DE1692003A1 - Process for tanning vegetable matter containing oil and protein - Google Patents

Description

PA te NTA N WA'L TE PATENT Attorney DIPL.-ING. R. MOLLER-BORNER PATENTANWALT DIPL.-ING. HANS-H. WEY BERLIN-DAHLEM 33 PO DBI ELSKIALLEE 68 8 MÖNCHEN 22 W! D E N MAYE RSTR ASS E TEL. 0311 ■ 742907. TELEGR. PROPINDUS TELEX 0184057 TEL. 0811 225585 - TELEGR. PROPINDUS. TELEX 0524244

Munich, March 7, 1968

20th

Institut National de la Recherche Agronomique, Paris, and Produits Chimiques et Celluloses Rey, Velizy-Villacoublay,

Yvelines (France)

Process for tanning oil and protein-containing plants

Fabrics

The invention relates to vegetable substances containing oil and protein, in particular the production of oils, vegetable fats, Oil cake and other extracts from fruits, seeds and other vegetable oils and proteins Fabrics.

The invention is particularly directed to a method of improvement the raw materials and products from the technical processing of vegetable oil and protein-containing substances, that consists in that these substances are treated with at least one tanning agent, after which the oil and fat substances are treated separates these substances from the proteins contained in the treated vegetable matter. Therefor

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you can mix the tannin with the vegetable matter and mechanically pressing this mixture in the presence of water at a temperature above ambient and rub.

This treatment can be done with a solid powdered tanning agent as well as with a concentrated tanning solution; you can also choose a natural or use synthetic tannin extract and raw vegetable tanning agents

The treatment can preferably be carried out at a temperature above 50 ° C., the degree of humidity of the mixture of vegetable matter and tannin being set to between 10 and 15 % .

When treating plant substances such as peanuts, sunflower seeds, rape, cottonseed, soybeans, linseed and the like, about 3 to 20 % of commercially available tannin extract can be used.

When treating kernels, this treatment can be carried out, after the kernels have been peeled.

According to the invention, the tanning agent can be mixed with the oil-containing substances during oil extraction and in particular before rolling or press be intimately mixed.

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The method according to the invention leads to improved Vegetable fats and oils as well as vegetable oil cakes that have been de-oiled and have a higher nutritional value, in which the proteins are protected against bacterial deamination in the rumen.

The invention relates simultaneously to oils, fats, oil cakes and other extract substances from substances containing oil and protein, the in the method according to the invention as novel industrial products as well as fruits, seeds and other vegetable oils and proteins that have been treated with tannin Fabrics.

Processes for treating oil cakes with tannins in order to increase the nutritional value of the oil cakes are already known where the proteins are tanned insoluble and complexes are formed which are resistant to bacterial deaminases but are broken down by the esophageal protolytic enzymes.

Such tanning of the oil cake is harmless to animals, but increases the nutritional value for them, in particular, considerably for ruminants, which is due to the particular3 pronounced bacterial Deamination in the rumen is due.

A raw tanning agent as well as any tanning agent extracts, for example in powder form, can be used as the tanning agent. use as a paste, suspension, dispersion or solution in various solvents.

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The amount of tanning agent to be used varies depending on its tannin content. You choose them in dependence on the oil-containing seeds to be treated and on the type of protein to be deaminated. These amounts must be sufficient to render them completely insoluble and to convert them partially or completely into ammonia by suppressing microorganisms in the esophagus completely.

This amount is 15% for peanuts as well as for sunflower seeds and soybeans. It is 12% for rapeseed and only 6 % for flaxseed.

These technically optimal quantities can be reduced for economic reasons, but this is then at a cost the improvement of the treated products.

The method according to the invention not only improves this Value of protein, but also the extraction conditions and the properties of the extracted fats.

The tanning agents can also be used in the form of powder, paste or suspension or solution, but also use raw tannins, provided that these contain sufficient tannin to remove the proteins of the kernels and the other vegetable matter To protect substances containing oil and protein without changing the nutritional value of the consumer product, the oil cake and to risk the oils obtained in particular by this treatment.

