Method for producing glucosinolate-free oil and defatted meal from plant seeds of the brassicaceae family

Abstract

The present invention relates to a method for producing oil and defatted meal with a glucosinolate content of less than 30 micromoles / g from seeds of the Brassicaceae family, comprising: (a) grinding and hydrating the seeds in a seed:water ratio of 1:2 to 1:7; (b) heating the seed slurry to between 15°C and 50°C; (c) drying the fatty slurry by centrifuging and heating, or only heating, to a fatty slurry temperature of 70°C to 90°C; and (d) subjecting the resulting fatty meal to solvent extraction, producing a meal that is defatted with solvent and a miscella. The miscella is subjected to a separation of the solvent and crude oil, which is the first product of the method, and the solvent meal is subjected to a separation of the solvent and the dry meal, which is the second product of the method.

Description

[0001] PRODUCTION PROCESS OF GLUCOSINOLATE-FREE OIL AND DEFATTED FLOUR FROM SEEDS OF PLANTS OF THE BRASSICACEAE FAMILY

[0002] DESCRIPTION

[0003] TECHNICAL SECTOR

[0004] The present invention belongs to the technical field of the chemical industry. In particular, it relates to a new process for the manufacture of glucosinolate-free oil and defatted meal from seeds of plants of the Brassicaceae family, preferably from Ethiopian mustard seeds (Brassica carinata), using a novel extraction process based on an adaptation of the olive pomace and olive pomace extraction process.

[0005] BACKGROUND OF THE INVENTION

[0006] Ethiopian mustard (Brassica cari nata) is an oilseed species belonging to the Brassicaceae family, which also includes other species of the Brassica genus such as rapeseed (Brassica napus L), Indian mustard (Brassica juncea (L.) Czern.), black mustard (Brassica nigra (L.) Koch), rapeseed (Brassica rapa L), and the cabbage group (Brassica oleracea L.).

[0007] Several morphological and physiological characteristics of Ethiopian mustard contribute to its high productivity in dry environments where other Brassica species are limited. These characteristics include high drought tolerance, rapid development in the rosette stage with a robust root system, a long flowering period, non-dehiscent siliques, and relatively high salinity tolerance. Thus, Ethiopian mustard is considered an alternative of enormous interest in semi-arid agricultural areas, as well as throughout the Mediterranean basin and subtropical zones, because it shows better adaptation and agronomic performance, as well as greater resistance to most diseases and pests that affect other Brassica crops (Getinet A. et al., 1996a, Can. J. Plant Sci., 76: 387-392; Choudhary et al., 2000, Plant Breed, 119: 417-420; Rana, JS, 2005, J. Pest Sci., 78: 155-160).

[0008] In recent years, efforts have increased to develop new oilseed crops to produce biofuels such as biodiesel or sustainable aviation fuel, bioplastics and lubricants.

[0009] The FAIR CT96-1946 project (“Brassica carinata: New crop for biomass production for the non-food market”), carried out between 1996 and 1999 and in which companies and public research institutes from Spain, Italy, Greece and the United Kingdom participated (Alonso LC, et al., 1999, https: / / cordis.europa.eu / project / id / FAIR961946 / es) confirmed the enormous potential of this species and was the precursor of the interest generated in the last 10 years for the production of sustainable aviation fuel (SAF).

[0010] The main species selected for this purpose are members of the Brassicaceae family, such as the aforementioned Ethiopian mustard (Brassica carinata). Others include camelina or false flax (Camelina sativa), pennycress (Thlaspi arvense), and crambe (Crambe abyssinica). These species have been selected for producing good quality oil, for their hardiness, which allows them to be cultivated sustainably with few inputs, and for their ability to be grown as a non-food crop without displacing other food crops (Drenth, AC et al., 2015, Fuel, 153: 19-30). However, while global oil production from Brassica species represents 11.9% of total oil and fat production (Mielke T.(2024, “Global supply, demand, and price outlook of palm oil and other vegetable oils”, POC2024, Malaysia), the Codex Alimentarius only includes some Brassica species, such as mustard seed oil and rapeseed oil, but does not include the species B. carinata. Thus, since it cannot be used for food, Ethiopian mustard has attracted considerable interest from the energy industry in recent years for the production of biofuels. The main advantages of its cultivation, mentioned above, include its wide adaptation to dry climates and subtropical zones, where rapeseed cultivation faces various limitations, including shelling. Furthermore, due to its similarities to rapeseed, it offers the additional advantage of allowing the adaptation and use of all the machinery and cultivation techniques developed for the production of that species.

