ES2641963B2 - NICE TASTE AND ODOR SYRUP CONTAINING CARBOHYDRATES, MICRONUTRIENTS, AND NATURAL REFINED POLYPHENOLS OF ALGARROBA, AND METHOD FOR OBTAINING - Google Patents

Abstract

A syrup with a pleasant taste and smell containing carbohydrates, micronutrients and natural refined water-soluble polyphenols from the carob bean pod and process for obtaining it. # The syrup comprises 20-55% sucrose, 5-20% glucose, 2-18% fructose, 0.3 -5% other sugars, 6-19% cyclitols (mainly D-Pinitol), 0.4-3.5% potassium, 0.35-4% refined phenolic compounds and 0.3-8% organic and inorganic impurities. # The procedure encompasses the aqueous extraction of Water-soluble components present in the carob pod, purification by ultrafiltration by membranes, and refining with adsorbent agents, in order to separate the desired components from those that are not. # The field of application of the syrup obtained is equal to of other sugars and natural sugar syrups.

Description

D E S C R I P C I Ó N

NICE TASTE AND ODOR SYRUP CONTAINING CARBOHYDRATES, MICRONUTRIENTS, AND NATURAL REFINED POLYPHENOLS 5 OF THE ALGARROBA, AND METHOD FOR OBTAINING IT.

SECTOR OF THE TECHNIQUE

C13B 20/00; Purification of sugar juices [2011.01]

C13B 20/16; By physical means, e.g. osmosis or filtration [2011.01]

10 C13B 12/20; Using adsorption agents, e.g. active carbon [2011.01]

BACKGROUND OF THE INVENTION

Carob has been applied as a food product since ancient times. In fact, the existence of syrups from 15 carob beans that are mainly marketed in Mediterranean countries, such as Italy, Morocco, Portugal and even Spain, among others, in the form of sugary carob syrups is known. However, these correspond to the result of evaporating water on the first aqueous extract of the unpurified locust bean pod, containing a mixture of all the water-soluble elements 20 that exist in the locust bean pod, resulting in compositions with a strong color dark, which although sweet in taste due to its high sugar content, maintain strong tones of unpleasant taste and smell characteristic of carob, as described previously in the state of the art (see for example patent 25 ES2060544A1 and documents cited in it).

In addition, a solution is described in the state of the art for the use of the natural sugars of the carob, by obtaining a colorless and odorless syrup containing the sugars from the carob in a natural way (this syrup and its obtaining are

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described in patent ES2060544A1). However, this solution has important drawbacks:

a) On the one hand, it drastically reduces the content of micronutrients (demineralized) and polyphenolic compounds of the product, thus dramatically decreasing, as we will reason in-extensively later, the nutritional properties of the product with respect to which the carob bean has natural form or raw carob syrup previously discussed (Int. J. Food Sci. Nutr., 2007, vol. 58 (8), 652-658; Int. J. Mol. Sci. 2016, 17 (11), 1875 (1-20)).

b) On the other hand, it complicates the process of obtaining said sugar syrup in such a way that it is not very efficient and has a high environmental impact (as it has been described in the state of the art, for example in patent ES2284381A1), doing so little competitive compared to other sugars. This is mainly because for the bleaching and demineralized processes proposed in the aforementioned solution (ES2060544A1) it is necessary to use ion exchange resins, which must be regenerated with acidic, basic and / or high content solutions. in mineral salts (brines), generating waste (dirty brines) of difficult management and very polluting. Although a possible technical solution to this problem has been proposed through the use of a supercritical fluid extraction stage of carob carbohydrates (see patent ES2284381A1), it is not exempt from serious limitations that make it difficult to transfer on an industrial scale , related to the complex and expensive facilities required for working with fluids under supercritical conditions, such as high pressures, high temperatures, high safety requirements and very high production costs (see for example: RSEQ Annals, October-December 2003, N ° 4, 15-23). Although the use of supercritical fluids in the pharmaceutical and food industries has increased in recent years, it remains limited to products of very high added value for the reasons mentioned, a condition a priori not satisfied by sugars or sugar syrups, which are led by

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general to large volume markets where there is high competition between products from different sources.