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The intimate admixture of tannin according to the invention can be effected during the classic oil production, without essentially of the usual technical processes such as Chopping, peeling, rolling, pressing, extraction with solvents, heat treatment ("toasting") and debittering is departed.

It is particularly beneficial to add the tanning agent before rolling and after peeling, if necessary, to avoid loss of tannin. It is important that the tanning agent is distributed in the oil-containing matter is uniform and that effective contact is ensured between the tanning agent and the proteinaceous substances is. Rolling and pressing, both processes involved in oil extraction, allow effective contact between the Tannin and the protein, because their important mechanical action occurs during pressing and rubbing. Furthermore brings an increase in the water vapor that is usually introduced in oil production during pressing of humidity and temperature, which helps maintain contact between the various components of the mixture as well as to improve the reactivity and the affinity between the tannin and the protein.

The usual oil recovery procedures, which are carried out according to the treated oily substances as well as the ÜlmUhlentechnik changeable are sufficient to guarantee the effective

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ability of the method according to the invention, which one by determines the tanning of the proteins in the de-oiled oil cake.

The process according to the invention is explained in detail by means of the following examples.

example 1

You peel a certain amount of peanut kernels, which you then split into two parts. The first part is based on comparison The size of the hot grain is crushed, then treated in the usual way in oil production by rolling without any additives and then extracted with a solvent.

The second part of the kernels is crushed to rice grain size by means of corrugated rollers, 100 parts by weight of peanut kernels containing 95 % dry matter and 55 % protein-containing oil cake.

8 parts of tannin extract from chestnut wood in the form of atomized powder are added as homogeneously as possible. This addition can take place, for example, by uniformly sprinkling on a conveyor belt or by mixing in a continuous mixer. This homogeneous mixture is heated to 80 ° C. and its humidity is increased to about 10 to 12 % by spraying in steam before it is conveyed into flakes for roller pressing.

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Allowing the tanned mass verÄßt the roller press to rest about 12 hours, in order to promote the swelling of the proteins and the attachment of T _a nnins in their molecules. This mass is then subjected to the usual extraction with a solvent (hexane, essence B, etc.) and de-oiling.

In addition, the oil is subjected to the appropriate classic treatments such as degumming, decolorization, filtration, etc.

Example 2

As a modification, instead of treating the peanut-tannin extract mixture by roller pressing to flake this mixture is rolled with smooth rollers, and platelets 3 to 4 cm in diameter and about 1/10 mm thick are obtained. These platelets are pressed into strands by injecting steam to heat the mass to around 70 to 80 ° C and to increase its humidity to around 10 to 12 %. then

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these strands are extracted in the manner indicated in Example 1.

Example 3

According to another embodiment, the tannin extract is given by pulverizing a concentrated hot Solution in a horizontal mixer. Because of the amount of water introduced into the mass, the next steps are taken the mechanical treatment of the extraction in an anhydrous atmosphere, so that the oily substance bdi the Extraction reaches a suitable water content,

1üä830 / fH78 - 8 -

The de-oiled oil cake obtained from the comparison kernels and not treated with tannin is added, as is the oil cake oil cake treated according to the invention in artificial rumen, and they are brought with the rumen contents for 15 hours of a live sheep. Then one reproduces in vitro the phenomena of bacterial deamination the proteins as they occur in vivo in the rumen of the animal.

It is found that the proteins of the untanned oilcake are 65% soluble in the artificial rumen, with 61.2% of its total nitrogen being converted into ammonia.

In contrast, the proteins of the tanned oil cake are only 6.4% soluble, and only 4.8% of its total nitrogen becomes converted into ammonia.