[0011] In addition to oil, the extraction process from Brassica seeds yields a protein-rich meal with a balanced amino acid composition and high biological efficiency. However, the use of Brassica meal for animal feed is limited by the presence of toxic and antinutritional compounds called glucosinolates (Griffiths DW et al., 1998, J. Hort. Sci. Biotechnol., 73: 1-18), which constitute the plant's defense mechanism against pests and diseases. The glucosinolate content varies depending on the species, climate, soil type, and the plant's stage of development (Bellostas N., JC et al., 2007, J. Sci. Food Agrie., 87: 1586-1594).

[0012] There are more than 120 types of glucosinolates in eleven dicotyledonous families (Fahey, JW et al., 2001, Phytochemistry, 56: 5-51), of which the most frequent in Brassica species are sinigrin, sinalbin, gluconapin, and gluconasturtin. In the specific case of B. carinata, sinigrin constitutes more than 90% of its glucosinolates, which are present in the defatted flour obtained from Ethiopian mustard seeds at a concentration exceeding 100 pmol / g of flour. Thus, without the removal of sinigrin from defatted flour, it cannot be used in the European Union for the formulation of feed, as it does not comply with the maximum value authorized in the legislation of 30 mmol / kg of defatted flour (Directive 2002 / 32 / EC on undesirable substances in animal feed, as amended in accordance with the Annex to Commission Regulation (EU) No 1275 / 2013).

[0013] The removal of glucosinolates from defatted Ethiopian mustard flour is therefore an essential objective for the development of this new oilseed crop.

[0014] In order to solve this problem, several systems have been proposed for reducing the glucosinolate content in Brassica species, which can be grouped into:

[0015] 1. Genetic selection of varieties with low glucosinolate content;

[0016] 2. Physicochemical methods for their removal during the processing of oilseeds or in the treatment of their final products. These can be subdivided into: a) direct removal of glucosinolates; and b) conversion of glucosinolates into their metabolic derivatives, isothiocyanates, and the removal of these.

[0017] Genetic improvement has been successful for years in rapeseed (B. napus), rapeseed (B. rapa), and brown mustard (B. juncea). However, in B. carinata and other non-food species of the same family, no commercially viable glucosinolate-free variety with a glucosinolate content below 30 pmol / g of defatted meal has yet been obtained, which hinders the development of these species for the production of biofuels and aviation fuel.

[0018] In addition to genetic improvement, other alternative processes for the removal of glucosinolates present in Brassica species have been proposed in the state of the art. However, none of them have proven to be effective and economically viable (Tripathi, MK and Mishra, AS, 2007, Anim. Feed Sci. Technol., 132 (1-2): 1-2). Among others, the following have been described:

[0019] 1. Heat treatment: Depending on the temperature and exposure time, the initial glucosinolate content can be reduced by 63% to 95%. However, heating above 110 °C for more than 30 minutes alters the protein quality;

[0020] 2. Water treatment: Defatted Brassica meal can be hydrated with water at a 1:5 ratio (weight / volume) for 0 to 12 hours, which reduces the glucosinolate content by 36% to 90%. However, high dry matter losses in the extraction water limit its use.