The use of carob dates back to ancient Egypt, who collected their fruits for cattle, among other uses. The seed has also been formerly used as a unit of weight by Arab peoples, who called it "karat", taking it as a standard of weight against gold and precious stones (see for example, Compr. Rev. Food Sci. Food Saf. 2016, 15 (1), 6372) In addition, since its inception the fruit of the carob tree has been used as food, largely due to its high sugar content. However, at present, its use is mostly limited to the seed, which represents only 10% of the weight of the fruit, from which the LBG (E410) is extracted, used as a thickener, stabilizer and flavoring in food, pharmaceutical industries and mainly cosmetics. The rest of the fruit, the pod, representing around 90% by weight, is used and has been used until now mainly as a by-product for animal feed. However, this is changing recently since the pod of the carob fruit is rich in a wide range of compounds of high nutritional value and healthy bioactive properties, especially its content in bioactive polyphenols, and also in cycitols (mainly D-Pinitol ) and mineral salts (see, for example, high-impact and high-impact scientific reviews such as: Int. J. Food Sci. Nutr., 2007, vol. 58 (8), 652658; Int. J. Mol. Sci. 2016, 17 (11), 1875 (1-20)). Because of this, a significant number of researchers have recently recommended the inclusion of this product in the diet, claiming about the beneficial properties it provides, such as diabetes control, prevention of heart problems, the lower frequency of certain types of cancer, or its anti-inflammatory properties, among others ((Int. J. Food Sci. Nutr., 2007, vol. 58 (8), 652-658; Int. J. Mol. Sci. 2016, 17 (11 ), 1875 (1-20).) That is why the object of the present invention is focused on obtaining a sugar syrup of carob of high added value, which on the one hand has a pleasant smell, color and taste, but which in turn respects the nutritional qualities and

healthy that the product presents in its origin, a problem that until the

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Present invention was unsolved.

Additionally, the use of the carob pod to obtain value-added products such as the one presented here, foreseeably has a positive impact by stimulating the creation of carob crops, which have been shown to have a lower carbon footprint than other crops. when performing the life cycle and carbon footprint analysis (see Chem. Eng. Trans. 2010, 21,613-618).

In the scientific literature it has been found that ultrafiltration by membranes has potential application in the improvement of traditional cane sugar purification processes (See for example the following reference: Sep. Pur. Technol. 2001, Vol. 21 (3) , 247-259), and also in the separation of carbohydrates and polyphenols from certain fruit juices (reference Inter. Scholar. Sci. Res. Innovation 2007, vol 1 (10), 115-122). However, we have not found any reference on its application to the purification of sugary carob syrups. Surprisingly, in the course of our investigations we found that through an ultrafiltration operation on membranes it was possible to purify the juice from the aqueous extraction of the water-soluble compounds of the carob pod, sugars, cyclosols (mostly D-Pinitol), micronutrients and refined polyphenols, in such a way that they are separated in a simple and very efficient way from the unwanted compounds that would give it black color, and unpleasant taste and smell, allowing obtaining a flavor syrup economically and with minimal waste generation and pleasant smell, which contains carbohydrates, micronutrients and natural refined water-soluble polyphenols from the carob pod.

EXPLANATION OF THE INVENTION

This invention relates to a syrup of pleasant taste and smell, which contains carbohydrates, micronutrients and natural refined water-soluble polyphenols of the carob bean pod and a process for obtaining it. The syrup object of the present invention is obtained by means of a

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process of aqueous extraction of carob pulp, and subsequent application of physical refining methods, specifically ultrafiltration and neutral adsorbents, avoiding the strong cationic resins described in the state of the art (ES2060544A1), decolorizing and demineralizing ion exchange columns , since these drastically reduce the nutritional qualities of the product, raise its production cost and generate significant waste, so that with the process of the present invention the syrup obtained finally contains the minerals and water-soluble carbohydrates of the carob pulp and also an important part of the polyphenolic compounds that, as we have said before, are healthy, but nevertheless our syrup is free of those other compounds that give the traditional carob syrups negative organoleptic properties, such as an intense black color, as well as smell and taste drain nice.