The complex proteins of the tanned according to the invention Oil cakes are completely broken down by the protolytic enzymes of the esophagus (pepsin + trypsin). The amount of total nitrogen digested in vitro by these enzymes is 98.9% of the proteins in the tanned oil cake compared to 98.3% of the protein in the untanned oil cake,

The decomposition of the cellulose of raw cattle feed by the microorganisms of the rumen is caused by the tanning treatment

_Hi:; i: 3 0 / P έ. ? P.

the cores according to the invention are not changed. The cellulose from cereal straw that is introduced into the rumen is decomposed to 31.9% in the presence of tanned oil cake, while 32.8% is decomposed in the presence of untanned oil cake. If there is no oil cake at all, only 26.7 % will decompose. The properties of the oil cakes obtained in this way by the process according to the invention correspond to those of oil cakes which have been tanned using known processes, in particular those as described in the following publications:

F. Leroy. S.Z. Zelter. A.G. Francois, 1964

Protection of food proteins against bacterial

Deamination in the rumen. CR. Acad. S. Paris, 259 , L592-95.

F. Leroy. S.Z. Zelter. 1966

Tanning of proteins in peanut and soybean oil cakes and signs of deamination in the rumen of adult sheep. 9th Intern. Cong, of Animal Prod.,
Edinburgh, page 137.

F. Leroy. SZ Zelter. AC Francois. 1966
Protection of food proteins against bacterial deamination in the rumen. 7th Cong. Intern, de Nutr., Hambourg, as in French patents 1,453,261 and
1 461 364.

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During the extraction of the tile from tanned according to the invention Kernels are found to improve filterability is, so that the de-oiling is facilitated by solvents. The mucilages are also more strongly coagulated, like that that faster and more complete filtration and thus a better degumming of the oil is made possible.

The content of iron, copper and cobalt in the oil thus obtained is lower than that of oil, which does not contain tannin treated kernels is preserved, which increases the resistance of the oil to rancidity.

Finally, it should be noted that there is an oil that consists of tanned seeds are less likely to turn black by the action of heat than an oil made from untanned seeds Cores.

Example 4

The attempts at tanning oil cake have been made on a semi-industrial scale on peanut kernel eggs, the following Weight composition had:

Water 4.55 %

Fats (based on dry matter) 50.10% Acidity (expressed by oleic acid) 0.58 %

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A concentrated aqueous solution of tannin extract is used in such a way that 8 parts of dry tannin extract can be used per 100 parts by weight of cores.

The classic oil extraction techniques were used in the experiments applied. The stages of successive treatments were generally as follows:

1. Crushing (or rolling) the kernels,

2. Cooking the crushed kernels (about half an hour at 100 to 120 ° C, oil escaped from the kernels),

3. Pressing once or several times until a residue with 5 to 10% oil is obtained,

4. if necessary, re-heating to dry to a predetermined degree of moisture, and

5. Extraction with solvent to give a residue product with about 1 % oil.

The working technique described below was used in the various experiments below:

Test A: This _e V rsuch served for comparison. The treatment was carried out with peanut kernels that were not mixed with tannin.

Experiment Ba: After chopping the grains and before cooking, i.e. between the aforementioned steps 1 and 2, tannin increased, then became

ORIGINAL BATHROOM -52-

the treatment continued without interruption and without maturation or other rest periods at any further stage of the treatment.

Attempt Bb; As in the experiment Ba tannin is added, i.e. between levels 1 and 2, but it is moistened the product after step 3 again, i.e. after leaving the press, up to one Moisture level of 12%, then left the moistened product to rest (mature) overnight after which the product (step 4) was dried to a moisture content of about 3% and extracted in the manner indicated (5.).

Experiment D: Tannin was used as in experiments Ba and Bb closed, i.e. before cooking (2nd), but the product was moistened again after stage 2, i.e. after leaving the boiler, down to a moisture level of 12%. Then you let it go level 3 rest for four hours, after which the levels 3., 4. and 5. followed.

Experiment E: In this experiment, the tannin was added just before step 5. In this case it could Step 4 can be omitted because the tannin extract solution in the oil-containing product after last pressing process 3. e! was brought. Extraction was then carried out 5..

