannin-treated oilcakes prepared by known methods, particularly by the methods described in the following publications:

Leroy F, Zelter S. 2., Francois A. C., 1964 Protection of the Alimentary Proteins against Bacterial Deamination in the Rumen." C. R. Acad. S. Paris, 259, 1,592-1 ,595.

Leroy F, Zelter S. Z., 1966 Tanning of Peanut and Soya Oilcake Proteins and Deamination Phenomena in the Rumen of Adult Sheep." 9th intern. cong. of Animal Prod, Edinburgh p. 137.

Leroy F, Zelter S. Z., Francois A. C. 1966 Protection of the Alimentary Proteins against Bacterial Deamination in the Rumen." 7th intern. cong. of nutr., Hamburg, and the French Patent specification No. 1.453.261 and 1.461.364.

During the extraction of oil from seeds treated in accordance with the invention it is observed that the percolation is improved which facilitates the oil extraction by means of a solvent. Furthermore, the gums or mucilages exhibit better coagulation which allows for faster and more complete filtering and thus for better degumming of the oil.

The iron, copper, and cobalt contents of the resulting oil is lower than that of the oil obtained from seed which has not been treated with tannin; this enhances the resistance of the oil to rancidity.

Furthermore, it has been observed that the oil obtained from tannin-treated seed blackens less easily when exposed to heat, as compared to oil obtained from nontreated seeds.

EXAMPLE 4 Semi-industrial tannin-treating tests were conducted with cakes obtained from peanut grains having the following composition (by weight):

Water 4 .5 5% Fatty matter (related to the dry matter) 50. [0% Acidity (expressed in terms of oleic acid) 0.58%

A tanning extract in the form of a concentrated aqueous solution was added in an amount of 8 parts (by weight) of dry tanning extract for parts (by weight) of grains.

The test have been conducted in accordance with the conventional technique of the oil extracting industry. The successive treatment phases are generally the following:

i. Crushing (or flattening) of the grains 2. Baking of the crushed grains (for about half an hour at lO0-120 C. until the crushed grains disgorge the oil).

3. One or more pressing steps for obtaining a residual product which still contains 5 to 10 percent oil.

4. Reheating, if desired, with a view to drying the product to a predetermined moisture contents.

5. Solvent extraction, whereby a residual product containing about 1 percent oil is obtained.

The various tests hereinbelow have been conducted on the basis of the above-described technique.

TEST A This is a reference test. The treatment is effected on peanut grains without addition of tannin.

TEST B The tannin was incorporated after the crushing of the gains prior to the baking, i.e., between phases (1 and (2); the treatment was then continued without any maturing time or other resting periods during any of the subsequent treatment phases.

TEST C The tannin was incorporated as in the test B, i.e., between phases (1 and (2), however, after phase (3) i.e., upon leaving the press the product was rehumidified up to a moisture contents of 12 percent, and the humidified product was allowed to rest for 1 night (maturing) and then dried (phase (4)) to a moisture contents of about 3 percent; subsequent phase (5), i.e., the oil extraction was then carried out.

TEST D The tannin was incorporated as in test B and C hereinabove, i.e., prior to feeding the material into the baking device (phase (2)), however, the product was rehumidified after phase (2),

i.e., upon leaving the baking device, so as to have a moisture contents of 12 percent; the product was then allowed to rest (maturing) for 4 hours prior to phase (3), whereafter phases (3), (4), (5) were carried out in an uninterrupted fashion.

TEST E In this test the tannin was incorporated immediately prior to phase (5). In this case, phase (4) needs not to be carried out, the tanning extract solution being introduced in the oleaginous product which has just undergone the last operation of the pressing phase (3). Extraction phase (5) was then carried out.

In test E series the pressing phase (3) was effected by two successive steps: A first pressing step and a second and final pressing step, which is a well-known technique in the oil-making industry.

In test C the extraction was carried out successively on two batches of bags coming from the previous treatment phases. The corresponding products will be designated B1 and C1, respectively.

In a general way no particular difficulty in the extraction of the oil of the tannin-treated grains was encountered during the above tests. Furthermore, the tannin treatment by causing the flakes to harden prevents the formation of dust, and the clogging of the filters, which results in a decrease of extraction time. Thus, the utilization of a tanning extract improves the technology of extraction.

Hereinbelow indications will be given about the properties of the peanut cakes which were treated in the above tests, and he properties of the oils which were obtained.

1 Properties of Oil-free and Tannin-treated Peanut Cakes l l. Tests in the Artificial Rumen In the artificial rumen the ammoniacal nitrogen contents (NNH3) as found with respect to the total nitrogen contents of the cake. The results are indicated in table I hereinbelow:

percent 0 Table I shows clearly a decrease of the ammoniogenesis for all the preparations where the tannin was incorporated prior to the baking operation. Test E shows results less satisfactory for the industrial practice although the relative decrease with respect to the nontreated cake is still quite considerable.

l-2. Tests In Vivo Nutrition tests in vivo were conducted on male castrated fistulated lle de France sheep. The evolution of the soluble and insoluble nitrogenous complexes was examined in the rumen of the sheet after a meal comprising percent of tannin-treated oilcake which represented about 80 percent of the total nitrogen of the food ration.

Table I1 hereinbelow indicates the results.

