ES2284390B1 - USE OF CALCIUM CARBONATE AS A TECHNOLOGICAL COADYUVANT IN OIL AND FAT EXTRACTION PROCESSES. - Google Patents

Abstract

Use of calcium carbonate as a technological aid in the processes of oil and fat extraction. The present invention is related to the use of calcium carbonate as a technological aid in the processes of extracting oils and fats, more specifically virgin olive oil.

Description

Use of calcium carbonate as an adjuvant technological in the processes of extraction of oils and fats.

Field of the Invention

The present invention is related to the use of calcium carbonate as a technological adjuvant in oil and fat extraction processes, more specifically virgin olive oil

Background of the invention

Between 98% and 99% of the oil contained in the olives is made up of triglycerides that accumulate in mesocarp cells, in vacuoles, and in lesser Amount is dispersed in the cytoplasm.

In the extraction operation to obtain of quality olive oil you have to take care of many details, indispensable condition for its extraction is that it be done by physical and mechanical procedures and conditions, especially thermal, that do not produce any alteration. In These terms, European regulations define olive oils virgins as `` oils obtained from the fruit of the olive tree only by mechanical procedures or other procedures physical, in conditions that do not cause the alteration of the oil, and that they have not undergone any treatment other than washing, the decantation, centrifugation and filtration, excluding oils obtained by solvents, by adjuvants of chemical or biochemical action, or by procedures of resterification and any mixture with other oils nature (Annex of Regulation EC 1513/2001).

Quality oils are obtained when starting of whole olives, healthy and in an ideal state of maturation process as quickly as possible, because the storage or atrojado triggers fermentative processes on the fruit. The milling or crushing operation aims to break the pulp cells, mesocarp, and cause oil to leak out Vacuoles content. Until 1960 olive technology had used only the roller mills, but today they are used hammer mills with which a high degree can be obtained  of efficacy in cell rupture, although they cause emulsions in the paste when turning at high revolutions (3,000 rpm).

Industrial fatty yield is related with the degree of grinding, regulated in the hammer mill by the diameter of the sieve or grid perforations (light of the sieve). Usually and depending on the olive variety milled sieve light should increase as the olive maturity index.

The mechanically released oil must leave cell tissues in the form of small drops that in turn can lead to larger drops to form bags that can separate as a continuous phase. This stage takes place in a heat sink, within very strict temperature limits so as not to favor the loss of volatile products, responsible of the aroma of the oil, and that oxidation processes are not initiated and rancidity Virgin olive oil is considered as the oily juice of a fruit, olive, and with a good preparation it they must keep their aroma, flavor and components unaltered minorities that characterize it.

The temperature and duration of the shake results in the increase in oil yield in the extraction, whatever the extraction system: pressure, centrifugation or percolation. However, this increase in temperature and beat time has a negative impact on the quality and content of antioxidants and vitamins in virgin olive oils (Hermoso et al ., 1998).

In an industrial process, the extraction performance ranges from 80% to 90% of the total oil because all the oil present in the olives is not released, there is something left in the cells that have not broken, in the colloidal system of olive paste (microgels) and bound in emulsion form with vegetation water. The difficulty of releasing this oil lies in the fact that the droplets of dispersed or emulsified oil are surrounded by a lipopropylene membrane.
theine (phospholipids and proteins) that keep them in that state, making it difficult to bind them (Boskou, 1998).

To get a good quality oil, both From the nutritional point of view as an organoleptic, it is necessary to:

to)

Starting from healthy and whole fruits, preferably collected from the tree.

b)

Optimal state of maturation and humidity, to avoid adding water to the process.

C)

Process the olives freshly collected within a period not exceeding 24 hours.

d)

Breaking most cells avoiding the formation of emulsions.

and)

Shake the paste at moderate temperature and without lengthening the beating time excessively.

Any professional in an oil mill knows that under the aforementioned operating conditions performance industrial can fall, on many occasions, between 10 and 20% of the fat content. You can easily lose between 2 and 4 kg of oil per 100 kg of olive when calls appear "difficult pastes" or emulsified pastes.