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In each test series, the pressing (3rd) was carried out in two successive ones Stages carried out: a first pressing and a second final pressing, as in the classic one Procedure in oil production.

Likewise, in experiment Bb, the extraction was carried out one after the other with two samples which came from the previous process steps. The corresponding products are referred to below as Bb ₁ and Bb ₂ .

In general, the above attempts have no particular ones Difficulties in the extraction of the tanned oil cake with it. On the other hand, avoids the tanning, so a retention of the flakes, the formation of dust and clogging of the filter, resulting in a decrease the extraction time leads. The use of tanned extract thus favors the extraction technique.

In the following, on the one hand, the properties of the peanut oil cakes that have been defatted and tanned by the above experiments are presented and on the other hand the properties of the oils obtained are given.

1. Properties of the defatted and tanned peanut oil cake a) Experiments in the artificial rumen

In the artificial rumen, the content of ammonia nitrogen (N-NH ₃ ) (found and calculated), based on the total nitrogen content of the oil cake, was measured. the

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The results are compiled in the following table.

Table I (ammonia formation) Experiment A Ba Bb ₁ Bb »DE

^Ν-ΝΗ 3 found
calculated

% Total nitrogen, - _q , _{13 5 13 s 7 ß} 11 2Q Tl of the oil cake ^{öö | d ld} ' ^{5 1} ^' ** ^r ' ^b * ■■ *: *** öijm based on

100 % untanned- 100 23.5 22.4 12.8 20.6 58.2

th oil cake

Relative decrease 0 -77.2 -77.6 -87.2 -79.4 -41.8

Table I shows very clearly a reduction in ammonia formation in all attempts in which the tannin has been added before cooking. Experiment E yields less interesting results for practice, although the relative decrease in the untanned oil cake is still very noticeable is.

b) In vivo experiments

They were performed in vivo on male, castrated sheep lambs of the Ile-de-France breed conducted nutritional studies. The formation of soluble and insoluble nitrogen compounds in the rumen of the sheep after administration was examined a meal containing 20% tanned oil cake with about 80% total nitrogen.

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The results are shown in Table II below. The tests were carried out with oil cake, which had been treated in the same way according to tests Ba and Bb, where test A was used for comparison

Table II digestion time (hours) '0 Ϊ 2

oil cake
N-np ♦ A.
Ba Port N-NH ₃ ** A. Ba Port N-np-NH ₃ *** A.
Ba Port

100 162 146 100 156 142 100 124 110 100 139 143 100 150 141 100 108 102 100 192 149 100 166 142 100 147 121

* N-np - concentration in mg of non-protein nitrogen (expressed as ammonia nitrogen plus soluble non-ammoniacal nitrogen) in 100 ml of rumen fluid

** N-NH ₃ - concentration in mg of ammonia nitrogen in 100 ml of rumen fluid

*** N-np-NHo concentration in mg of non-protein nitrogen and non-ammonia & chem nitrogen in 100 mol rumen fluid

In Table II, the value 100 has been given the comparison A in the numbers obtained. The numbers given for the Oil cake Ba and Bb are relative values based on the

Comparative base value 100.

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2. Properties of the oils obtained

The four oils obtained from Experiments A, Ba, Bb and D above were prepared in a conventional manner as follows cleaned:

- Degumming and neutralization

- discoloration

- deodorization

The following was observed:

a) During the neutralizing degumming, the greatest percentage of total losses for the Test Ba determined oil obtained. Meanwhile, the coefficients of decrease of neutralization, i.e. the percentages Details of the total loss for the acidity of the oil, each as follows:

oil A. 5.51 oil Ba 5.60 oil Port 2.88 oil D. 5.00

The coefficient of best cleaning was found for the oil Bb obtain. In all cases, the oils treated with a tannin extract gave the best results.

b) If you look at the four crude oils (mixture of pressed and extracted Oils) compares, evidently contains dit, by berbung received much less phosphorus, i.e. mucus, than

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the comparison oil. This property can be used for treatment of oils that contain more! phospholipoids than peanut oil, E.g. the oils from rapeseed, linseed, soybeans and the like are used.