[0021] 3. Treatments with water and metallic solutions, for example, applying copper sulfate (3.1 g / L) to rapeseed flour dried at 60 °C achieves a 90% reduction in the glucosinolate content, including the inactivation of isothiocyanates and oxazolidinethione;

[0022] 4. Solid fermentation, by which the glucosinolates present in rapeseed flour are completely degraded by the use of Rhizopus aligosporus and Aspergillus spp. under aerobic conditions for 10 days at 25 °C;

[0023] 5. Micronization, extrusion, and microwave heating at a frequency of 2450 MHz for 2.5 minutes. In this case, decomposition increases with moisture content and exposure time to the treatment.

[0024] In the state of the art, it is also possible to find patents relating to oilseed treatment processes to achieve the elimination of the glucosinolate content present in them or to extract their hydrolysis derivatives, such as mustard essence, which is used in food.

[0025] For example, application number US2005 / 031768 describes a method for producing and extracting allyl oil (allyl isothiocyanate or mustard essence) from sinigrin present in Brassica juncea seeds. The key step in this process is the grinding of the mustard seeds, after which water is added to activate the endogenous enzyme myrosinase. The enzyme myrosinase, or thioglucoside glucohydrolase, is found in all plant tissues of Brassica species. This enzyme, in the presence of water, catalyzes the hydrolysis of glucosinolates after cell rupture (Hóglund AS et al, 1991, Plant Physiol., 95: 213-221), producing glucose, sulfate and, depending on the pH and / or other factors, some of the following products: isothiocyanates, nitriles, cyanoepithoalkanes and thiocyanates (Bones AM and JT Rossiter, 1996, Physiol. Plant, 97: 194-208).These degradation products are responsible for the biological action of glucosinolates. Thus, in the process described in application US2005 / 031768, once the myrosinase enzyme is activated, it converts glucosinolates into allyl isothiocyanate, which is then distilled under moderate temperature conditions (40 °C to 50 °C) and reduced pressure (approximately 45 mm Hg or 6 kPa). One of the objectives of this patent application is precisely to obtain mustard essence or allyl isothiocyanate.

[0026] Patent EP3253227 describes a process for removing sinigrin from a meal fraction obtained from Brassica carinata oilseeds. This process involves heating the oilseed to a temperature of 80°C to 150°C and applying pressure before, during, or after oil extraction. Optionally, the patent also allows for the addition of external myrosinase after oil extraction to remove sinigrin from the meal by converting it into a volatile isothiocyanate. However, it is questionable whether the process described in patent EP3253227 is suitable for removing sinigrin across the entire claimed temperature range.In this regard, it is important to note that between 70 °C and 90 °C (the standard temperature for oilseed extraction), endogenous myrosinase is inactivated, which can lead to the production of defatted meal with glucosinolates exceeding the maximum of 30 mmol / kg authorized in the EU for use in animal feed. Between 90 °C and 120 °C, the glucosinolate content may be partially reduced due to some degradation caused by the temperature, but complete elimination of the sinigrin present in the meal fraction would not be achieved. Above 120 °C, a large proportion of the glucosinolates may be eliminated, as they are thermolabile. However, at high temperatures, protein degradation is accelerated through the Maillard reaction (Anderson-Hafermann, JC et al., 1993, Poultry Science 72:326-333).

[0027] Thus, none of the processes known to date allow obtaining a defatted flour from oilseeds of the Brassicaceae family that has a glucosinolate content within the values ​​accepted for use in animal feed. The present invention provides a solution to this technical problem.