The fields of application of the product provided by the present invention should be contemplated in those uses similar to those of other sugars and sugary syrups, including colorless and odorless sugary syrups from the carob bean described in the state of the art, but with the following benefits : i) Lower production cost than known sugary syrups, including lower production costs than colorless and odorless carob sugar syrups (approximately 40% lower than the latter); ii) Lower environmental impact on its production than known sugary syrups, including colorless and odorless carob sugar syrups (approximately 50% lower energy consumption and 45% less water, compared to the latter) ii) Organoleptic properties suitable for a more extensive use than traditional black carob syrup with an unpleasant taste and smell and iii) Better nutritional characteristics than the colorless and odorless carob syrups described in the state of the art, due to their micronutrient content and refined polyphenols

To obtain this product, a colored carob syrup,

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Pleasant taste and smell, which contains carbohydrates, micronutrients and natural refined water-soluble polyphenols from the carob bean pod, a series of research studies were conducted aimed at obtaining a natural carob extract in which they would have been removed in a simple way and effective by physical methods the negative characteristics of the juice, such as its intense black color, as well as its smell and taste excessively intense and bitter, but, in contrast to the state of the art (ES2060544A1), that this be carried out selectively , so that not only carbohydrates and cyclitols (mainly D-Pinitol) remain in the syrup, but also micronutrients (eg mineral salts, since the carob pod is very rich in, for example, potassium that has important functions at the muscular and nervous system level), and a part of water-soluble polyphenols, for their proven health benefits (see for example Int. J. F ood Sci. Nutr., 2007, vol. 58 (8), 652-658; Int. J. Mol. Sci. 2016, 17 (11), 1875 (1 -20)). For this, new techniques were investigated, such as ultrafiltration with membranes, which allow to discriminate between permeate (obtained broth) and rejection (excess broth) by range of molecular sizes, and the use of adsorbent agents, avoiding in any case cationic resins and the demineralizers described in the state of the art since they entail the disadvantages of a high production cost and an important generation of waste with high environmental impact.

In order to obtain the product according to this invention with the aforementioned properties, the problem to be solved was focused on achieving a technically feasible process that would allow, in a cost-effective, efficient and environmentally friendly manner, to obtain the sugars, cyclosols (mainly D-Pinitol), micronutrients and healthy polyphenols that carob naturally possesses, but in such a way that the syrup obtained had adequate organoleptic and nutritional qualities, that is, that it had a pleasant taste and smell and a commercially acceptable color, not intense black, at the same time. that, as we have said, there would not be a drastic decrease in its beneficial qualities for health with respect to

original raw material, which has great nutritional benefits that

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It is interesting to preserve. Therefore, all research and development efforts focused on these points.

With respect to the extraction phase of water-soluble organic compounds and mineral salts, it is known that the carob pulp is formed by a multitude of cells bounded by a cell wall permeable to dissolved substances, but that however there is also an ectoplasmic membrane which before ripening the fruit seems to be only permeable to water, but not to dissolved substances. It is also known that in the dried fruit, said ectoplasmic membrane loses that property, allowing the passage of certain water-soluble molecules, such as sugars.

In the course of our investigations we discovered that, like carbohydrates, the mineral salts of interest (micronutrients), as well as the healthy water-soluble polyphenols that we want to extract and preserve in syrup, are extractable from the carob pod with water at temperatures normal, making temperature rise unnecessary, which is an advantage with respect to obtaining sugars from other natural sources, such as beets (see for example the information contained in ES2060544A1 and the documents cited therein).

With respect to the purification of the must, or juice resulting from the aqueous extraction of the carob pulp, there is a great variety of agents and procedures described in the state of the art for the stages of coarse filtration, fine filtration, clarified, discolored and deodorized, such as purification with whitewash, lime and alumina, bentonites, activated carbon, exchange and demineralizing resins or a combination of the above. However, none of them alone or in combination, provides the desired product, a carob syrup of suitable color for the food industry, not black, and pleasant taste and smell, which contains not only carbohydrates, but also Natural refined water-soluble micronutrients and polyphenols of the carob pod.