C) The best quality of the oils is determined after tanning with regard to acidity and with regard to ÜV absorption. The values for the UV absorption are as follows:

- at 232 oi / U (diene compounds of oxidation) Oil A 2.88 Oil Ba 2.46 Oil Bb 2.46 Oil D 2.64

- at 270 m ^ u (triene compounds of oxidation) Oil A 4.50 Oil Ba 4.38 Oil Bb 3.84 Oil D 3.60

This test on deodorized oil shows that the treatment tannin improves the oxidation resistance of the oils.

d) Finally, organoleptic properties were found after storage for 55 days. These samples were then subjected to a taste test, whereby the following order was unanimously determined;

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D-Bb-Ba-A.

The differences found by the jury between the oils D ₁ Bb and Ba were slight, while the comparative oil A was clearly out of the ordinary and had an unpleasant taste.

A summary of these experiments shows that if the tanning of the kernels does not change the characteristics of the Oils obtained by pressing and extraction brings with it the purification result due to the introduction of tannin is influenced, and that this last process, like other things, favors the shelf life of the oil.

The invention is of course not restricted to the examples described. The person skilled in the art can do numerous make obvious changes without departing from the scope of the invention.

Patent claims:

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Claims (10)

PA TBN TA N WÄL rk PATENTANWALT DIPL-ING. R. MDUER-BORNER PATENTANWALT DIPL.-ING. HANS-H. WEY BERLI N-DAHLEM 33 PO DB IELS KIALLE E 68 8 MÖNCHEN 22 -WIDENM AYER ST RASSE TEL. 0311. 762907 TELEGR. PROPlNDUS TELEX 0184057 λ £ TEL. 0811 225585 TELEGR. PROPINDUS · TELEX 0524244 Institut National de la Recherche Agronomique, Paris, and Produits Chimiques et Celluloses Ray, Velizy-Villacoublay, Yvelines (France) claims 1. Process for tanning vegetable oils containing oil and protein Substances from which the protein components are extracted are, characterized in that a tanning agent is added to the substance mentioned before the oil and fat components be separated. 2. The method according to claim 1, characterized in that after the addition of the tanning agent to the vegetable substance the two are mixed and that the resulting mixture is mixed in the presence of water at a temperature above normal Temperature mechanically presses and rubs. 3. The method according to claim 1 and 2, characterized in that the G _e mixture of vegetable matter and tanning agent is heated to a temperature above 50 ° C and that the moisture level of the mixture is set to a value between 10 and about 15% . 1üa83Q / (K78 - ² - 4. The method according to any one of claims 1 to 3, characterized in that that the tanning agent is added in the form of a solid powder. 5. The method according to any one of claims 1 to 3, characterized in that the tanning agent in the form of a concentrated Solution is added. 6. The method according to any one of claims 1 to 5, characterized in that the tanning agent consists essentially of consists of a tannin extract. 7. The method of claim 6, wherein the vegetable matter consists of peanuts, sunflower seeds, haps, cottonseed, soybeans, linseed and the like, characterized in that that to the vegetable substance about 3 to 20%, based on the weight of the vegetable substance, des Tannin extract added. 8. The method according to any one of claims 1 to 7, wherein the vegetable substance consists of kernels, characterized in that that the tanning agent is added after the pips have been peeled. 9. Extract product of a vegetable oil and protein-containing S, open, e.g. oil, oil cake or the like, characterized in that, that before the extraction of this product, the vegetable substance according to one of the claims 1 to 8 is treated with tanning agent! 10. Plant-based substance containing oil and protein, characterized in that that it is subjected to at least one tanning process according to claims 1 to 8. ¹⁰ ^ lP-'QJLZ S