DD150689A5 - PROCESS FOR IMPROVING THE PROPERTIES OF RAW PROTEINS OF ANIMAL ORIGIN - Google Patents

Abstract

Process for improving the properties of crude protein powders or meals of animal origin, characterized in that the powders or flours are treated with an extraction mixture of ammonia or ammonium hydroxide and an organic solvent, and after removal of the extraction mixture the residue of the powders or flours is washed with water.

Description

Berlin, August 27, 1980 AP A 23 J / 220 470 57 246/18

Process for improving the properties of crude proteins

Field of application of the invention

The invention relates to a process for improving the properties of crude proteins of animal origin by reducing their content of lipid compounds and water-soluble compounds which have negative influences on odor, taste, nutritional value and tolerability. Adverse effects on the odor have, for example, Secondary products of oxidation reactions of unsaturated fatty acids; Certain constitution peptides evoke bitter taste. Nucleic acids can lead to pathological conditions (gout, urinary stones) »The availability of crude proteins in feed and especially in foodstuffs is severely limited by the content of such compounds.

The process according to the invention is used in the production of feed and foodstuffs.

C characteristic of the known technical solutions

According to known methods, the lipids are extracted from crude proteins of animal origin by organic solvents or separated by mechanical methods, such as separating.

The disadvantage here is the duration of the extraction. The treatment of the dried crude proteins with organic solvents, such as hexane or chlorinated hydrocarbons, is time-consuming and leads to products which, owing to the residual fat

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contents (1 to 4 %) are neither odorless nor taste stable. The mechanical separation of fats in so-called separators is very energy-intensive and likewise leads to products which are neither odorless nor tasteless due to residual contents of lipoid compounds of 1 to 2 % .

It has also become known from US Pat. No. 3,143,425 to use aqueous ammonia (NH, OH) and an organic solvent in order to avoid bitter losses during the extraction of hops by formation of humic acid. Aqueous ammonia acts as a chemical reactant, exploiting the effect of the hydroxyl ion (OH).

, Object of the invention

The aim of the invention is to provide a method by which lipoid compounds, such as Pettoxydationsprodukte, nucleic acids, peptides with high content of hydrophobic amino acids, and certain carbohydrates, such as. As lactose from crude proteins of animal origin, can be easily removed in order to increase the protein content, which is crucial for the nutritive value, and to improve the taste of the products »

Presentation of the essence of the invention

The invention has for its object to find a suitable extraction agent and suitable extraction conditions.

According to the invention, the process for improving the properties of animal proteins by reducing their content of lipid compounds and water-soluble compounds is carried out in such a way that the dried

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powdered materials with an extraction mixture of ammonia or ammonium hydroxide and an organic solvent of general formula I.

in which either IL · and R _{2 are} hydrogen and η is one, zv / ei or three, or in which R .. the hydroxy group and R _? Hydrogen, methyl or. Ethyl and η is two or three, treated and washed after removal of the extraction mixture, the residue of the powder or flours with water.

Used as dried and powdered materials are crude proteins of animal origin which are considered protein carriers, eg, fish meal, krill meal, whey, milk and skimmed milk powder *

Suitable solvents of the formula I are alcohols, such as methanol, ethanol, n-propanol and isopropanol, into consideration. Preference is given to methanol and ethanol, in particular methanol.

In addition to the alcohols mentioned, glycols and their monoethers of the formula I, namely glycol and monomethylglycol, are also suitable.

Ammonia can be added to said solvents in gaseous form or as a concentrated aqueous solution (NH, OH). The choice is made according to the water content of the powder or flour as well as the amount and water content des'eingesetzten solvent. NH, OH is suitable for powders with low moisture content (0 to 15 %) , but NH ^ better for raw materials with higher water content (10 to 30 %) »

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The removal of the lipid compounds depends on the total water content, which is in% by weight based on the amount of solvent used, and on the NH.sub.2 concentration in% by weight, based on the solvent used.