Technological adjuvants are used, in the extraction, with the aim of recovering most of the oil retained by the pastes. These substances are usually added in the thermobatcher and help correct the cellular structure, modify the physical-mechanical properties of the pastes and facilitate the separation of the oil. In Spain, hydrated magnesium silicate (natural talc) has been used since 1986 (Order of January 13, 1986 of the Ministry of Health and Consumption) and since 1989 (Order of November 30, 1989 of the Ministry of Health and Consumption) carbohydrase (pectinases, cellulases and hemicellulases) from Aspergillus aculeatus . However, European regulations prohibit, as indicated above, the use of biologically active technological adjuvants in the production of virgin olive oils, there being no alternatives to the use of talc as a technological adjuvant for the extraction of virgin olive oil and extra virgin

The rise in temperature and duration of the shake results in the increase in oil yield in the extraction, however, said increase has an incidence negative about the quality of virgin olive oils. By therefore, another relevant feature for adjuvants technological is that with their employment yields of extraction higher or similar to those obtained with the increase of the temperature, but maintaining the quality of the oils. This circumstance makes it even more difficult if substances can be obtained alternatives that can be used in these processes.

Brief Description of the Invention Definitions

Technological aid : any substance that is not consumed as a food ingredient itself, that is intentionally used in the transformation of raw materials, food products or their ingredients, to meet a specific technological objective during treatment or transformation, and that may result in the unintended, but technically unavoidable, presence of residues of said substance or its derivatives in the finished product, provided that such residues do not present a sanitary risk and have no technological effects on the finished product (Royal Decree 3177/1983 of Nov. 16).

The present invention provides a new Technological adjuvant, calcium carbonate and / or limestone, in oil and fat extraction processes.

Understanding that calcium carbonate is authorized as a food additive, and due to its high weight specific (2.72 g / cm3), which makes it easily removable by centrifugation, studies were carried out for use of calcium carbonate (CAS-Nº 471-34-1; EINECS 207-439-9) and limestone (CAS-No. 1317-65-3; EINECS 215-279-6) as adjuvants technology in the processes of extracting oils and fats, more preferably vegetable oils, even more preferably oil of olive, and even more preferably virgin olive oil and / or extra virgin

Finally, the characteristics have been analyzed of the oils obtained with the use of the adjuvant, checking that all of them meet the quality specifications regulated by the European Union, which would grant them the qualification of "extra virgin olive oil" and that there are no differences  statistically significant among the oils obtained with or without adjuvant (witnesses).

Thus, a first aspect of the present invention is related to the use of a compound that comprises calcium carbonate as a technological adjuvant, preferably in the food industry, more preferably in processes of extraction of oils and fats, more preferably oils vegetables, even more preferably olive oil, and even more preferably virgin olive oil or extra virgin olive oil. In a preferred embodiment of this aspect of the invention the Technological adjuvant is limestone. Hereafter this compound will be called "compound of the invention".

In a second embodiment of the first aspect of the invention the compound of the invention comprises a wealth of calcium carbonate of at least 90%, successively and more preferably at least 95, 98, 99%, and even more preferably 99.28%.

In a third embodiment of the invention and according to the second embodiment of the invention, the compound of the invention has a humidity of less than 5%, more preferably less than 3% and still more preferably less than 1%.

In a fourth embodiment of the invention and according to any of the previous embodiments, the compound of The invention has a maximum particle diameter of 55 µm, more preferably less than 44 µm; more preferably between 10-0.1 µm and in successively more embodiments Preferred between 5-1 µm, 4-1.5 um, 3.5-2, 3-2.5, and even more preferably an average diameter of 2.65 µm.

In a fifth embodiment of the invention and according to any of the previous embodiments, the compound of the invention is used in doses of at least 0.01%, in successively more preferred embodiments of the 0.01-30%, 0.1-20%, 0.5-10%, 1-5%, and even more preferably 1% or 3%.

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Brief description of the figures

Fig 1: Variation of extraction performance according to the olive variety and the percentage of calcium carbonate added.

Fig 2: Variation of extraction performance due to the addition of calcium carbonate.

Fig 3: Performance interaction graph of carbonate dose extraction for two temperatures

Fig 4: Performance interaction graph of  extraction versus temperature.

Fig 5: Response surface for yield, keeping the temperature constant at 30 ° C.