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After continuing with our investigations, it was surprisingly proven that the purification of the juice of the first extraction by using ultrafiltration by membranes, gave excellent results in the separation of those organic and inorganic species that were desired (carbohydrates, cyclyols such as D -Pinitol, micronutrients and refined water-soluble polyphenols) selectively with respect to that other important part of unwanted organic species, which were mostly responsible for the negative organoleptic properties. Surprisingly, it was also discovered that this permeated juice of ultrafiltration in membranes, could be further refined in its organoleptic qualities, until obtaining more palatable tones of flavor and smell, through a simple and very efficient operation of passage through a column filled with an agent adsorbent, without loss in its nutritional properties. Although the application of these neutral adsorbent agents has been reported in the state of the art as very disadvantageous, due to their high inefficiency, when used on juice from the crude aqueous extract of carob (see the information contained in patent ES2060544A1), we discover unexpectedly, when some of these adsorbents were applied to the previously ultrafiltered juice, they greatly increased their effectiveness, and furthermore, their subsequent regeneration could be carried out simply and efficiently, by means of environmentally friendly processes, with virtually no waste generation. Among the adsorbent agents tested successfully are active carbon and neutral adsorbent resins (non-cationic, anionic, or demineralizing), which, as said, were greatly increased by receiving the juice after the ultrafiltration operation on membranes, with respect to the inefficient results obtained by passing the non-ultrafiltered juice.

Specifically, according to the present invention, the purification of the juice, resulting from the aqueous extract of the carob bean pod, by ultrafiltration by membranes and subsequent contact with an adsorbent agent, was carried out as follows:

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The prefiltered juice (coarse filtration) is conducted to a membrane ultrafiltration equipment, consisting of: i) two tanks, one for entering and receiving the recirculated juice, and another for leaving the permeated juice, ii) a passage through membranes where it has place the ultrafiltration and iii) a pump that keeps the juice in recirculation as well as adequate pressure and flow rates.

Surprisingly, the membranes used for a molecular level separation of the compounds of interest, from those other unwanted compounds, are those of pore sizes in the range of 1 KDalton (1000 dalton) to 150 KDalton, more specifically those around at 1, 5, 8, 15, 50 and 150 KDalton, obtaining the best results with the pore size membrane of 1 KDalton or less. This stage of membrane ultrafiltration is a process of continuous purification, since the volume at the exit of permeated and purified juice is replaced in the inlet tank with virgin juice of the first extraction.

After membrane ultrafiltration, the juice obtained has a yellow-orange color. This product can be concentrated (evaporating water) to the desired Brix degrees, preferably between 65-75 Brix, obtaining an appetizing honey-colored syrup, of pleasant organoleptic qualities, since its smell and taste have been considerably improved with respect to the juice of game that would give rise to syrup or traditional carob syrup.

Moreover, the treatment with adsorbent agents of the juice obtained after

the ultrafiltration operation on membranes, such as activated carbon or

non-cationic, anionic or demineralizing adsorbent resins, gives rise to

an even more refined product, with shades of color, smell and taste more

soft. Surprisingly, in our investigations we discovered that

adsorbent agents employed greatly increased their effectiveness and

acting capacity, when used on the ultrafiltered membrane juice, with

regarding its use on non-ultrafiltered juice, with refining capabilities

for juice volumes between 10 and 50 higher according to this

invention. Thus, in our invention the use of this type of

adsorbent agents, which is not recommended in the state of the art for the

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processed of sugary carob syrups, it becomes a recommended operation after ultrafiltration, since it is efficient (allows the treatment of large volumes of juice), economically viable (1050 times less adsorbent agent is needed than without previous ultrafiltration and also This agent becomes easily regenerable) and environmentally friendly (the waste generated by regeneration of the adsorbents is practically nil). All of this, according to what is described in the present invention, performing a membrane ultrafiltration operation prior to the use of the adsorbent agents. The adsorbent agents used with satisfactory results were: activated carbon, bentonites, as well as neutral adsorbent resins, which further improve the process significantly with respect to the ionic resins used in the state of the art (ES2060544A1). Thus, we use with good results among other neutral resins, the following: polystyrene resins, polystyrene resins crosslinked with divinylbenzene, acrylic resins and cyclodextrin-based resins. The best results were obtained by using as an adsorbent activated carbon, both powder and granular.

