WO2009115635A1

WO2009115635A1 - Method for recyling by-products by means of the reconstitution of fats useful in animal feeding-stuffs

Info

Publication number: WO2009115635A1
Application number: PCT/ES2009/070068
Authority: WO
Inventors: Enrique De Pablos Pérez
Original assignee: Norel, S.A.
Priority date: 2008-03-19
Filing date: 2009-03-18
Publication date: 2009-09-24
Also published as: ES2325854A1; CL2009000670A1; ES2325854B1; AR071004A1

Abstract

The invention describes the recycling of free fatty acids and/or of oleins as residual by-products from the refining of vegetable and/or animal fats. The reaction thereof with optionally residual glycerol or glycerine in turn originating from biodiesel production processes leads to reconstitution thereof as triglycerides or fats with fatty acid contents that are identical or similar to the starting vegetable and/or animal fats in the refining method that yields the residual fatty acids. The fats thus reconstituted, which are obtained by reconversion of the residual oleins and/or fatty acids, are used in animal feeding-stuffs and offer similar energy levels to those of natural fats.

Description

RECYCLING PROCEDURE OF SUBPRODUCTS THROUGH RECONSTITUTION OF USEFUL FATS IN ANIMAL FEEDING

Field of the invention

The invention is attached to the technical sector of recycling by-products and their conversion into useful elements. Recycled waste is by-products, on the one hand, from the refining of fats and / or vegetable and / or animal oils, in the form of fatty acids and oleins. Another by-product necessary to carry out the process of the invention is glycerol or residual glycerol from biodiesel production. Specifically, the useful elements that are achieved after the recycling process of these wastes are reconstituted fats, useful as ingredients of nutritional compositions or feed, in the breeding of livestock and poultry.

Description of the State of the Art

The formation of fats from the esterification of glycerol or glycerin with free fatty acids is known. This process usually starts with purified reagents. That is, both fatty acids and glycerin itself have high levels of purity, which make them expensive. It is, among others, for that reason, why the fats thus obtained are not profitable in animal feed.

It is not known, however, any process of reconstitution of fats from industrial by-products with lower levels of purity, such as residual fatty acids from the processes of refining of vegetable and / or animal fats, nor the own residual glycerin that is formed in biodiesel production procedures.

The disposal of these wastes is technically complex and expensive, given their poor solubility in water and other liquid wastes of an aqueous nature. That is why it is necessary to find an effective recycling method for them. At present, the feed industry uses the refining oleins of edible vegetable oils, such as soybean oil, sunflower, rapeseed, olive, etc., as additive nutrients for animal feed. However, the energy value of these oleins compared with the reconstituted fats according to the present invention is very limited. The low cost of these wastes, together with the savings created with their recycling according to the process of the invention, allow cost savings such that, the use of the reconstituted fats according to the patented process, in animal feed, turns out to be fully effective from a purely functional point of view, with the addition of being absolutely profitable in economic terms.

Fats have a number of advantages, both nutritional and not strictly nutritional, which make their inclusion in feed convenient. Among the not strictly nutritional are: they control the formation of dust and improve the palatability, consumption, structure and appearance of the feed and also lubricate the machinery which allows to improve its performance and its useful life. From a nutritional point of view, fats have advantages such as: they allow to increase the energy concentration of the feed, reduce caloric stress and, due to their lower heat increase, improve energy efficiency per kcal of metabolizable energy.

The key criterion for assessing a fat is its net energy content. This value depends fundamentally on its raw energy content and its intestinal digestibility, which fundamentally depends on its ability to solubilize and form micelles in the intestine. Due to the peculiarities of the digestive system of ruminants (in which the supplementary fat affects the microorganisms of the rumen, which hydrogenate and saturate the fatty acids released in the rumen by hydrolysis of triglycerides), the absorption of fats is different in its case is that in the case of monogastrics, so that the assessment of the utility of the same fat for animal feed will be different as it will be applied for the feeding of ruminants or monogastrics.

In addition to the net energy content, other important criteria when considering the inclusion of a fatty material in a feed are its availability and relative price compared to other energy sources. In accordance with these criteria, there is a growing interest in the use in animal feed of fatty materials obtained by the processing of fats from natural sources. Due to their lower price, the by-products of various industries whose raw material is fat and, in particular, oleins (residues of edible fat refining), lecithins, fats of fats, distillates from the industry of the industry stand out glycerol and distillates from fat refining.