Fig 6: Variation of extraction performance according to the olive variety and carbonate percentages Calcium and talc employees.

Fig 7: Carbonate Granulometric Analysis calcium used in the tests.

Detailed Explanation of the Invention

The effectiveness of the technological adjuvant proposed (calcium carbonate and limestone) has been evaluated at laboratory level using performance analyzer Abencor for three important varieties of olives: Picual, Hojiblanca and Arbequina, with different maturity rates.

The results obtained in the tests show  stated that the use of micronized calcium carbonate allows to increase the extraction yields up to 4.51 kg of oil per 100 kg of olive in the Picual variety, 4.37 kg of oil per 100 kg of Hojiblanca olive and 2.63 kg of oil per 100 kg of olive variety Arbequina, with respect to the tests carried out without the use of adjuvants, said quantity depending on the variety, index of maturity and moisture of the olives, resulting in greater efficacy in the treatment of emulsified pastes, also called "pastes difficult. "

The following embodiments of the invention are not intended to be limiting thereof and only the Illustrate for your best understanding.

Examples of realization Example 1 Calcium carbonate used

The characteristics physicochemical calcium carbonate used to the realization of the following embodiments will be show below:

- Carbonate richness calcic 99.28% - pH 8.2 - Specific weight 2.72 gr / cm3 - Hardness 3 - Apparent density 1.20 gr / cm3 - Specific surface 5.8 m2 / gr

The following table shows other technical characteristics of the calcium carbonate used and in Fig 7 shows a graph in which its granulometry

one

The tests have been carried out with samples of olives ( Olea Europea L. ) of three varieties: Picual, Hojiblanca and Arbequina, the first from Jaén and the other two from Gilena (Seville). All samples have been characterized by determining the maturity index (Uceda and Frías, 1975), humidity and volatile materials in an oven at 105ºC and the oil content according to the soxhlet method (EEC Regulation 2568/91). The results are shown in the following table (Table 1).

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TABLE 1 Characterization of the samples of olives

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Example 3 Oil extraction and performance

The oils have been extracted using the Abencor yield analyzer. This equipment consists, essentially, of the three basic elements to simulate, at the laboratory level, the industrial process of obtaining virgin olive oil: hammer mill, thermobatcher and solid centrifuge, and a series of auxiliary elements (Martínez et al ., 1975).

The general working conditions are detailed then while the water temperature of the blender and shake time are specified in each section of experimental results:

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Screen Diameter mill: 5.5 mm.

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Whipped olive dough: 500 g.

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Centrifugation time: 1 min.

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Hot water addition (approx 50 ° C) for carryover: 100 mL.

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Centrifugation time with Water added: 1 min.

After centrifugation the oil obtained it has been decanted in a test tube for at least 3 hours, it has been filtered with filter paper and stored at 4 ° C in an atmosphere of N_ {2} until its analysis.

It has also taken a sample of the pomace that remains in the centrifuge to determine the amount of oil retained in it, using the soxhlet method, and be able to evaluate by difference with the initial oil, present in olives, the extraction yield (kg of oil per 100 kg of processed olives). This method has been chosen instead of determine the yield by the volume of oil obtained for being more precise, since the gravimetic measures are perform more accurately than volumetric ones.

Several experimental designs have been made ranging from simple comparison of returns with use or no carbonate at the dose variation thereof in order to Determine the optimal dose. Designs have also been made full 2 2 factories and response surfaces, Box-Behnken, to jointly evaluate the addition of carbonate, the temperature and the beat time of the paste olive (Montgomery, D. C. Design and Analysis of Experiments Limusa Wiley. Mexico, 2002.).

In all cases a statistical treatment of the results, using for analysis of variance (ANOVA) the Statgraphics statistical package Plus 5.1 of Statistical Graphics Corp., Rockville, MD, USA and for the statistical designs of experiments the computer program Design-Expert version 6.0.6 of Stat-Ease Inc., Minneapolis, USA.

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Example 3.1

Carbonate Efficiency

Specific application tests have been carried out of calcium carbonate using doses of 1% and 2%. In table 2 the results obtained for olives samples are shown Picual, Hojiblanca and Arbequina, beating in all cases the olive paste at 30ºC (water temperature of the thermobatcher)  for 55 minutes

Likewise, Table 2 shows the values of the statistical parameter p resulting from the ANOVA and the result of applying the procedure of the smallest differences Fisher significant (LSD).