Specifically, the ultrafiltered membrane juice is passed through a column filled with granular activated carbon of vegetable origin based on coconut bark. During the passage of the juice a part of the dye molecules that have survived the passage through ultrafiltration accompanying carbohydrates and minerals, are stopped by partial adsorption on the surface of the adsorbent agent, in this case activated carbon, due to weak electrostatic interactions of Van-der-Waals type. However, carbohydrates and micronutrients, of great affinity for the liquid (aqueous) phase, pass through the column without being retained. As a consequence, the juice at the exit has a smaller load of those coloring molecules that are also those that still give it a certain, although low already, bitter hue to carob. The advantage of using neutral adsorbent agents such as those discussed in the present invention (activated carbon, bentonites or neutral resins), is that the adsorption of the dye molecules is weak and therefore

Thus, the adsorbent agent can be easily regenerated by inverting the

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process, that is, causing desorption with hot water or hydroalcoholic mixtures, without the use of brines, or acidic or basic solutions of high cost and environmental impact, which would be the case in ionic and demineralizing resins.

The syrup thus obtained, after concentrating evaporating water to the desired Brix degrees, is a natural carob syrup, honey-colored, with a pleasant smell and taste, containing carbohydrates (sucrose, glucose and fructose), cyclitols (mainly D-Pinitol), micronutrients (eg high potassium content), and healthy refined polyphenols, which has the following advantages compared to existing syrups from carob:

1) On the raw carob syrup:

Elimination of the intense black color, and the unpleasant taste and smell characteristics that hinder its commercialization as sugary syrup.

2) On the totally colorless and demineralized carob syrup described in the state of the art (ES2060544A1):

Better nutritional properties and healthy properties, for its contribution in essential micronutrients such as potassium and for its content in refined polyphenols. Lower cost and lower environmental impact on its production.

Therefore, and according to a first aspect, the present invention provides a natural carob syrup consisting of the following components:

Sucrose: 20-55%

Glucose: 5-20%

Fructose: 2-18%

Other sugars: 0.3-5%

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Cyclitols (mainly D-Pinitol): 6-19%

Potassium: 0.4-3.5%

Phenolic compound (flavonoids, glycosylated flavanols and hydrolysable tannins): 0.35-4%

Organic and inorganic impurities: 0.3-8%

Where the percentages are expressed in weight of the dry matter and the intervals given in such a way that the possible logical variations due to the particular origin of each fruit, such as its variety, the parameters that affect the harvest (rains, terrain) are contemplated , etc.), among others.

Additionally, and in accordance with a second aspect of the invention, there is provided a process for obtaining the natural extract of the carob bean of the composition mentioned above, which encompasses the following steps:

1. Carob cleaning.

2. Thick chopping.

3. Separation of pod and seed.

4. Thin slicing.

5. Aqueous extraction of the water-soluble components of the sheath.

6. Pressing.

7. Coarse filtering.

8. Ultrafiltration in membranes.

9. Treatment with an adsorbent agent.

10. Concentration

BRIEF DESCRIPTION OF THE DRAWINGS

PROCESS DIAGRAM.

5 Figure 1. Diagram of the constituent stages of the process.

CLEANING THE ALGARROBA ^ THROCKED THICK

^ SEED AND SEED SEPARATION ^ FINE TROCEED ^

^ WATER EXTRACTION ^ PRESSED ^ THICK FILTER ^

^ ULTRAFILTRATION IN MEMBRANES ^

10 ^ TREATMENT WITH AN ADSORBENT AGENT ^ CONCENTRATION

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PREFERRED EMBODIMENT OF THE INVENTION

1. Carob cleaning.

The carob fruit comes from the field, so it is usually accompanied by a series of foreign elements, foreign to the fruit 5 such as earth, stones, branches or possible metallic elements, among others. Therefore, the first operation to be carried out is the cleaning of all these elements outside the carob fruit, to obtain a clean fruit, allowing the entry into the chopping phase under adequate hygiene conditions. This cleaning is carried out both manually and mechanically in the case of metal objects.