Summary Description of the Invention

The invention describes the recycling of free fatty acids and oleins as residual by-products from the refining of vegetable and / or animal fats. Its reaction with the residual glycerin or glycerol optionally, in turn, from the biodiesel production processes, gives rise to its reconstitution into triglycerides with the same or similar fatty acid contents of vegetable and / or animal fats or oils which was split in the refining process, which gives rise to residual fatty acids. So if we take residual fatty acids from palm oil, we will obtain mono, di and triglycerides of the same oil, as if we start with olive, sunflower, rapeseed, coconut, etc. fatty acids, we will reach polyglycerides similar to those of the origin through the reaction of said fatty acids with the stoichiometrically necessary amount of glycerol or with slightly higher amounts thereof, following the process of the invention, described herein. The result will be a reconstituted fat with the same or similar characteristics as the fatty acids or oleins from which we start, with the same melting point of origin, or with very small differences, if any. The final acidity (in mgKOH / g fat) varies between 3 and 20, depending on the oleins or starting fatty acids, preferably 3-15 (<5 for crude palm oil, for example) and the treatment in terms of temperature and time, to which they are subjected. This acidity can be corrected by adding a small amount of a base, preferably calcium, by optionally filtering, to achieve the separation of the soaps formed. Detailed description of the invention

The present invention describes a productive process of vegetable or animal fats, from free fatty acids or residual oleins from fat refining processes. Residual free fatty acids will be converted into fats of the same starting fatty acids, that is, from palm oil refining, residual fatty acids from palm oil will be recycled, reconstituting palm oil, from an olein of residual fatty acids. from the sunflower refining we will obtain a sunflower oil and so on, with other fatty acids or oleins without being mixed beforehand to obtain mixed fats, although the invention also contemplates the previous mixture in which case the result would give the same proportion of fatty acids in fat, that the proportion thereof starting.

Olein is understood as the mixture of free fatty acids, triglycerides, water and impurities resulting from the fat refining process. In oleins, although the major component is free fatty acid, the percentage of triglycerides is important (greater than 30%). On the contrary, in free fatty acids, the free fatty acid component is markedly majority, compared to a marginal triglyceride composition of 0 to 3%.

Among the preferred fatty acids used as by-products for carrying out the present invention are: palm oil fatty acids PFAD (Palm Fatty Acid Destilled), coconut oil, coprah, olive oil, oil oleins Sunflower oil, soybean oil, rapeseed oil and oil refining of tallow, butter, etc.

The fatty acids that most commonly form part of the fats and oils to be recycled in the present invention are long chain fatty acids such as oleic, stearic, palmitic, myristic, lauric, linoleic and linolenic. Also appear shorter chain fatty acids such as: butyric, capric, caprylic and caproic. The free fatty acid content of these by-products varies between 45% and 98%, with the rest of the by-product being triglycerides of the corresponding fat.

For example, palm fatty acids have an approximate composition of:

97% free fatty acids.

1% triglycerides plus water.

2% impurities

The oleins of other vegetable oils have approximately:

Between 55 and 65% of free fatty acids.

Between 30 and 45% triglycerides.

Between 5 and 15% of water and impurities.

These by-products have an energetic value for the feeding of monogastric animals, proportionally diminished, that is, the lower the percentage of free fatty acids.

The described invention consists in revaluating these by-products by converting them into reconstituted whole fats (triglycerides) without varying their original fatty acid composition.

Said residual fatty acids are reacted under specific conditions, with commercial or residual glycerol or glycerin, derived, in turn, from biodiesel production processes. Such by-products can be received concentrated and purified. If they are not purified, it is preferable to carry out a purification prior to their addition to the reaction. In any case, they can also be used without purification, provided they have a percentage of water and impurities not exceeding 20%.

All this is achieved with the reaction of fatty acids or oleins with the stoichiometric amount of glycerol or slightly higher amounts thereof, of the order 3-15%. The resulting products have been tested in comparison to the source fats giving nutritional results similar to the original ones.

The reaction of fatty acids with glycerol is carried out in reactors with suitable stirring and at a temperature between 140 ° and 200 ⁰ C, for a time ranging from 1 to 48 hours being able to apply lower temperatures and employing more time or temperature and less time , depending on the melting points of fatty acids or oleins. For example, the melting point of the PFAD ranges between 40-42 ⁰ C. The average range of 150 ° and 48 hours could be set for melting points of 40 ° to 42 °.