TABLE 2 Yields (kg of oil / 100 kg of olives)

3

From Table 2 it follows that the use of carbonate calcium improves extraction performance by 1.37 points (kg of oil / 100 kg of olive) for the Picual 1 sample; at 0.98 points for the Picual 2 sample; at 3.73 points for the sample of Hojiblanca (which represents a 19% increase in performance); Y 2.56 points for the Arbequina sample.

The difference in performance observed between  Picual 1 and Picual 2 samples are related to the increase of the maturity index. The increase in this index decreases the need to use the adjuvant, that is, this is especially useful for olives with low maturity index, principle of campaign, and for those that originate difficult pastes, as per example the frozen olives.

The data in Table 2 has been represented in Figure 1 and it shows graphically the increase in extraction performance obtained, in all cases, due to the addition of calcium carbonate.

Example 3.2

Determination of the recommended dose

There have been two series of experiments with samples of Picual and Arbequina olives to determine the doses most appropriate use of calcium carbonate.

Table 3 shows the data of performance for Picual 4 and Arbequina samples. The milkshake of the  olive paste has been made at 30 ° C (water temperature of the heat sink) for 55 minutes.

TABLE 3 Yields (kg oil / 100 kg olives) for different doses of carbonate added

4

The values in Table 3 have been represented in Figure 2 by points, observing how, in both cases, the extraction yield increases with the percentage of added calcium carbonate, until reaching a maximum value from which seems to be a small decrease in performance, probably due to the oil that is retained in the carbonate itself.

The data in Table 3 have been adjusted, by non-linear regression with the Systat SigmaPlot 9 program Software Inc., to the following equations, where R is the yield (kg of oil / 100 kg of olives) and C is the dose of calcium carbonate added (%).

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R = 18.73 + \frac{5.0805 \ C}{0.1881 + C} - 0.0856 \ C\ hskip0,5cm (1) For the Picual variety:

 \ hskip1,6cm 

R = 18.73 + \ frac {5.0805 \ C} {0.1881 + C} - 0.0856 \ C

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R = 22.33 + \frac{3.5129 \ C}{0.3305 + C} - 0.1854 \ C\ hskip0,5cm (2) For the Arbequina variety:

 \ hskip1cm 

R = 22.33 + \ frac {3.5129 \ C} {0.3305 + C} - 0.1854 \ C

The previous equations have been used to represent the solid lines of Figure 2, observing a good fit, and to determine the optimal value of adding calcium carbonate

For the Picual variety the optimal dose of Carbonate addition is 3.1%, which would give an oil yield 23.24% maximum, ie 4.51 kg more oil per 100 kg of olives against non-use of carbonate (24.1% of increase).

For the Arbequina variety the optimal dose of carbonate is 2.1%, which would give a maximum yield of 24.96%, is In other words, 2.63 kg of oil per 100 kg of olives versus the non-use of carbonate (12.8% increase).

However, as can be seen in Figure 2 these maximums are not very pronounced and therefore there is a range wide variation of the dose of calcium carbonate added without that this significantly undermines the performance of extraction.

Example 3.3

Combined study of carbonate dose and temperature of smoothie

In order to know simultaneously what effect has the batter temperature of the paste and the dose of carbonate used, and check if both factors interact among them, a complete 2 2 factorial design has been carried out with the sample of Picual 3 olives. Table 4 shows the design experimental and the yields obtained, maintaining the general experimental conditions and beating pasta olive in all cases for 20 minutes.

TABLE 4 Experimental design and yields

5

In view of the results you get the Next information:

to)

Value Medium: (16.06 + 17.11 + 17.96 + 18.20) / 4 = 17.33%

b)

Temperature effect: (-16.06 + 17.11-17.96 + 18.20) / 2 = 0.64%

C)

Carbonate Effect: (-16.06-17.11 + 17.96 + 18.20) / 2 = 1.49%

d)

Interaction Effect: (16.06-17.11-17.96 + 18.20) / 2 = - 0.40%

First of all it has been proven that the observed variation in performance is due to a real effect of each factor and not the experimental error, for this purpose they have made three replicas of a point, obtaining a standard deviation of 0.25 and a standard error of 0.15. Then we can accept that All effects have statistical significance.