Particularly good test results could be achieved with powder, flour-solvent weight ratios of 1: 3 to 1:10 in the case of methanol and ethanol and 1: 8 to 1:15 in the case of propanol, glycol and the monoglycol ethers. The ammonia concentration, based on the amount of solvent, was 1 to 20 wt .-%, preferably 5 to 15 % _t, in particular 7 to 12 Gew # - / ö, the sum of the amounts of water resulting from cell mass, solvent and optionally from aqueous ammonia be 0 to 30 wt, -%, preferably 0 to 20% _t preferably 0 to 10 wt .- / i ?, based on the used amount of solvent.

The deletion of the fats from the dry raw products is carried out so that the flour or powder is suspended in the solvent and reintroduced or NH-OH added. Suitably, the "By mixing the suspension by agitation Treatment temperatures are generally in the range of -. 20 to + 60 ⁰ C, v / obei a range of + 5 to +50 C, especially from + 10 to + 30 G is preferred. The treatment time is from 5 to 180 minutes and is preferably from 35 to 60 minutes The treatment is generally carried out at normal pressure.

After completion of the solvent-ammonia treatment, the defatted residue is separated from the solvent by known methods such as centrifugation, filtration and sedimentation.

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Preference is given to filtration. The solid residue obtained can be treated again for the most complete removal of the lipids with an organic solvent of the formula I. The residue can be dried to remove residual solvent and ammonia. This is expediently carried out under reduced pressure, preferably 80 to 150 Torr, and elevated temperature, preferably 40 to 50 ° C. The so defatted and dried products are almost odorless and have a lighter color than the starting materials.

The liquid phase separated from the solid residue by the above-mentioned process contains ammonia and lipoid compounds. The solvent used can be separated from the fats by vacuum distillation and reused. The fats remaining after this can be subjected to the usual methods of fuming refining.

The defatted and optionally dried flours are then taken up in water. Preference is given to quantities of water which are in the weight ratio of 1: 1 to 1:30, in particular 1: 5 to 1:15, to the powder or flour. The amount of water is at least such that stirring of the suspension is possible.

The pH during the water treatment should be in the range of 4 to 9 »5, preferably 5 to 9 * 0 ,, and is optionally adjusted to this range." This is especially necessary if not or not completely dried flours from the first Extraction stage, which then also contain residual amounts of ammonia, which can lead to a too high pH. The purpose of the extraction is to reduce the content of undesired substances such as nucleic acids, bitter peptides or carbohydrates, such as

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Lactose, as well as the functional properties of the protein, such as. B. Shaping or emulsifying ability to improve »

The extraction is generally carried out in a temperature range of 30 to 95 C at atmospheric pressure. Preference is given to temperatures of 40 to 70 C, more preferably 50 to 60 ⁰ C. The extraction time can be depending on the extraction temperature and amount of water 5 to 120 minutes, good results are achieved with 25- to 45-minute extraction time · For the separation of solid and liquid components is the Suspension, preferably at temperatures of 10 to 30 ⁰ C, filtered. Other geei, sedimentation and centrifugation.

to 30 ⁰ C, filtered. Other suitable separation methods are

The solid phase is freed of liquid residues by known methods, ie freeze-drying, vacuum drying or spray-drying.

The products have more pleasant taste and odor properties, very high water binding capacity and a significantly higher protein content than the starting compounds.

The products treated according to the invention have a particularly low content of lipoid compounds (0.03 to 0.8% by weight) and nucleic acid (0.0 to 0.5% by weight), which is why they are used as animal feed and especially as food are particularly suitable.

The process according to the invention avoids the disadvantages of known solvent extractions, v / ie large amounts of solvent, long treatment times or physical Treruiprozesse with high energy consumption.

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In contrast to the process using US Pat. No. 3,143,425 using ammonia, the conditions in the process according to the invention are different. The water content of the extraction mixture is lower. It is not the effect of the Hydroxylions exploited, but the solvent power of ammonia · (NH-,)> which in the absence of water or at only low hydroxyl ion concentration according to the equation

dissociated and thereby removed in the presence of an organic solvent of general formula I from crude proteins of animal origin, the interfering for their use lipoid compounds and water-soluble compounds.

Moreover, the ammonia used in the present invention not only acts as a solvent, but also changes the mechanical structure of the crude proteins, thereby decreasing the extraction time and improving the extraction efficiency.