[0028] DESCRIPTION OF THE INVENTION

[0029] A first object of the invention is a process for manufacturing oil and defatted flour from seeds of at least one plant of the Brassicaceae family, comprising oil, in a percentage between 25% and 45% by weight, glucosinolates, in a concentration greater than 30 micromoles / g of seed, and at least one enzyme consisting of the enzyme myrosinase, wherein said process is characterized in that it comprises: a) crushing the seeds to a size preferably between 0.1 and 0.5 mm and hydrating the crushed seeds in water in a seed:water ratio preferably between 1:2 and 1:7, resulting in a seed paste, as well as the release of the glucosinolates and myrosinase initially contained within the seeds; b) subjecting the seed paste to a heating process, at a temperature preferably between 15 °C and 50 °C, and more preferably between 45 °C and 50 °C,for a preferred time of 15 to 90 minutes, more preferably 30 to 90 minutes. This step can be carried out in a thermomixer, controlling the temperature to avoid overheating and, consequently, the destruction of myrosinase. During this step, the glucosinolates are degraded, transforming into isothiocyanates by the action of myrosinase, achieving a degradation of more than 90% of the glucosinolates at the end of the step, as well as obtaining a fat slurry ready for the next step, drying; c) drying the fat slurry obtained after the thermomixing step by centrifugation and heat, or by heat alone. The centrifugation can preferably be carried out at a rotation speed of 4000 to 5000 rpm, for the time necessary to achieve a moisture reduction of at least 10% in the fat slurry.preferably until the fat slurry reaches a moisture content of around 60%. Centrifugation offers the additional advantage of significantly reducing the metal content that may be present in the fat slurry. In turn, the heat drying stage allows for the evaporation of isothiocyanates, primarily allyl isothiocyanate (or mustard essence), if the Brassicaceae plant is of the species B. carinata. Being volatile, isothiocyanates evaporate along with water and other volatiles due to the heat, generating a fat meal that is sent to a subsequent extraction stage. In this drying stage, heat can be applied to the fat slurry until it reaches a temperature preferably between 70 °C and 90 °C. Furthermore,The drying stage can be carried out for as long as necessary to reduce the moisture content of the fat meal to a value preferably below 12% and, at the same time, eliminate myrosinase and volatilize isothiocyanates (and other possible volatile compounds) and water, resulting in cooked fat meal with a low glucosinolate content, where, for the purposes of this patent, a low glucosinolate content is defined as a concentration of less than 30 micromoles / g of flour; d) the fat meal obtained in the previous stage is sent to a solvent extraction stage (preferably hexane), resulting in solvent-defatted flour and a micelle consisting of oil and solvent. This extraction stage can be carried out using a conventional pomace oil extractor. The micelle is then subjected to a solvent separation process (preferably hexane).which can be reused in the solvent extraction stage, and crude oil, the first final product of the process. Similarly, the solvent-extracted meal is then subjected to a desolventizing process, in which the (dry) meal and the solvent are separated. The solvent can again be reused in the solvent extraction stage. The resulting meal, the second final product of the process, is defatted, glucosinolate-free meal suitable for animal feed.

[0030] Preferably, the plant of the Brassicaceae family consists of a plant of the genus Brassica and, more preferably, of the species Brassica carinata (Ethiopian mustard).

[0031] The seeds used in the process can be either dried seeds or seeds harvested at the plant's physiological maturity, when they have a high moisture content (between 25% and 35% by weight in the case of seeds from the species Brassica carinata). This is also the point at which the glucosinolate and myrosinase content is at its peak. The claimed process offers the advantage of not requiring the seeds with a high moisture content to undergo a drying process prior to the first stage of seed crushing. At the same time, it allows for a reduction in the amount of water required in the hydration stage compared to that needed when using dried seeds.Using the seeds at the plant's physiological maturity also allows harvesting 15 to 20 days earlier and planting a second crop after the harvest, thus keeping the extractor active for longer.

[0032] In a preferred embodiment of the invention, when the species is Brassica carinata, in which more than 90% of its glucosinolates are sinigrin, after the heating stage and prior to the drying stage, the fat mash can be subjected to a recovery step for the isothiocyanates generated in the process, preferably if these consist of allyl isothiocyanate (or mustard essence). This recovery step can preferably be carried out by distillation. However, the main purpose of the claimed process is the removal of glucosinolate content from the flour obtained from said process; therefore, the recovery of the isothiocyanates generated in addition to the flour and oil, the main products of the process, is merely a particular preferred embodiment of the invention and is not essential to the object of the invention.