A preferred embodiment of the invention is to use a temperature between 170 ° and 19O ⁰ C, for 4 to 6 hours, with vacuum application (10-25, preferably 16 mmHg) and using as reaction catalysts, zeo litas and / or diatomaceous earth, in concentrations of each catalyst of up to 5%. The reaction occurs with stirring (350-1000 rpm), preferably at 600 rpm. The catalysts used can be found in the sepiolites of the manufacturers, for example: Tolsa, Sepiolsa, Zeocat, Foret, etc ... One of the preferred zeo litas used is NaY, but natural zeo lita can also be used.

The optimum procedure is automatic, the preferred heating is heating with thermal oil, the addition of glycerol and the filling of the reactor with the raw material will preferably be automatic. Among the fatty acids or oleins that can be used are all those used in human or animal, agricultural or animal feed such as palm, coconut, palm kernel, soy, sunflower, rapeseed, corn, olive, linseed, butter, tallow, etc. .

At the end of the process a cooling of the reaction mass is carried out to be stored and transported. The cooling time will be proportional to the melting temperature of the source fat. The cooling step is carried out with a heat exchanger to take advantage of the energy that dissipates in it, this can be done by exchanging the hot product with the slightly higher melting temperature depending on the diffusion of fatty acids from departure. The fats thus reconstituted, obtained by reconversion of the residual fatty acids are used in animal feed. For this and that they are commercially attractive it is necessary to reduce its residual acidity since this could mean the rejection of the clients or a strong reduction in its price. In the present invention the elimination of said acidity has been resolved by a process with calcium hydroxide, if necessary.

Different non-limiting examples of the present invention are shown below, in which, in the form of tables, the effects of the addition of reconstituted fats, in particular reconstituted palm fat compared to natural fats, on food are shown of, specifically for the example, chickens.

EXAMPLE 1: EFFECT OF LEVEL AND THE SOURCE OF FAT ADDED TO THE DIET ON THE PRODUCTIVITY OF CHICKENS FROM 1 TO 21 DAYS OF AGE

Reconstituted fat level Raw palm

0% 2% 4% 6% 4%

1-11 days

GMD, g 22.1 22.5 22.8 22.8 22.8

CMD, g 27.1 27.8 28.1 28.4 27.4

IC 1.26 1.23 1.23 1.25 1.21

11-21 days

GMD, g 49.1 52.0 52.2 52.7 55.2

CMD, g 69.1 70.8 75.8 75.7 73.9

IC 1.45 1.36 1.48 1.44 1.34

1-21 days

GMD, g 34.9 36.6 36.8 37.1 38.2

CMD, g 47.1 48.3 50.8 51.7 49.6

IC 1.35 1.32 1.38 1.38 1.31

Mortality,% 1.1 0.0 0.4 0.0 0.3 EXAMPLE 2. EFFECT OF THE TYPE OF FAT ADDED TO THE DIET ON CHICKEN PRODUCTIVITY, FROM 1 TO 21 DAYS OF AGE

Reconstituted raw palm fat

4% 4%

1-11 days

GMD, g 22.8 22.8

CMD, g 28.1 27.4

IC 1.23 1.21

11-21 days

GMD, g 52.2 55.2

CMD, g 75.8 73.9

IC 1.48 1.34

1-21 days

GMD, g 36.8 38.2

CMD, g 50.8 49.6

IC 1.38 1.31

Mortality,% 0.4 0.3

EXAMPLE 3: I THINK ENERGY VALUE

GMD: Daily Average Weight Gain

CMD: Average Daily Consumption

CI: Growth Index

EB: Gross Energy

AME: Apparently Metabolizable Energy EXAMPLE 4: SYNTHESIS OF THE RECONSTITUTED FAT GLICEROL MONOLEATO IN THE PRESENCE OF A ZEOLITE CATALYST

The binder or binder used is an inert clay material.

The zeolite used is NaY.

The acid used in the reaction is oleic and alcohol is glycerol (propane triol). The stirring speed at which the reaction is carried out is 600 rpm.

The water that is formed during the esterification process is eliminated continuously.

EXAMPLE 5. EFFECT OF THE INCLUSION OF CRUDE PALM RECONSTITUTED IN FEED FOR POST-DESTINED LECHONS

objective

The objective of this example is to determine the effect on the productive parameters of the inclusion of Reconstituted Crude Palm (PCR) in the feed of freshly weaned piglets as an alternative energy source to butter. The start and end date of the study is July 2008.

Material and methods

-Experimental animals: A total of 36 male piglets were used, weaned at 21-25 days, with an initial average weight of 6.5 kg ± 0.5 kg. The piglets were grouped taking into account the initial live weight. All animals were monitored individually at the start of the test.

