BR102016017869B1 - Process for obtaining crystallization seeds, crystallization seeds and use thereof - Google Patents

Abstract

PROCESS FOR OBTAINING CRYSTALLIZATION SEEDS, CRYSTALLIZATION SEEDS AND USES THEREOF The present invention relates to a process for obtaining crystallization seeds, potential in accelerating and modifying the crystallization of fats, as well as crystallization seeds in forms more stable polymorphs (Beta form) and, therefore, viable for application in chocolates, accelerating or making the tempering step unnecessary.

Description

FIELD OF THE INVENTION

[1] The present invention is part of the food and beverage area and refers to a process for obtaining crystallization seeds using mixtures of fully hydrogenated soybean oil (hardfat), potential in accelerating and modifying crystallization. of fats, as seeds of crystallization in more stable polymorphic forms and, therefore, viable for application as seeding in chocolates and for the development of substitutes of cocoa butter for use in chocolates.

FUNDAMENTALS OF THE INVENTION

[2] Cocoa butter (CM) is the main component in chocolates, characterizing the continuous phase of the product as a dispersing matrix for the solid particles of cocoa, sugar and milk (LOISEL et al., 1998). This fat can crystallize in 6 polymorphic forms, each with a different thermodynamic stability and melting point, identified as I, II, III, IV, V and VI, or by the Greek letters, y, α, β' and β, the VI form being the most stable (WILLE & LUTTON, 1966). By ensuring adequate sensory attributes and stable microstructure, the V or βV form is the most desirable polymorph for chocolate (HINDLE, POVEY & SMITH, 2002). The chocolate tempering process is fundamentally a controlled crystallization in which, through thermal and mechanical treatments, a specific percentage of crystals is produced in the most stable form of MC (HARTEL, 1991). From an efficient tempering, it is possible to facilitate the release, avoid the formation of fat-bloom in the cooling and storage and obtain a final product with good characteristics of brightness, texture (snap) and fusion.

[3] Chocolate production in Brazil totaled 800 thousand tons in 2013, with consumption of 790 thousand tons, approximately following the volume produced (ABICAB, 2014). Due to the significant national production of MC and chocolates, the replacement of their crystallization processes is a strategic issue from an industrial point of view. This is due to the fact that, in large-scale production, it is difficult to control the temperature at this stage, in addition to having disadvantages in terms of energy and space costs (HACHIYA, KOYANO and SATO, 1989).

[4] In search of new pre-crystallization processes, a new technique known as seeding has been progressively studied to replace the tempering process. In this technique, active nucleating agents or crystallization seeds with a melting point above 34 °C would be added directly to the chocolate, after the conching step and before the chocolate application step, either by molding or by coating. KOYANO and SATO, 1989). According to Schenk and Peschar (2004) the crystallization seeds must contain the information of crystalline packing, inducing the crystallization of fats in a desirable polymorph.

[5] Numerous advantages are pointed out due to the application of crystallization seeds in chocolates: less sensitivity to temperature variations, speed, obtaining higher quality fatty products (LONCHAMPT & HARTEL, 2004), acceleration of crystallization, effective crystallization between mixtures of vegetable fats and CM, the decrease in the incompatibility of CM with milk fat (ZENG, BRAUN & WINDHAB, 2002) and the delay of fat-bloom (SVANBERG et al. 2013).

[6] Most studies and patents involving the development or application of crystallization germs use MC as a raw material, applied already in the βV polymorphic form, desirable in chocolates (DESCAMPS & KEGELAERS, 2009; FAGES, LETOURNEAU and GONUS, 2006; FICHTL, DIETRICH and SCHLIEHE-DIERKS, 2013; KINTA and HARTEL, 2010).

[7] There are several methods of producing crystallization seeds in the literature, mainly from MC. Among them, the use of supercritical fluid stands out (FAGES, LETOURNEAU and GONUS, 2006; FICHTL, DIETRICH and SCHLIEHE-DIERKS, 2013).

[8] In a few studies, the use of active nucleating agents composed of triacylglycerols (TAG) such as tripalmitin (PPP) or the use of mixtures of PPP and l-palmityl-2-oleoyl-palmitin (POP) and between tristearin (SSS) and l-stearyl-2-oleoylstearin (SOS) (GWIE et al. 2006; PORE et al. 2009). There are few researches that use different raw materials for the production of nucleating agents. Lopes et al. (2015) developed spray cooling crystallization seeds employing soybean, cotton, palm and crambe hardfats, fully hydrogenated vegetable oils, which have a homogeneous composition of TAGs with high melting points.