[0033] In a particular embodiment of the invention, the drying stage of the fatty slurry is preferably carried out using a traditional drying method, such as those used in the process of treating olive pomace and / or pomace for the extraction of pomace oil.

[0034] Olive pomace, also known as wet olive oil pomace, is considered a byproduct of olive mills (Order TED / 92 / 2022) used for the production of virgin olive oil. As defined in this order, it is a material containing the organic remains of milled olives and a variable amount of water, obtained through two-phase centrifugation oil extraction systems. In the olive pomace treatment process, it arrives at the drying facility with a moisture content of between 65% and 75% and a fat content of between 2.5% and 3%. In the drying facility, the moisture content is reduced to less than 12%. The drying equipment used in olive pomace treatment processes can be classified as follows:

[0035] Direct or adiabatic dryers, in which the solid is directly exposed to a stream of hot gas, usually air. There are different models, depending on the type of flow: gas flow over a static bed of solids or through a preformed bed of solids; rain action in a rotary dryer; fluidized bed of solids; parallel gas-solid flow in a pneumatic flash dryer, etc.;

[0036] Indirect or non-adiabatic dryers, in which heat is transferred to the solid from an external source, for example, steam. Generally, the solid is in contact with a metal surface that either contains the heat transfer fluid or is heated electrically;

[0037] . direct-indirect dryers, heated by dielectric, radiant or microwave energy.

[0038] Olive pomace, like alperujo, is also considered a byproduct of olive mills (Order TED / 92 / 2022). As defined in this order, olive pomace is a material consisting of the residual olive paste, containing a variable percentage of water and oil depending on the extraction system used. Specifically, high-fat olive pomace comes from traditional press mills, mills with three-stage centrifuges, and those with a mixed extraction system. The choice of drying equipment and the number of drying stages varies depending on the condition of the high-fat olive pomace. In particular, olive pomace from press extraction has a moisture content of 25% and a fat content of between 6% and 8%. In turn, wet pomace from extraction with a continuous 2 and 3 phase system has a moisture content of more than 50% and a fat content of between 3% and 5%.

[0039] The equipment traditionally used for drying grape pomace is a rotary dryer or kiln (trommel), although other alternatives exist that improve the efficiency of the process. The rotary trommel dryer is typically used for drying granular or powdered material. The trommel consists of a horizontal cylinder that rotates and is slightly inclined to facilitate the movement of the product undergoing the drying process, which is discharged at the end of the cylinder. Inside, the product (the wet pomace) comes into direct contact with a stream of hot air that circulates either parallel (equal current) or countercurrent. In equal current systems, the product to be heated and the hot air flow in the same direction, with the hot gases at a higher temperature coming into contact with the wetter products. This reduces the loss of volatiles and the risk of fire.The countercurrent system has the advantage of achieving a greater reduction in the product's moisture content, as the drier solids come into contact with the hottest gases. However, its main drawback is the increased risk of fire. Typically, the temperature of the hot air used for drying is between 400 °C and 800 °C. At this temperature, the pomace heats up and loses its excess water through evaporation. In specific applications, several drying units can be used, arranged in series.

[0040] The drying of the fatty slurry in the claimed process may be carried out using any of the olive pomace or grape pomace drying systems, as previously described.

[0041] Following the drying process, the extraction process can be carried out continuously or in batches. In the batch process, the oil content of the material being extracted can exceed 25% by weight, while in the continuous process, it is recommended that it be less than 25% by weight.

[0042] In a particular embodiment of the invention, the fat flour can be mixed, prior to extraction with hexane, with pomace (with a high percentage of cellulose) or any other compound that allows reducing the fat content of the flour, preferably by an amount between 12% and 25% by weight.

[0043] In a preferred embodiment of the invention, in order to facilitate the action of hexane and prevent caking during extraction, the oil meal may be pre-subjected to a pelleting or rolling process, forming sheets with a thickness preferably between 0.13 and 0.30 mm. Preferably, the pelleting may be carried out in a screw press which, in addition to pelleting, allows the oil content of the oil meal to be reduced to a value equal to or less than 35% by weight, thus enabling continuous extraction. In a particular embodiment in which pomace (or another equivalent compound) is added, this pelleting or rolling step will be carried out after the addition of the pomace and prior to solvent extraction.