-Accommodation:

The animals were housed in a clean and disinfected ship provided with 6 boxes with 6 animals per box. Each box had individual feeders and troughs. The environmental control of the room was consistent with the temperature and ventilation needs of the animals.

-Experimental diets:

Two types of feed were manufactured, formulated according to the FEDNA (Spanish Foundation for Animal Nutrition Development) raw material tables, with the aim of covering the needs for piglets of these ages established by the NRC (National Research Council of the USA). ), using quality raw materials and respecting the appropriate inclusion levels (Table 1). The moisture content, crude protein, crude fat, crude fiber and ashes of each feed were determined in triplicate.

The feed was administered in presentation flour in bags of 25 kg. All diets will be supplied ad libitum throughout the experience.

-Experimental design:

The test consisted of 2 experimental treatments:

• Treatment 1: I think butter.

• Treatment 2: I think Reconstituted Crude Palm. Each treatment was replicated 3 times, each replica being formed by 6 piglets at the start of the test. The distribution of the treatments was done by blocking the room effect, in order to avoid the effect of temperature differences, air currents, etc.

750 kilograms were needed per treatment. For treatment 2 it took 30 kilograms of Reconstituted Crude Palm.

Three periods were established, two of two weeks each and one of 4 weeks that encompassed the previous two, during which the type of feed was maintained:

• 3-5 weeks of age (6-9 kg of weight) with 6 animals per replica.

• 5-7 weeks of age (9-16 Kg. Weight) with 6 animals per replica.

• 3-7 weeks of age (6-16 kg of weight) with 6 animals per replica.

Controls and data collection

During the development of the test the following parameters were measured:

• Productive parameters:

-Number of animals per box at 3, 5 and 7 weeks of life. -Live weight per box at 3, 5 and 7 weeks of life. -Weekly feed consumption per box. -Mortality: writing down date, age of the animal and weight.

With the data taken, the following values are obtained per replication:

• Live weight at 3, 5 and 7 weeks of age. • Average daily gain of 3-5, 5-7 and 3-7 weeks of age.

• Average daily consumption of 3-5, 5-7 and 3-7 weeks of age.

• conversion rate 3-5, 5-7 and 3-7 weeks of age. • Mortality.

Statistic analysis

The data will be analyzed by the GLM procedure (General Linear Model: statistical procedure that compares two populations that differ in a few parameters) from SAS (statistical package that is used to analyze the results obtained from the test). The data obtained will be analyzed according to the type of replica and age. The model includes the type of diet:

And _and -. = Μ + _j + e _and treatment -

. _Yy: The random to study variable, the variable statistically analyzed: weight gain, consumption, mortality and conversion rate. . μ: Mean of the random variable to study.

. treatment _j : Factor whose effect on the random variable is to be studied. In this case the inclusion of the reconstituted palm or the use of lard in the piglet feed.

. e _lj: model error.

Table 1. Experimental feed

Table 2. Laboratory analysis

RESULTS

Table 3: Average weight of animals

Treatment Average weight 21 days Average weight 35 days Average weight 49 days (Kg) (Kg) (Kg)

Control _{6 2} l 9.34 14.99

PCR 621 9/76 16.55

C. V. * 0.41 4.81 5.99

Pr> F ** (λ89 (Ul 0.0213

(Subscripts x, y indicate trend being P <0.10; a, b indicate significant differences being P <0.05)

The animals that received the feed that included the Reconstituted Raw Palm finished the test with greater weight than the animals that received the control food with Manteca as a source of fat.

Table 4. Average Daily Gain of animals

Average earnings Average earnings Average earnings

Daily treatment 21-35 days (Kg) daily 35-49 days (Kg) daily 21-49 days (Kg)

Control 0.184 0.404 0.314 PCR 0.209 0.482 0.368

C. V. * 14.98 10.44 9.96

Pr> F ** 0.93 0.84 0.88

The differences in gain were not statistically significant, however, the growths of the animals that received the feed with PCR were always higher than those of the animals that received the control feed. As a result, higher weights were obtained as seen in Table 3. Table 5. Average daily consumption of animals

Average consumption Average consumption Average consumption

Daily treatment 21-35 days daily 35-49 days daily 21-49 days (Kg) (Kg) (Kg)

Control 0.290 0.736 0.544 PCR 0.325 0.811 0.609

C. V. * 14.50 5.68 7.44

Pr> F ** 0.92 0.82 0.87

In the same way as in earnings, differences in consumption were not statistically significant. However, the consumption of the animals that received feed with PCR were higher than those of the control treatment during the whole test.