2. Thick chopping.

The cutting is carried out in a hammer mill, adjusted to break the pod into pieces of adequate size, without damaging as far as possible the seed or garrofín, which separates intact from the pod. In this way, an excessively coarsely cut locust bean pod is obtained for aqueous extraction (diameter around 2 cm). This diameter is excessive for extraction since thicker sizes require longer extraction times for water to penetrate inside the sheath and soluble products diffuse into the aqueous phase. However, a cut of 20 the finest pod is not possible at this point since this would cause the seed to break, compromising its use.

As for the operating conditions, it is necessary to avoid heating at this stage by friction that can lead to a rise in temperature and degradation of sugars. Thus, the temperature is controlled 25 at all times so that it is below 40 ° C.

3. Separation of pod and seed.

The product obtained after the previous stage of thick chopping, goes to a sieve that separates the seed from the thick sheath pieces.

This sieve acts automatically by a spring vibration system driven by a low consumption motor.

4. Thin slicing.

The thick sheath pieces are taken to a new cutting hammer 5 that now crushes them to the right size for a correct extraction operation (approximately 0.5 centimeters in diameter). Excessive crushing generates a large amount of fines that subsequently complicate the filtering processes. Therefore, the size of the slices is adjusted to a compromise situation, in which the extraction times are not too long, but the amount of fines produced is not excessive.

As with thick chopping, in terms of operating conditions it is necessary to avoid friction heating, always checking that the temperature does not exceed 40 ° C.

5. Aqueous extraction of the water-soluble components of the sheath.

The extraction is carried out in a discontinuous reactor, with a ratio

between chopped pod and water of between 1.3 and 3 liters of water per kilogram of chopped pod. Contact times with good agitation are low, around 30-45 minutes, insufficient for the proliferation of microorganisms, avoiding unwanted fermentation and other abnormal biological processes. The temperature for extraction is between 15 and 35 ° C.

6. Pressing.

Taking into account that the carob pod has a high tendency to absorb moisture, with the capacity to retain around its weight in water, and that the process performance depends largely on the effectiveness of this stage of separation of the juice from the residual organic vegetable matter, it is clear that it is essential to use a pressing method as efficient as possible.

In the course of our investigations, methods of

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industrial presses in continuous and discontinuous, obtaining satisfactory results with roller and piston presses, with the difference that the first works in continuous and the second in discontinuous.

The temperature for this pressing operation is between 15 and 5 at 35 ° C and the times depend significantly on the type of press used.

7. Coarse filtering.

The juice obtained after the pressing operation carries a significant amount of solids of varying sizes. These must be removed before moving on to the next stage of membrane ultrafiltration, since otherwise they would cause significant problems.

In the course of our investigations we discovered that it is essential that coarse filtration be carried out sequentially, up to the degree of final fineness required. That is, a series of sieves of increasingly thinner thickness 15 have to be used, since if only the finest sieve screen is used, the broth obtained will have the same quality, but the filter will suffer from repeated obstructions that will cause fluid operation impracticable.

After several tests, we found that an effective sieve sequence 20 that allows continuous work in a fluid manner, includes filtering at approximately 300, 100 and 40 microns. In addition, in the market there are varied solutions that allow the mechanical cleaning of the sieves continuously, without the production having to stop at logical working times.

The juice thus obtained still has an important load of solids in a suspension of less than 40 microns in size, although this is much lower than the initial one, and does not pose a serious problem for the next stage of membrane ultrafiltration, since it is not capable of obstructing the ducts in the membranes, which have a much larger diameter, and also do not imply a limiting decrease in the fluidity of the juice, which must be continuously

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recirculating by the action of a bomb. However, the final syrup must be free of suspended particles and therefore, in order to determine the nature and proportions of them and thus refine them in their withdrawal after this coarse filtration operation, we carry out a particle size analysis by light scattering methods, finding that they are in approximate proportions between 2-7%, with sizes always greater than 0.1 microns.