The tests were conducted with cakes treated in conformity with tests B and C, the reference cake being the cake resulting from test A.

Table II Digestion time 'N.nP= concentration in milligrams of nonproteic nitrogen (i.e., ammoniucal N soluble nonammoniacal N) for I00 milliliters of rumen liquid.

"N-NHI! concentration in milligrams of ummoniacal nitrogen for I00 mil liliters of rumen liquid.

"N.nP.NH3 concentration in milligrams of nonummoniacul nonproteic nitrogen for I00 milliliters of Rumen liquid.

In table II the value has been assigned to the results obtained at zero time for each material. The indicated values concerning cakes B and C are relative values related to the base 100 of the reference material.

2. Properties of the Resulting Oils Four oils prepared during the above tests (A, B, C and E) are refined by a conventional method comprising the successive treatment steps of:

degumming and neutralization decoloration deodorization The following observations are recorded:

2l: During the degumming (demucilaginating) and neutralizing operation the most favorable percentage of the total losses was obtained for the oil resulting from test B. However, the neutralization carrying off coefficients (i.e., the percent ratios of the total losses at the acidity degree of the oil) are the following in the order of decreasing quality:

Oil A 5.5l Oil 8 5.60 Oil C 2.88

Oil D 5.00

Thus oil C shows the best refining coefficient. In all phases the oils which has been treated with a tanning extract gave the best results.

22: When comparing the four raw oils (mixture of pressure oil and extraction oil) it is seen that the tannin-treated oils have a lower phosphor contents and thus a lower contents of gums than that of the reference oil. This property may be advantageously used in the treatment of oils having a higher contents of phosphor lipid than that of the peanut oil, such as colza oil, linseed oil, and soya oil.

23: The tannin-treated oils exhibit better properties as far as acidity and ultraviolet absorption are concerned. The following results were obtained with ultraviolet rays:

at 232 mp.(dienic oxidation compounds) Oil A 2.88 Oil 8 2.46 Oil C 2.46 Oil D 2.64

at 270 mmtrienic oxidation compounds) Oil A 4.50 Oil 8 4.38

Oil C 3.84 Oil D 3.60

These tests which were conducted on deodorized oil show that the tannin treatment improves the resistance of the oils to oxidation. 24: The organoleptic data have been recorded after conservation for a period of 55 days. The samples were examined at that time by a testingjury who arrived at the following classification:

The difference observed by the jury between oil D, C and B was hardly noticeable, but the reference oil A was clearly put aside and its taste was considered less pleasant.

it follows from these tests that the tannin treatment of peanut does not result in a modification of the indices of oil obtained by pressing and extraction, while the refining conditions are favorably influenced by the addition of tannin, the latter improving furthermore the conditions of conservation of the oil, all other data being equal.

While certain features of this invention have been described in detail with respect to various embodiments thereof it will, or course, be apparent that other modifications can be made within the spirit and scope of the invention, and it is not intended to limit the invention to the exact details set forth above, except insofar as they are defined in the following claims.

What is claimed is:

l. in a method of treating an oleaginous and proteinic vegetable substance including the steps of submitting said vegetable substance to mechanical pressure and friction forces in the presence of water, at a temperature higher than normal ambient temperature, and separating the oily constituents of said vegetable substance from the proteinic constituents thereof, the improvement which comprises adding a tannin-containing substance to said vegetable substance prior to said step of submitting said vegetable substance to said pressure and friction forces, and adjusting the amount of water such that it corresponds to a moisture content of about 10 to 15 percent of said vegetable substance prior to separating said oily constituents from said proteinic constituents, and separating said oily constituents from said proteinic constituents.

2. The method of claim I, wherein said tannin-containing substance is a tanning extract in the form of a solid powderous substance or in the form of a concentrated solution.

3. The method of claim 1, wherein said tannin-containing substance is a tanning extract, the amount of said tanning extract added to said vegetable substance being about 3 to 8 percent of the latter.

4. A product consisting at least in part of the proteinic constituents of an oleaginous and proteinic vegetable substance, when said product is obtained by the method of claim 1.

5. A product consisting at least in part of the oily constituents of an oleaginous and proteinic vegetable substance, when said product is obtained by the method of claim I,

6. The method of claim 1, wherein said vegetable substance is constituted by a substance selected from the group consisting of peanut, sunflower, colza, cotton, soya and, linseed, and wherein about 3 to 20 percent of tanning extract are added to said vegetable substance, related to the weight of the latter.

Claims

2. The method of claim 1, wherein said tannin-containing substance is a tanning extract in the form of a solid powderous substance or in the form of a concentrated solution.
3. The method of claim 1, wherein said tannin-containing substance is a tanning extract, the amount of said tanning extract added to said vegetable substance being about 3 to 8 percent of the latter.
4. A product consisting at least in part of the proteinic constituents of an oleaginous and proteinic vegetable substance, when said product is obtained by the method of claim 1.
5. A product consisting at least in part of the oily constituents of an oleaginous and proteinic vegetable substance, when said product is obtained by the method of claim 1.
6. The method of claim 1, wherein said vegetable substance is constituted by a substance selected from the group consisting of peanut, sunflower, colza, cotton, soya and, linseed, and wherein about 3 to 20 percent of tanning extract are added to said vegetable substance, related to the weight of the latter.