Table 6. Food Conversion indices conversion index index conversion index

Conversion treatment 21-35 daily 35-49 days daily 21-49 days days

Control 1.57 1.82 1.74 PCR 1.56 1.69 1.66

C. V. * 5.23 4.93 3.38

Pr> F ** 0.87 0.0256 0.0930

The differences in the conversion rate were significant in the period 35-49 days. The animals had arrived with greater weight at day 35, with which they were able to take better advantage of the food (conversion rate 130 grams better). For the entire test, a tendency towards significance is observed in favor of CRP (differences of 80 grams). Table 7

Mortality (%) Mortality (%) Mortality (%)

Treatment 21-35 days 35-49 days 21-49 days

Control 0 0 0 PCR 2.77 0 2.77

C. V. * 0.46 0 0.46

Pr> F ** 0.37 0.99 0.37

^ Variation Coefficient: statistical parameter used to describe the homogeneity of the population studied.

** The value F is one of the results of the GLM. Pr> F is the probability as much for one that a value cannot be said if it is from one group or another within the population. The smaller F is, the better the treatments are distinguished.

The animals had normal health throughout the test, with only one drop in the entire test in the PCR treatment. Stool consistency was acceptable in both treatments throughout the test.

The addition of PCR to a piglet feed helps to improve the final weight of the animals, as well as their conversion rate in the 4 weeks after weaning.

From the examples given, especially from comparisons with raw palm, in the same concentration it can be seen that the differences in productivity and energy value between reconstituted and natural fat are practically negligible. Moreover, it is also observed that both parameters, productivity and energy value of the feed, increase as we increase the concentration of reconstituted fat, within the test values.

Claims

1.- Recycling process of fatty acids or residual oleins by reconstitution of fats characterized by reacting said fatty acids or residual oleins with glycerol in an amount, at least stoichiometric and at a temperature higher than 100 ⁰ C, for a period of time greater than 96 hours.

2. Method according to claim 1 characterized in that the glycerol is added in an amount between 3-15% higher than the stoichiometric.

3. Method according to any of claims 1 or 2, characterized in that the glycerol added to the reaction is also of residual origin.

4. Method according to any of claims 1 to 3, characterized in that the fatty acids or residual oleins used in the reaction are preferably from the fat refining.

5. Method according to any of claims 1 to 4, characterized in that the residual glycerol added in the reaction is preferably derived from the biodiesel production industry.

6. Method according to any of claims 1 to 5 characterized in that the residual fatty acids used in the reaction are of plant origin.

7. Method according to claim 6 characterized in that the fatty acids are selected from residual fatty acids from the refining of: palm oil, coconut oil, coprah, olive oil, sunflower oil oleins, soybean oil oleins, rapeseed oil oleins.

8. Method according to any of claims 1 to 7 characterized in that the residual free fatty acids from the refining of palm oil are reacted with glycerol at a temperature of 170 ° -200 ° C for 5-12 hours.

9. Method according to any of claims 1 to 5 characterized in that the residual fatty acids used in the reaction are of animal origin.

10. Method according to claim 9 characterized in that the fatty acids are selected from residual fatty acids from the tallow or butter refining.

11. Method according to any of claims 1 to 10, characterized in that the acidity of the reconstituted fat obtained can be reduced, if necessary, by the addition of calcium hydroxide to the reaction medium, after the formation of the fat.

12. Method according to any of claims 1 to 11 characterized in that the reaction occurs in the presence of vacuum.

13. Method according to any of claims 1 to 12 characterized in that the reaction occurs in the presence of catalysts in a concentration up to 5%, preferably zeolites and / or diatomaceous earths.

14.- Reconstituted fats based on free fatty acids and / or residual oleins and glycerol, which have reduced acidity when partially saponified with calcium hydroxide.

15. Reconstituted fats according to claim 14 from the refining of fats, oils or oleins, vegetables and / or animals.

16. Reconstituted fats according to any of claims 14 or 15 wherein optionally the glycerol that constitutes them, also has its origin as a byproduct of biodiesel production,

17. Use of the reconstituted fats of claims 14 to 16 in animal feed.

18. Use according to claim 17 in feeding monogastric animals.

19. Use according to claim 18 in feeding pig piglets.

20. Use according to claim 17 in poultry feeding, preferably in chicken feeding.