[0044] One of the main advantages of the claimed process is that it allows for a reduction of glucosinolates by more than 90% by weight compared to the initial glucosinolate content in the oilseeds used in the process. This results in a defatted meal with a glucosinolate content of less than one-third of the maximum value authorized in the European Union for animal feed formulations (30 pmol / g of defatted meal), preferably with a content of less than 10 pmol / g of defatted meal. Specifically, when using B. carinata seeds as the raw material for the process, these glucosinolates will be primarily sinigrin.

[0045] Additionally, as described above, the claimed process offers the advantage of being adaptable to a traditional drying method commonly used in the treatment processes of olive pomace and / or olive pomace, as these processes are suitable for extracting oil from seeds with very high moisture and very low fat content.

[0046] Additionally, the invention relates to the use of the claimed defatted flour for human and / or animal consumption

[0047] While the claimed process is particularly suitable for the manufacture of oil and defatted meal from the seeds of at least one plant of the Brassicaceae family, in a further embodiment it can also be used in corn starch production plants, where hydrated seeds are processed to extract their starch. After starch extraction, the seeds are dried to produce what are known as dried distillers grains (DDG), which can then be subjected to a solvent extraction process. Thus, the adaptation of the olive pomace and olive pomace extraction process can also be carried out in these types of plants, intended for the production of corn starch.

[0048] DETAILED DESCRIPTION OF THE INVENTION

[0049] In order to demonstrate the effectiveness of the invention, a series of tests on specific embodiments of the claimed process have been carried out, both at the Institute for Sustainable Agriculture (CSIC) in Córdoba and at the Institute of Fat (CSIC) in Seville. These tests, as well as the results obtained in each, are described in detail below:

[0050] ESSAY 1

[0051] This trial was conducted at the CSIC Institute for Sustainable Agriculture in Cordoba.

[0052] First, the oilseeds were selected, which consisted of B. carinata seeds from a harvest in the municipality of Isla Mayor (province of Seville, Andalusia) from the year 2023 / 2024, where at least 2 different populations of B. carinata were sown.

[0053] The selected seeds were ground and hydrated in water at seed-to-water ratios of 1:1 and 1:3. They were then incubated at 45°C for four periods: 30, 60, 90, and 120 minutes. After this time, they were dried at 80°C for 24 h. Two replicates were performed for each treatment. Glucosinolate analysis of the dried wholemeal flour was carried out by high-performance liquid chromatography (HPLC), according to the method described in Velasco, L. and Becker, HC, 1998, Plant Breeding, 117: 97-102.

[0054] Trial 1 Results

[0055] The results of trial 1 demonstrated that both the 1:1 seed / water dilution and the 1:3 dilution, as well as all incubation periods, resulted in a highly significant reduction in the total glucosinolate and sinigrin content. The original seed had a total glucosinolate content of 74 mmol / kg of seed, of which 92.9% by weight was sinigrin. Without removal during the extraction process, this seed would yield flour with a glucosinolate content of 114.3 mmol / kg of flour, exceeding the EU maximum of 30 mmol / kg. In this trial, a reduction in glucosinolate content of 99.93% by weight was achieved in the 1:3 dilution and 95.61% by weight in the 1:1 dilution.Therefore, the glucosinolate content in the resulting flour would range from 0.08 to 5.0 mmol / kg of flour from a 1:3 and 1:1 dilution, respectively, well below the legal limit of 30 mmol / kg established in Commission Regulation (EU) No 1275 / 2013 for products intended for animal feed. The results also confirmed that there were no significant differences between the different incubation times to which the seeds were subjected for each of the dilutions (1:1 and 1:3).