Carbonate addition has a greater effect than temperature rise, since an carbonate addition 1% increase performance by 1.49 points (9.3% increase in performance) while the temperature rise of 20ºC to 40ºC only increases the yield 0.64 points. This conclusion is very interesting because working at low temperature oils of better quality are obtained.

On the other hand, we observe a small interaction effect between temperature and added carbonate,
-0.40%, as shown in Figures 3 and 4 of the interaction graphs.

The interaction graphics show that the lines are not parallel, then the effect of temperature is higher for a 0% carbonate concentration than for a 1% carbonate concentration, and the effect of adding carbonate is higher at low temperature, 20 ° C, which has temperature high, 40º.

Example 3.4

Combined study of carbonate dose and time of smoothie

Similar to the previous one, to the sample of Picual 3 olives has been made a complete factorial design 2 2 to simultaneously know the effects of the time of olive paste smoothie and carbonate addition to it About oil yield. Table 5 shows the design experimental and the yields obtained, maintaining the general experimental conditions and water temperature of the heat sink at 20 ° C.

TABLE 5 Experimental design and yields

6

In view of the results you get the Next information:

to)

Value Medium: (16.06 + 19.04 + 17.96 + 19.76) / 4 = 18.21%

b)

Time Effect: (-16.06 + 19.04-17.96 + 19.76) / 2 = 2.39%

C)

Carbonate Effect: (-16.06-19.04 + 17.96 + 19.76) / 2 = 1.31%

d)

Interaction Effect: (16.06-19.04-17.96 + 19.76) / 2 = - 0.59%

In this case the increase in shaking time It has a greater effect than the addition of carbonate, observing that the effect due to the addition of carbonate, 1.31%, is very similar to that obtained previously, 1.49%.

There is also a slight effect of interaction, -0.59%.

Example 3.5

Combined study of carbonate dose, temperature and milkshake time

To optimize the extraction performance of oil depending on the shake temperature, the beat time and the carbonate addition has been done an experimental design based on the Response Surface Methodology, which we allows you to inspect a response, which can be displayed as a surface, when experiments investigate the effect it has varying quantitative factors in the values that a dependent variable or response. That is, it is about finding the optimal values of the independent variables or factors that Maximize the answer.

TABLE 6 Experimental design and yields

7

The data obtained have been adjusted to a model explanatory using the statistical package Design-Expert Below is the corresponding model adjusted to the temperature factors (T), time (t) and carbonate dose (C), Equation (3), and in Table 7 the analysis of variance is shown.

(3) Performance (%) = -7.81089 + 1.35475 \ T + 0.042107 \ t + 18.235C - {} \ hskip3cm - 0.0187 \ T2 - 1.995 \ C2 - 0.718 \ T \ C + 0.010225 \ T2 \ C

TABLE 7 Analysis of variance for the model tight

8

In Table 7 you can see that a value of F equal to 80.42 implies that the model is significant, that a value of the Lack of Adjustment equal to 0.63 implies that it is not significant with respect to the pure error and that the value of the coefficient of adjustment determination 0.9737 reasonably agrees with the prediction 0.9283, so it can be considered that the model obtained serves to predict the performance of the extraction as a function of the three operation variables studied.

In order to analyze the influence of each experimental point on the model, diagnoses were made Leverage statistics, standardized residual and distance of Cook in the answer, finding that these were within the normal ranges, so you can say that the model is stable in the range studied.

To observe the effects of the factors, in the  interval studied, on the response (performance) the perturbation graph. For this, two were kept constant factors varying the other within the design range and it determined the value of the response variable, observing that the factor that has less influence on performance is the temperature. Therefore, in Figure 5 the response surface and corresponding contour plot, depending on the factors time and dose of carbonate added to a temperature of 30 ° C.

The optimization has been done through the methodology of the desired function using the statistical package  Design-Expert with which the solutions shown in Table 8.