[9] Hardfats represent low-cost industrial fats with great potential in modifying and accelerating the crystallization of cocoa butter (RIBEIRO et al. 2013). Lipid microparticles (SLM) or soy hardfat-based crystallization seeds obtained by Lopes et al. (2015) demonstrated the need for storage under controlled temperatures (between 25 and 45°C) for 1 to 139 days, aiming at the transition from unstable polymorphic forms (a) , obtained after particle production, to stable forms (β) . Storage at 45°C for 24 hours allowed the transition to the β form. However, it was found in the same study that high temperatures favored the agglomeration of SLM.

[10] Previous studies have already demonstrated the possibility of accelerating the polymorphic transition of hardfats with the addition of oils. The addition of 20% canola oil, for example, to soybean, rapeseed and cotton hardfats was able to promote the polymorphic transition from α to β after crystallization at 0°C (DE MAN, DE MAN & BLACKMAN, 1989). In another study, the addition of 1.5% and 5% of D-limonene, an essential oil, to cocoa butter and cocoa butter equivalent fat (CBE) enabled the polymorphic transition from the βV form to the more stable form. βVI during crystallization at 25°C (MIYASAKI et al. 2015).

STATUS OF THE TECHNIQUE

[11] The document entitled "Acceleration of polymorphic transition of cocoa butter and cocoa butter equivalent by addition of D-limonene" on behalf of Miyasaki, E. K et al., refers to the evaluation of the polymorphism of crystallized samples of Butter soft (Brazilian) cocoa (CB) and Cocoa Butter equivalent (CBE), with and without addition of 1.5% (m/m) and 5% (m/m) of D-limonene. The proposed invention differs from that document mainly because of the addition of D-limonene in another raw material, soy hardfat, with a composition of fatty acids (FA) and triacylglycerols (TAG) substantially different from the CB and CBE mentioned in the document.

[12] It is worth mentioning that in the document in the name of Miyasaki, a crystallization in the continuous lipid phase of CB and CBE with and without addition of D-limonene at room temperature (25°C) is reported, whereas in the present invention it does not treat from a simple static crystallization but from the production of microparticles (seeds) of soy hardfat added with D-limonene, crystallized by the spray cooling atomization process.

[13] Differently from that document, the present invention relates the use of the potential accelerator of the polymorphic transition of D-Limonene, verified in static crystallization of CB, for the production of stabilized crystallization seeds (β form), which demonstrates the novelty of the idea. Thus, the idea is not just a simple application of D-limonene in a different lipid base, but the production of microparticles stabilized by means of this monoterpene.

[14] The document entitled "The Effect of Limonene on the Crystallization of Cocoa Butter" in the name of Ray, Joydeep et al., refers to the evaluation of the crystallization behavior of CB after addition of 5% (m/m) of D-limonene. Such document discloses a static crystallization of CB with and without the addition of D-limonene at a temperature of 20°C. In a different way, the present invention does not deal with a simple static crystallization, but with the production of microparticles (seeds) of soy hardfat added with D-limonene, crystallized by the spray cooling atomization process. In addition, the present invention also differs from that document in that D-limonene is added to another raw material, soy hardfat, with a composition of fatty acids (FA) and triacylglycerols (TAG) substantially different from CB.

[15] Additionally, in a different way as in the document in the name of Ray, Joydeep et al., the present invention relates the use of the potential accelerator of polymorphic transition of D-Limonene, verified in static crystallization of CB, for the production of stabilized crystallization seeds (β form), which demonstrates the originality of the idea. Thus, the idea is not just a simple application of D-limonene in a different lipid base, but the production of microparticles stabilized through this monoterpene, aiming at application in chocolates and other industrial products or processes.

[16] The paper entitled "Impact of Limonene on the Physical Properties of Reduced Fat Chocolate", in the name of Do, T. A. L et al., refers to the effects on texture (hardness) and viscosity of chocolate with the direct addition of D-limonene (3% w/w in relation to the chocolate mass). In addition, the interest in D-limonene, present in this document, consists of its possible partial replacement of CB in chocolate, aiming at the production of chocolates with reduced fat content. It can be seen that D-limonene was applied directly to chocolate, mainly aiming at its effects on physical and mechanical properties and not on accelerating its crystallization. In the present invention, in a totally different way, D-limonene is carried by the crystallization seeds, being in the future applied in chocolates in this form, aiming at accelerating or eliminating the tempering stage.