8. Ultrafiltration in membranes.

The juice obtained after the coarse filtration operation is taken to the entrance tank to the ultrafiltration equipment by membranes. At this point, the juice contains, on the one hand, suspended particles of less than 40 microns and not greater than 0.1 microns, and on the other hand, dissolved, organic species (carbohydrates, cyclitols such as D-Pinitol and mainly polyphenols), and inorganic ( among them potassium, magnesium and calcium ions). This juice can be concentrated, where you would get a traditional syrup of traditional carob (sugary because of its high sugar content), black color, very intense flavor and smell of carob. However, that product has limited applications as has been explained extensively before. Additionally, as we have discussed above, this juice can be subjected to bleaching and demineralized operations using ion exchange and demineralizing queens, to obtain a completely colorless sugar syrup, with a fruity sweet taste and smell, as described in the state of art (ES2060544A1). However, the process for this, as has already been reasoned, is expensive, has a high environmental impact and results in a product that has lost an important part of its nutritional properties, since it is completely exempt from the minerals it provides carob, some of them of great importance as potassium, and is also exempt from all the healthy polyphenols that contain carob at its origin, backed by recent scientific studies of the highest level (see for example Int. J. Food Sci. Nutr ., 2007, vol. 58 (8), 652-658; Int. J. Mol. Sci. 2016, 17 (11), 1875 (1-20)). Our goal was to find a method of

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Purification of the juice that allowed discriminating between those unwanted molecular components that infer the product some negative properties of color, smell and taste, which we therefore wanted to remove, and those other molecular components of the juice that without negatively affecting its organoleptic properties, provide the desired nutritional and healthy properties of carob.

Through the ultrafiltration operation by membranes, first of all, a juice that is completely clarified, that is to say absent of suspended particles, is achieved. In addition, a juice that is no longer black, but has a yellow-orange color, once concentrated similar to honey. Additionally, the juice obtained has greatly lowered the tones of flavor and smell characteristic of carob that they do not like, being much softer. Surprisingly, the thorough chemical analysis of this juice indicated that, in addition to carbohydrates and cyclites, it still contains a large part of polyphenolic compounds of healthy properties.

Preferably, the membrane ultrafiltration equipment consists of an inlet and receiving reservoir of recirculated juice, an outlet tank of the permeated juice through the membrane, and a pore-sized 1000 dalton (1KDalton) membrane passage. The operation is carried out continuously, so that the volume of permeate juice is replenished with virgin juice in the inlet tank. The working temperature is between 30-40 ° C, so that, without degrading the sugars or the rest of the components dissolved in the water, the fluidity is maximum and with it the permeate flow.

After this membrane ultrafiltration operation, the juice obtained has a yellow-orange color. This product can be concentrated (evaporating water) to the desired Brix degrees, preferably between 65-75 Brix, obtaining an appetizing honey-colored syrup, of pleasant organoleptic qualities, since its smell and taste have been greatly improved with respect to the juice of game that would give rise to syrup or traditional carob syrup.

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9. Treatment with an adsorbent agent.

The treatment with certain neutral adsorbent agents (not cationic, anionic or demineralizing resins), of the juice obtained after the ultrafiltration operation on membranes, results in an even more refined product, with even softer and palatable shades of color, smell and taste. . Surprisingly, the adsorbent agents employed have very high efficiencies and the ability to treat very large ratios of treated juice volume (Ljugo) versus adsorbent weight (Kg. Absorber): Ljugo / Kg. Adsorbent. This relationship is much more favorable now, according to the present invention, which it was with the non-ultrafiltered juice, obtaining ratios even of Ljugo / Kg.adsorbent = 100 L / Kg, when it has been proven that the non-ultrafiltered juice saturates the same adsorbent agent with ratios even less than 10 L / Kg. Surprisingly, the treated juice retains an important part of the nutritional and healthy properties of carob in its origin.

Preferably, the juice obtained after the 1KDalton membrane ultrafiltration operation was passed through a column filled with granular activated carbon of vegetable origin based on coconut bark, a process in which all carbohydrates, cyclitols (mostly D- Pinitol) and minerals pass without being retained, as well as an important part of polyphenols, flavonoids, glycosylated flavanols and hydrolysable tannins, while the part of the dye molecules with the worst flavor and smell that still remained are stopped by partial adsorption on the surface of the adsorbent agent, due to weak electrostatic interactions of the Van-der-Waals type. This surprising preferential affinity can be attributed to the particular chemical nature of the worst tasting and odor coloring substances present in carob, characterized by the presence in its structure of aromatic rings, as well as phenolic groups and carboxylic groups, all capable of interacting with the adsorbent as we have commented. Therefore, the juice has after passing through the column filled with adsorbent, a bright yellow-gold color, which once concentrated to 65-75 Brix gives rise to a syrup

golden very pleasant to the palate, smell and sight.