[0056] The results of trial 1 are shown in Table 1, where the control corresponds to the seeds and the rest of the treatments (1 to 8) to the fat flour:

[0057] Table 1

[0058] TEST 2. Institute of Fat (CSIC) of Seville

[0059] This trial was conducted in a pilot plant, specifically at the experimental protein and oil extraction plant of the Instituto de la Grasa in Seville. For the trial, seeds of the CSIC-BC-17 variety, produced in Carmona, Seville, during the 2023 / 2024 growing season, were used. The process began by crushing the seeds and adding water at a ratio of 1:2 to 1:7 seed / water. The 1:5 dilution was selected for its superior flowability to continue the process.

[0060] The slurry, consisting of crushed seeds and water, was incubated for 60 minutes at 45–50°C to convert glucosinolates to mustard essence, a reaction mediated by the endogenous enzyme myrosinase, which is released when the seeds are crushed. Aliquots were taken at time zero and at 30 minutes for subsequent glucosinolate analysis. The experiment was replicated in two batches (50 liters each), and three glucosinolate readings were taken for each treatment to calculate the average.

[0061] The drying was carried out in two ways: by centrifugation and subsequent drying by heat in an infrared plant or using only infrared, without centrifugation.

[0062] In summary, essay 2 comprised:

[0063] . an incubation stage in 3 time periods: Control (0 min); 30 min and 60 min;

[0064] . a drying stage using 3 treatments: Control, Infrared Only and Centrifugation and infrared;

[0065] . two replicas (batches) of 50 liters each.

[0066] After the drying stage, the dried fat meal underwent oil extraction with hexane, and the fat content, fatty acid profile, acidity, metal content in the oil, and protein content of the defatted meal were analyzed. All these analyses were performed in CSIC laboratories in Seville and Córdoba. The fat content was determined using the Soxhlet method, which is standard practice in food analysis.

[0067] Trial 2 Results

[0068] Glucosinolate content

[0069] The results of trial 2 regarding glucosinolate content are shown in Table 2. As can be seen, the reduction in glucosinolates was highly significant in all treatments, compared to the results obtained using untreated seeds. Furthermore, no significant differences were observed between treatments, i.e., between 30 or 60 minutes of incubation or between drying with centrifugation and infrared versus drying with infrared alone.

[0070] The results show that the claimed process allows for a reduction of more than 90% in the total glucosinolate content of B. carinata fat meal. The total glucosinolate content in the fat meal was 88.5 micromoles / g in the untreated meal, and 5.7 and 9.2 micromoles / g in the tests performed with batches 1 and 2, respectively. Considering that the fat meal contains approximately 35% fat by weight, the maximum glucosinolate concentration in the defatted meal is 136.15, 8.76, and 14.15 micromoles / g of dry meal for the control, batch 1, and batch 2, respectively. Both results (8.76 and 14.15 micromoles / g of dry flour) are well below the legal limit of 30 micromoles / g for B. carinata flour to be used in animal feed.

[0071] Table 2

[0072] TOT = Total content, SI N = Sinigrin, PRO = Progoitrin, and 4-OH = 4-hydroxyglucobrasicin. Units are, in all cases, micromoles / g of dry fat flour. Fat content

[0073] Table 3 shows the results for the fat content (RG%) of the product from the treatments, compared to the control. As can be seen, there are no significant differences between the control and the hydrated, incubated, and dried treatments; therefore, it can be stated that the claimed process does not affect the fat content of the final product.

[0074] Table 3

[0075] Fatty acid content in the oil

[0076] The fatty acid profile of B. carinata seed oil (control) and that of the different treatments of crushing, hydration, incubation (30 and 60 min) and drying (with or without centrifugation) are shown in Table 4. As can be seen, there are no differences between the treatments and the control, so it can be concluded that the quality of the oil with respect to fatty acids is not altered by the treatments of crushing, hydration, incubation and drying.

[0077] Table 4

[0078] TRIAL 3. Institute of Fat (CSIC) of Seville.