Ausführungsb EXAMPLE

The process is described by the following examples:

example 1

100 g fish meal with a residual moisture content of 5 % _t 8.4% crude fat (after acid hydrolysis), 56 % crude protein (Nx6.25), 2.8 % nucleic acid and 16.4 % ash were suspended in 400 ml methanol. While stirring the suspension, 15 g of NH-j-Ga3 were introduced and dissolved. The mixture of methanol,

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Ammonia and flour were stirred for 45 minutes at 20G.

To separate the solid and liquid phases, the mixture was filtered and the solid residue was washed twice with 100 ml of methanol. After renewed filtration, all filtrates were combined. This brown solution contained the lipoid compounds of the starting substance used. Methanol and ammonia were removed by vacuum distillation (100 torr, 40 ° C). The residue, which was 15.2% by weight of the dry matter used, was a brown, strongly fishy-smelling oil. :

The solid residue of the extracted flour obtained by filtration was dried in vacuo (100 torr) at 40 ^° C. for 5 hours. There were obtained 78 g of defatted flour with a residual moisture of 3 % , which had only a weak fishy odor and a lighter color than the starting material had.

To reduce the level of unwanted water-soluble compounds, this flour was suspended in 600 ml of water. The pH of the suspension homogenized by stirring was 6 _f 9o

After raising the temperature to 55 C was 20 minutes v / pus stirred, cooled to 30 ⁰ C and isolated by filtration in solid and liquid phase. The resulting sediment was again mixed with 300 ml of water and stirred at 20 C for Minuten0 minutes. It was then filtered again and the sediment was dried under reduced pressure. Thus, 68 g of a protein concentrate could be obtained, which due to the strongly reduced typical odor can find much wider application than the original product,

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Example 2

100 g fishmeal was extracted as described in Example 1, but instead of gaseous NH4, 40 ml concentrated KH.OH (33 / oig) were used as reagent,

Example 3 .

The procedure was as in Example 1, but 30 g NHo were used »

Example 4

In a procedure as in Example 1, ethanol was used as the solvent instead of methanol,

Example 5

The procedure was as in Example 1. Instead of methanol, i-propanol was used as solvent,

Example 6

The starting material used was 100 g of krill flour with a residual moisture of 4.7%, 11.2 % crude fat, 54 % crude protein, 3.4 % nucleic acid and 15.3 % ash. The product was subjected to the process steps described in Example 3. Thereafter, 60.4 g of a protein concentrate with only a slight odor could be isolated,

Example 7

As starting material, the krill flour described in Example 6 was used and extracted according to the conditions described in Example 3. However, after degreasing to a complete drying of the solvent-moist

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Resigned refrained. The thoroughly extracted filter cake with a pesticide content of 58 % was suspended in 800 ml of water, the pH being adjusted to 9.0, owing to the ammonia remaining in the moist mass,

The temperature of the suspension was raised with stirring to 50 C and after 45 min, the pH is adjusted by addition of HCl to 5.8 »Thereafter, a further 15 min. At 65 ⁰ O further stirred, then cooled to 40 C und'filtriert , The resulting sediment was dried, leaving 57.3 g of a protein concentrate containing 85 % protein,

Example 8

The procedure was the same as described in Example 7, but using ethanol instead of methanol as the solvent,

Example 9

In one process, as described in Example 6, i-propanol was used as solvent instead of methanol,

Example 10

The starting material used was 100 g of whole milk powder with a residual moisture content of 3.5 %, 26 % protein, 26.2 % fat and 7 % ash.

The powder was suspended in 800 ml of ethanol and while stirring the mixture 25 g of IJHo gas at 10 ⁰ C introduced and dissolved. While slowly warming to 30 ^° C., the mixture was stirred for 30 minutes and then filtered to separate the solid and liquid components and the filter

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cake washed twice with 150 ml of ethanol. The collected filtrates were concentrated by vacuum distillation (100 torr, 45 C) to leave 35 g of a yellow paste consisting mainly of extracted fat.