[17] US200625B1 relates to the production of reduced/low fat chocolate by adding up to 5% (m/m) of D-limonene before, during and after the conching step. The present invention, on the other hand, differs from this document mainly in that D-limonene is carried by the crystallization seeds, and will be applied in the future in chocolates in this form and not in the continuous form, aiming at accelerating or eliminating the tempering step. It is also worth mentioning that in the document US200625B1, D-limonene was applied directly in the step prior to tempering, demonstrating the differences in the objectives of its addition to the product.

[18] Thus, as can be seen, the effect of D-limonene on the acceleration of polymorphic transitions and crystalline stabilization of cocoa butter (MC) is well known and documented in the prior art. However, such use is restricted to this raw material as a continuous lipid phase, not being directed to the manufacture of chocolates, in particular, to accelerate or make the tempering step unnecessary, objective of the present invention. The chocolate tempering stage has the function of forming nuclei of crystallization of the lipid phase of chocolate, with the formation of approximately 4% of stable beta-type crystals, through a specific heat treatment. These crystals, of a triacylglycerol nature, are responsible for structuring the crystal lattice in this stable form (beta), which characterizes quality chocolate.

[19] The direct addition of D-limonene to the chocolate mass does not fulfill the technological function of tempering, as this compound does not form triacylglycerol crystals. It is the use of soybean oil hardfat, composed of triacylglycerol molecules in the form of microparticles, which has the function of providing these stable beta crystals, in levels corresponding to those used in tempering, aiming at their replacement as a technological process. The D-limonene incorporated into the soy oil hardfat microparticle demonstrates the ability to accelerate the polymorphic transition and stabilization of the lipid microparticle, so that it can be applied as such; since this transition is very slow and requires specific heat treatment for stabilization.

[20] Thus, from the present invention, it is clear that in order for the tempering process to be replaced by the addition of microparticles (seeding), they must have a lipid nature equivalent to cocoa butter or substitutes, that is, triacylglycerol composition. , so that they can direct the characteristic polymorphic transitions and stabilization of these components. D-limonene, therefore, acts as an additive for the microparticle composed of soybean oil hardfat.

OBJECTIVES OF THE INVENTION

[21] The present invention aims to propose a process for obtaining crystallization seeds under the more stable beta polymorphic habit, composed of mixtures between fully hydrogenated (hardfat) soybean oil and different concentrations of D-limonene or canola oil. , obtained by spray cooling technique.

[22] Additionally, it is an object of the present invention to crystallization seeds with a smooth and homogeneous surface, in a spherical shape and without agglomeration as a product to be applied in chocolates and other lipid bases to accelerate or direct crystallization. It is still an objective of the present invention to propose the use of said crystallization seeds in sowing in the industrial production of chocolates, accelerating or making the tempering step unnecessary; as a microbiological control and also in applications in palm oil or in stearin as nucleating agents, for the induction of crystallization in the beta polymorphic form, collaborating for the development of cocoa butter substitutes, aiming application in chocolates.

BRIEF DESCRIPTION OF THE FIGURES

[23] FIG. IA shows the micrograph of pure soybean hardfat seeds performed at 25°C at 150x magnification, 500μm bar;

[24] FIG. 1B shows the micrograph of soybean hardfat seeds with 5% D-limonene addition performed at 25°C at 150x magnification, 500μm bar;

[25] FIG. 1C shows the micrograph of soybean hardfat seeds with 7.5% canola oil addition performed at 25°C at 150x magnification, 500μm bar;

[26] FIG. 2A shows the diffractogram (short spacing) of soy hardfat microparticles at times 0, 2, 7, 19 and 26 days at 25°C without addition of oils;

[27] FIG. 2B shows the diffractogram (short spacing) of soy hardfat microparticles at times 0, 4, 7, 19 and 26 days at 25°C with addition of 7.5% canola oil; and

[28] FIG. 2C shows the diffractogram (short spacing) of soy hardfat microparticles at times 0, 2, 7, 19 and 26 days at 25°C with addition of 5% D-limonene.