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TABLE 8 Optimal adjusted model

9

On the other hand, the adjusted model allows us also compare different job options as shown in Table 9

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TABLE 9 Different options for the variables of operation

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For operating conditions considered normal, 30ºC temperature and 55 min shake, not using carbonate, yield 18.31%, and use 1.5% carbonate, yield 22.68%, represents an improvement of 4.37 points, that is, a 24% improvement in performance.

Carbonate allows working at temperatures low, 20ºC, obtaining more performance, 23.54%, than working at high temperatures, 40 ° C, 20.25% yield, for a time of 90 min shake

In the extreme case of working at temperatures low 20ºC and shake times low 20 min, the yield between Do not use 12.65% carbonate or use it, 20.60%, it is a 7.95 point improvement that results in a performance improvement of 63%.

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Example 3.6

Comparison between calcium carbonate and talc

In order to compare the extraction efficiency between calcium carbonate and talcum, technological adjuvants of physical action and therefore of the same nature, it has conducted a series of trials using doses of 1% and 2% of both. The talc used, Talcoliva brand, is marketed by the Luzenac Group company.

Table 10 shows the results. obtained for samples of Picual and Arbequina olives, beating in all cases the olive paste at 30 ° C (temperature of water from the heat sink) for 55 minutes.

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TABLE 10 Yields (Kg of oil / 100 kg of olives)

eleven

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The data in Table 10 have been represented in Figure 6 and it shows graphically the increase in extraction performance obtained, in all cases, due to the addition of a technological adjuvant and as the addition of calcium carbonate improves performance with respect to the addition of talcum powder.

Once the corresponding treatment has been carried out  statistical data we conclude that there are no differences significant for a 95% confidence level (p = 0.05) between the yield obtained using the same dose of carbonate or talc, however, at the level of averages, the yield obtained with carbonate exceeds the yield obtained in most cases with talcum powder

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Example 3.7

Quality of the oils obtained with calcium carbonate

To evaluate the quality of oils obtained, using calcium carbonate, have been taken into account the quality criteria established in Regulation (EC) No 1989/2003 of the Commission of November 6, 2003 amending the Regulation (EEC) No 2568/91, concerning the characteristics of the olive oils and olive pomace oils and on their analysis methods. Table 11 shows some results.

TABLE 11 Oil quality parameters obtained

12

Once the corresponding treatment has been carried out  statistical results obtained allow us to affirm that no there are significant differences, for a 95% confidence level, in the quality parameters between the controls and the oils obtained with carbonate. In all cases they could be granted the rating of "extra virgin olive oil" according to the European regulations

Claims (20)

1. Use of a compound comprising carbonate calcium as a technological aid for oil extraction and fats 2. Use according to the preceding claim wherein said adjuvant is limestone. 3. Use according to the preceding claim wherein the  Oil to extract is a vegetable oil. 4. Use according to the preceding claim wherein the  Vegetable oil is olive oil. 5. Use according to the preceding claim wherein the  Olive oil is of the virgin or virgin olive oil type extra. 6. Use according to any of the claims previous where the compound has a rich carbonate calcium of at least 90%. 7. Use according to the preceding claim wherein the  compound has a richness in calcium carbonate of at least 95% 8. Use according to the preceding claim wherein the  compound has a richness in calcium carbonate of at least 99% 9. Use according to the preceding claim wherein the  compound has a humidity of less than 5%. 10. Use according to the preceding claim wherein The compound has a humidity of less than 3%. 11. Use according to the preceding claim wherein The compound has a humidity of less than 1%. 12. Use according to the preceding claim wherein the compound has a maximum particle diameter of 55 \ mum. 13. Use according to the preceding claim wherein The compound has a maximum diameter of less than 44 µm. 14. Use according to the preceding claim wherein The compound has an average diameter of 2.65 µm. 15. Use according to the preceding claim wherein The dose of compound used is at least 0.01%. 16. Use according to the preceding claim wherein The dose of compound used is at least 0.1%. 17. Use according to the preceding claim wherein the dose of compound used is between 0.1-30% 18. Use according to the preceding claim wherein the dose of compound used is between 1-5% 19. Use according to the preceding claim wherein the dose of compound used is 3%. 20. Use according to claim 19 wherein the dose of compound used is 1%.