The solid residue of the extracted powder obtained by filtration was dried in vacuo (100 torr, 45 C, 4 hours). This left 62.8 g of a white protein product freed of the typical odor and taste of milk. The .functional properties improve significantly by the described type of fat extraction. The degreased product is suitable, for example, as a protein additive in baked goods or as a base material for foams.

Example 11 .

The procedure was as described in Example 10, but using methanol instead of ethanol as a solvent.

Example 12

The starting material was the whole milk powder used in Example 10, which was degreased according to the conditions specified therein. '

However, after degreasing, complete drying of the solvent-moist residue was dispensed with. The thoroughly extracted filter cake with a solids content of 54 % was suspended in 500 ml of water, wherein the pH value was adjusted to 9.0, due to the remaining in the solvent-moist mass of ammonia.

After raising the temperature in the aqueous stirred suspension to 50 ⁰ C was carried out after 15 minutes, a pH shift by addition of HCl to 4.5, wherein

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by precipitation of egg white a flocculent precipitate formed. The mixture was then stirred for 15 min. At 20 C v / eiger and then filtered from the precipitate formed. The filter cake was washed once with 200 ml of water, then suspended in 100 ml of water and the pH adjusted to 7.0 with NaOH and freeze-dried. The white odorless dry product (25.1 g) is a protein isolate with very good foaming and emulsifying properties ·,

Example 13

The starting material used was 100 g of skimmed-milk powder with a residual moisture content of 4.3 %, 1.1 % fat, 36 % protein and 7.8% ash and subjected to the conditions mentioned in Example 10.

Thereafter, 75.3 g of a white, tasteless product with a protein content of 46.0 % were obtained .

Example 14

100 g of skim milk powder as used in Example 13 were treated according to the process steps described in Example 12.

It was thus possible to produce 37.2 g of a white, odorless and tasteless protein isolate with very good foaming and emulsifying properties.

Table 1

Some analytical data of the products before and after the process Wt% on dry matter

Starting materials 5 100 g of flour or powder Crude fat wt. % Nucleic. Wt .-% Protein weight % end products Quantity. (S) Crude fat wt. % Ilukleins. Weight % Protein weight % , kind 8.4 2.8 56 68.0 0.4 0.7 78.0 fish 8.4 2.8 56 70.1 0.6 0.7 75.2 fish 8.4 2.8 56 66.7 0.2 0.6 79.4 Pi sch 8.4 2.8 56 67.2 0.4 · 0.7 78.5 fish 8,4 / 2.8 56 73.1 0.9 0.8 74.9 fish 11.2 3.4 54 "60.4. 0.7 0.9 78.2 krill 11.2 3,4 ' 54 57.3 0,5. 0.7 85.0 Krill; ' 11.2 3.4 54 57.9 '* 0.6 0.8 83.5 krill 11.2 3.4 54 61.2 1.1 0.8 76.7 krill 26.2 • - 26 62.8 < 0.9 .39,8 whole milk 26.2 - 26 62.0 0.7 - 40.1 whole milk 26.2 - 26 25.1 0.5 - 91.2 · whole milk 1.1 - 36 75.3 0.05 • - 46.0 " skimmed milk 1.1 -. 36 37.2 ' 0.04 - 92.4 skimmed milk In game 1 2 3 4. 5 6 7 8th 9 , 10 11 12 13 H

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Claims (3)

invention claim Process for improving the properties of crude protein powders or meals of animal origin, characterized in that the powders or flours are mixed with an extraction mixture of ammonia or ammonium hydroxide and an organic solvent of general formula I wherein either R- and Rp are hydrogen and η is one, two or three, or wherein R- is the hydroxy group and Rp is hydrogen, methyl or ethyl and η is two or three, treated, and after separation of the extraction mixture, the residue of Powder .or flours with water washes · 2 * Method according to item 1, characterized in that the total V / assergehalt during the extraction 0 to 30 wt%, preferably 0 to 20'Gew. ~%, in particular 0 to 10 wt .-%, based on the amount of solvent used, is. 3 * Method according to the points 1 and 2, characterized in that the NHL content during the extraction of 1 to 20 wt .-%, preferably 5 to 15 wt .- ^, in particular 7 to 12 wt. ~ / S, based on the amount of solvent used is.