[0079] This study analyzed the metals present in the oil after extraction. The aim was to determine whether centrifuging some of the water during the drying process would remove some of the metals, which must be eliminated through oil refining processes for the manufacture of aviation fuel.

[0080] The results are shown in Table 5. As can be seen, the centrifugation process allows a significant reduction in the metal content, which is a great advantage, since metals poison the catalysts in the hydrotreated vegetable oil (HVO) treatment processes, used for the production of sustainable aviation fuel.

[0081] Table 5

Claims

CLAIMS 1. A process for the manufacture of oil and defatted flour with a glucosinolate content of less than 30 micromoles / g of dry flour from seeds of at least one plant of the Brassicaceae family comprising oil, in a percentage between 25% and 45% by weight, glucosinolates, in a concentration greater than 30 micromoles / g of seed and at least one enzyme consisting of the enzyme myrosinase, wherein said process is characterized in that it comprises: a) crushing the seeds and hydrating the crushed seeds in water in a seed:water ratio between 1:2 and 1:7, resulting in a seed porridge, as well as the release of the glucosinolates and myrosinase initially contained within the seeds;b) subjecting the seed mash to a heating process at a temperature between 15 °C and 50 °C, at which temperature the glucosinolates are transformed into isothiocyanates by the action of myrosinase, until a degradation of more than 90% of the glucosinolates is achieved at the end of the stage, as well as obtaining a fat mash that is sent to the next stage, drying; c) drying the fat mash obtained after the heating stage by centrifugation and heat, or only by heat, at a fat mash temperature between 70 °C and 90 °C, at which temperature the myrosinase is eliminated, the isothiocyanates and water are evaporated and a fat meal is obtained that is sent to a subsequent extraction stage;d) the fat meal obtained in the previous stage is sent to a solvent extraction stage, resulting in a solvent-defatted meal and a micelle comprising oil and solvent, where the micelle is then subjected to a solvent separation process and crude oil, the first final product of the process, and where the solvent meal is then subjected to a desolventizing process, in which the solvent and dry meal, the second final product of the process, are separated, which consists of defatted meal with a glucosinolate content of less than 30 micromoles / g of dry meal.; 2. Process according to claim 1, wherein the heating stage is carried out for a period of 15 to 90 minutes.

3. Process according to claim 1 or 2, wherein the centrifugation is carried out cape at a speed of 4000 to 5000 rpm.

4. Process according to any one of claims 1 to 3, wherein the solvent is hexane.

5. Process according to any one of the preceding claims, wherein the solvent separated from the micelle and / or solvent-coated flour is reused in the solvent extraction stage.

6. Process according to any one of the preceding claims, wherein the plant consists of a plant of the genus Brassica.

7. Process according to claim 6, wherein the plant is of the species Brassica carinata.

8. Process according to claim 7, wherein at least 90% by weight of the glucosinolates are sinigrin and wherein the isothiocyanates comprise at least allyl-isothiocyanate.

9. Process according to any one of the preceding claims, wherein the seeds are dry seeds or seeds with a moisture content between 25% and 35% by weight, harvested at the time of physiological maturity of the plant.

10. A process according to any one of the preceding claims wherein, when the species is Brassica carinata, in which more than 90% of its glucosinolates are sinigrin, after the heating stage and prior to the drying stage, the fat slurry is subjected to a recovery stage, by distillation, of the isothiocyanates generated in the process.

11. Process according to any one of the preceding claims, wherein the drying stage of the fatty slurry is carried out by a drying method employed in the treatment of olive pomace and / or pomace for the extraction of pomace oil.

12. Process according to claim 11, wherein the drying is carried out in a rotary oven or trommel.

13. A process according to any one of the preceding claims, wherein, prior to solvent extraction, the oilseed meal is mixed with pomace.

14. A process according to any one of the preceding claims, wherein, prior to solvent extraction, the oilseed meal is subjected to a pelleting or rolling process to facilitate oil extraction, forming sheets with a thickness between 0.13 and 0.30 mm.

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