The operation is carried out at a temperature between 25-35 ° C, adjusting the flow through the column so that the contact times between the juice and the adsorbent agent are adequate, according to the recommendations of the manufacturer (each employee's neutral adsorbent agent has its own).

10. Concentration

The juice from the previous stages of ultrafiltration and treatment with neutral adsorbents, which is between 24-27 Brix, must be concentrated, evaporating water, up to 65-75 Brix, which are the appropriate values for commercialization. This operation has to be carried out avoiding that the juice suffers from intense thermal stress, taking care that the temperatures do not exceed 55-60 ° C for as short a time as possible. In the market there are many industrial solutions for this purpose, 15 being the one we have used in the course of our investigations, a vacuum concentrator of the descending film type.

DOCUMENTS CITED

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and mineral contents of carob (Ceratonia siliqua) fruit, flour and syrup ”. Int. J. Food Sci. Nutr., 2007, vol. 58 (8), 652-658.

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Claims (4)

5 10 fifteen 1. A syrup of pleasant taste and smell, which contains carbohydrates, micronutrients and natural refined water-soluble polyphenols of the carob pod, more specifically constituted by the following components: Sucrose: 20-55% Glucose: 5-20% Fructose: 2-18% Other sugars: 0.3-5% Cyclitols (mainly D-Pinitol): 6-19% Potassium: 0.4-3.5% Phenolic compound (flavonoids, glycosylated flavanols and hydrolysable tannins): 0.35-4% Organic and inorganic impurities: 0.3-8% 2. A process for obtaining the syrup of pleasant taste and smell, which contains carbohydrates, micronutrients and natural refined water-soluble polyphenols of the carob pod, according to claim 1, characterized in that it comprises the following steps: a) Carob cleaning, performed manually and mechanically. b) Thick chopping, in a hammer mill, adjusted to break the pod into pieces of size such that it is possible to separate the pod from the seed or garrofin, leaving it intact. c) Separation of pod and seed. d) Thinly chopped, bringing the thick sheath pieces to a new hammer chopper that crushes them to a new size smaller than that obtained in coarse slicing, this new size being able to allow an operation of extraction after said fine chopping e) Aqueous extraction of the water-soluble components of the sheath, with 5 low contact times, from 30 to 45 minutes. f) Pressing. g) Coarse filtering, using sieves arranged sequentially, from more than 300 microns, to about 40 microns. h) Ultrafiltration of the juice of the previous stage (g) through membranes, 10 obtaining a permeated juice by pores of size equal to or less than 150 KDalton, which is a totally clean product of suspended solids, with a color load of less intensity than the juice of the previous stage, and pleasant smell and taste properties. i) Concentration of the juice to levels of 65-75 Brix, to obtain a marketable syrup of pleasant taste and smell containing carbohydrates, Natural refined water-soluble micronutrients and polyphenols of the carob pod. 3. Process for obtaining the syrup of pleasant taste and smell according to claim 2, characterized in that it comprises prior to the step of The concentration of the juice, an additional stage of treatment with an adsorbent agent, such as activated carbon or neutral resins, of the ultrafiltered juice, in order to improve its organoleptic properties. 4. Use of the carob fruit to obtain a pleasant flavor and smell syrup containing carbohydrates, micronutrients and polyphenols 25 natural refined water-soluble carob pod according to the procedure defined in claims 2 to 3. DRAWINGS FIGURE 1. PROCESS DIAGRAM CLEANING THE ALGARROBA ^ THROCKED THICK ^ SEED AND SEED SEPARATION ^ FINE TROCEED ^ 5 ^ WATER EXTRACTION ^ PRESSED ^ THICK FILTER ^ ^ ULTRAFILTRATION IN MEMBRANES ^ ^ TREATMENT WITH STILL ADSORBENT AGENT ^ CONCENTRATION