DETAILED DESCRIPTION OF THE INVENTION

[29] The present invention relates to a process for obtaining crystallization seeds under the more stable beta polymorphic habit, composed of mixtures between fully hydrogenated soybean oil (hardfat) and different concentrations of D-limonene or canola oil. comprising the following steps: a) melting the soy hardfat, for example in a water bath, jacketed tanks or in a microwave oven, at a variable temperature from 70 to 90°C, preferably from 75 to 80°C until complete melting of the fat crystals; b) adding from 1 to 15%, preferably from 5 to 7.5% w/w, of D-limonene or from 1 to 15% of canola oil, preferably from 5 to 10% w/w; c) heating the mixture under stirring in the range between 70 and 90°C, preferably from 75 to 80°C through a heating plate for 2 to 5 minutes for complete solubilization of the added oils; d) stabilizing the half jacketed mixture, for example in jacketed tank, under controlled temperature of 70 to 90°C for 6 minutes; e) atomize the mixture in a spray cooling system, which can consist of a container kept at a temperature between -10° to 10°C, preferably between -2° and 0°C, using a 0.2 to 2 mm atomizing nozzle , preferably from 0.7 to 1mm and compressed air pressures ranging from 0.5 to 5 kgf/cm2, preferably between 1.0 and 2.0 kgf/cm2 at room temperature; f) pack the crystallization seeds obtained in Pouch-type packaging, metalized and with zip or in another packaging system that is a barrier to water vapor, light and gases; and g) storing in closed containers in a temperature-controlled chamber of 10 to 30°C, preferably -25°C.

[30] Crystallization seeds were produced by the method described above and using the spray cooling technique initially with the addition of up to 1 to 15% D-limonene or canola oil to the soybean hardfat, resulting in a relatively loose powder and with no agglomeration.

Characterization of Seeds Morphology

[31] The analyzes of the morphology and microstructure of the crystallization seeds were performed on the samples soon after their production and after 7, 15 and 30 days of storage in a controlled temperature chamber at 25 °C, to investigate possible visual changes that occurred. in seeds during storage.

[32] The seed surface was evaluated by Scanning Electron Microscopy (SEM). An aluminum base (1.4 cm in diameter by 0.6 in thickness) was used with double-sided copper tape and a layer of colloidal graphite. Then the seeds were pulverized and fixed in this structure, and the samples were analyzed in a table-type microscope with variable voltage acceleration of 10 kV, with an increase of 150 times.

[33] The crystallization seeds produced are visually presented in the form of relatively loose powders with no agglomeration. Scanning electron microscopy (SEM) showed its spherical shape and confirmed the absence of agglomeration. In addition, they showed a smooth and homogeneous surface, proving the beneficial effect of D-limonene on hardfat crystallization and on the formation of crystallization seeds.

Mean diameter and particle size distribution

[34] The volumetric mean diameter and size distribution of the microparticles were determined in a particle size distribution analyzer with a laser diffraction system. The samples were dispersed in an aqueous solution containing 0.5% (w/w) of the Tween® 20 emulsifier and then added to the equipment's dispersion unit, which was filled with distilled water. The analysis was conducted at room temperature (25°C) and the mean diameter (D50) was calculated from seven replicates and considering the mean diameter of a sphere of the same volume (D[4,3]) • Polydispersity was evaluated by the span index, calculated by (D90 - Dio)/Dso, corresponding to the diameters of 10, 50 and 90% of the distribution. The polydispersity index indicated the particle size variation.

[35] This analysis was carried out on the samples immediately after their production and after 7, 15 and 30 days of storage in a controlled temperature chamber at 25°C, to investigate the appearance of possible agglomeration during storage.

[36] The average diameter (Dso) of the microparticles is 150 and 200μm. By way of comparison, the literature indicates a range of microparticles diameter from 5 to 500 μm for a satisfactory application as crystallization seeds, thus, the microparticles have this application potential.

polymorphic habit

[37] The polymorphic habit of the seeds was determined by X-ray diffraction, according to the AOCS Cj 2-95 method (AOCS, 2009). A Diffractometer was used using Bragg-Brentano geometry (θ:2θ) with Cu-Ka radiation (k = 1.5418 Â, voltage of 40KV and current of 30mA). Measurements were obtained with steps of 0.02° In 2θ and acquisition time of 2s, with sweeps from 15 to 30° (2θ scale). The identification of the polymorphic form was determined from the values of short spacings (distances between parallel acyl groups in triacylglycerol) characteristic of the crystals.

[38] The seeds were analyzed for polymorphic habit after 1, 2, 7, 19 and 26 days in storage at 25°C, with t = 1 corresponding to 18 hours after production. FIG. 2A shows the diffractograms of the soybean hardfat sample without added oils and FIG. 2B of sample with 7.5% canola oil added and FIG. 2C with addition of 5% D-limonene.

[39] The soybean hardfat sample without the addition of oils (Figure 2A) was found to crystallize in the less stable polymorphic form ot, observed by the characteristic peak at 4.14 Â. Even during storage of the sample for 26 days at 25°C, no polymorphic transition was observed. In contrast, the sample added with canola oil showed a complete polymorphic transition from the α form to the β form in just 4 days of storage at 25°C (Figure 2B), through the definition of peaks related to the short spacings characteristic of the β form. at 5.21 Â (referring to β-testearin), 4.60 Â, 3.84 Â and 3.69 Â from t = 4.

[40] As can be seen in the diffractogram of Figure 2C, well-defined peaks referring to the β form are visualized at 5.21 Â (referring to β-trystearin), 4, 60 Â, 3.88 Â and 3.73 Â for the sample with the addition of D-limonene to the soy hardfat from time t = 1 (18 hours after the production of the microparticles), which demonstrated the rapid polymorphic transition of the fat crystals. Although D-limonene represents a terpene, whose structure is quite different from a triacylglycerol molecule, this essential oil was able to affect the crystallization behavior of triacylglycerols (TAG) from soybean hardfat, accelerating the polymorphic transition much more efficiently than the addition of canola oil, which has TAG with chain size AG very close to those found in hardfat, despite being predominantly unsaturated.

APPLICATIONS OF THE PRESENT INVENTION

[41] Among the numerous applications that the technology proposed in the present invention presents, its direct use in sowing or seeding in the industrial production of chocolates stands out, inducing the formation of crystals also in the β form, desirable in this type of product with to speed up or make the expensive tempering or pre-crystallization step unnecessary.

[42] Other technological applications of crystallization seeds obtained in the β-polymorphic form include the application in palm oil or in stearin as nucleating agents, for the induction of crystallization in the β-polymorphic form, contributing to the development of substitutes for coconut butter. cocoa, aiming application in chocolates.

Claims (8)

1. Process for obtaining crystallization seeds, characterized by the fact that it comprises the following steps: a) melting the soy hardfat at a variable temperature from 70 to 90°C, preferably from 75 to 80°C, until complete melting of the fat ; b) adding from 1 to 15%, preferably from 5 to 7.5% w/w, of D-limonene or from 1 to 15% of canola oil, preferably from 5 to 10% w/w; c) heating the mixture under stirring in the range between 70 and 90°C, preferably from 75 to 80°C, from 2 to 5 minutes until complete solubilization of the added oils; d) stabilizing the mixture in jacketed medium under controlled temperature between 70 and 90°C for 6 min; e) atomize the mixture in a container cooled between -10° to 10°C, preferably between -2° to 0°C, using atomizing nozzle of 0.2 to 2.0 mm, preferably from 0.7 to 1 mm and pressure compressed air variable between 0.5 and 5.0, preferably between 1.0 and 2.0 kgf/cm2 at room temperature; f) packaging the crystallization seeds in metallized packages with a barrier to water vapor, light and gases; and g) storing in closed containers in a temperature-controlled chamber of 10 to 30°C, preferably at 25°C. 2. Process according to claim 1, characterized in that it uses the spray cooling technique. 3. Crystallization seeds characterized in that they are obtained by the process of claims 1 and 2 and are under the more stable polymorphic habit β. 4. Crystallization seeds, according to claim 3, characterized by the fact that they are spherical in shape, with a smooth and homogeneous surface and without agglomeration. 5. Crystallization seeds, according to claim 3, characterized in that they have an average diameter D50 between 150 and 200μm. 6. Crystallization seeds, according to claim 3, characterized by the fact that they present peaks referring to the β polymorphic habit at 5.21 Â, 4.60 Â; 3.88 Â or 3.84 Â and 3.73 Â or 3.69 Â. 7. Crystallization seeds characterized by comprising up to 1 to 15% of D-limonene or 5 to 10% of canola oil in their composition, being under the most stable polymorphic habit β, presenting peaks referring to the β form at 5.21 Â , 4.60 Â, 3.88 Â or 3.84 Â and 3.73 Â or 3.69 Â, spherical shape, with smooth and homogeneous surface, without agglomeration and average diameter D50 of 150 to 200μm. 8. Use of crystallization seeds as defined in claims 3 to 6 or 7, characterized by the fact that it is in the industrial production of chocolates.

Images