PL241184B1 - Innovative method of making modified fat - Google Patents

Abstract

The subject of the invention is an innovative method of producing a modified fat, the method characterized by the fact that the raw fat, i.e. vegetable oils, hydrogenated vegetable oils, animal fats, used frying oils, with a cloud point not lower than -11 ° C, pour point not lower than -18 ° C and a freezing point not lower than -21 ° C, subjected to a solvent separation process into a filtrate, which is a modified fat and a precipitate, the main component of which is solid glycerides, including a crystallization step and a filtration step, in the crystallization step the raw material is first diluted with a solvent containing 5% - 100% (m / m) methyl isobutyl ketone and 95% - 0% (m / m) methyl ethyl ketone, respectively, to obtain a solvent feed mixture, which is then cooled at a controlled rate with the simultaneous introduction of a cooled solvent in 1-6 portions, with a cooling rate within the range e 0.1 - 5.0 ° C / min., until reaching the temperature from -15 to -30 ° C, the ratio of the total amount of solvent to the raw material is in the range from 1.5: 1 to 7.5: 1 (m / m), and the size of the dilution expressed as the mass ratio of the solvent to the raw material is from 0.2: 1 to 4: 1 (m / m), and then in the temperature range from -15 to -30 ° C, the separated the residue, which is washed with a cold solvent of the same composition as the solvent used in the crystallization step, used in an amount of 0.1: 1 to 2: 1 (m / m) expressed as the weight ratio of solvent to raw material, and then distilled off from the filtrate solution solvent to obtain the final product, filtrate - modified fat with reduced: cloud point by 4 to 33 ° C, pour point by 4 to 31 ° C and pour point from 3 to 30 ° C, in relation to the values of these temperatures before subjecting the raw material to the separation process solvent on the filtrate and sediment.

Description

Description of the invention

The present invention relates to a method for producing a modified fat.

The modified fat can be used for the production of lubricants, and it can also be a raw material for the production of FAME, which can be used as a standalone fuel or as a fuel component.

Pro-ecological trends in many countries around the world lead to the introduction of environmentally friendly products. Changes in the quality and type of manufactured products are stimulated by technological progress and efforts to reduce the negative impact on the environment and to optimize the use of raw materials.

Many types of biological products are obtained from plant cultivation and animal husbandry all over the world. Natural oils and fats are mixtures of different glycerides due to the content of different fatty acid residues in the glycerides. The only factor determining whether a product is called fat or oil is its melting point.

Vegetable oils are triglycerides of fatty acids, which generally contain both saturated and unsaturated fatty acid residues, in proportions characteristic for certain species of oilseeds. The differences in the fatty acid composition depend on the growing conditions and are also related to specific plant varieties.

Vegetable oils used as base oils have many advantages, including high biodegradability, reduction of environmental pollution, compatibility with additives, high flash point, low volatility, high viscosity index and very good tribological properties. However, vegetable oils also have some disadvantages, such as the thermo-oxidative and hydrolytic stability is limited and, in some cases, due to high cloud and flow points, there is a reduction in flow at low ambient temperatures.

Vegetable oils and fats, apart from their main food use, are also used in the production of biofuel for diesel engines.

Also waste cooking oils are an alternative raw material for the production of FAME, they are used in place of edible vegetable oils. Used cooking oils are known as used oil or the abbreviation UCO (used coocking oil) adopted in Western Europe. All over the world, especially in developed countries, large amounts of waste cooking oils and animal fats are available. Edible oils will change significantly at elevated temperatures due to the many chemical and physical reactions that take place, such as oxidation, hydrolysis, cyclization, isomerization, oligomerization and polymerization.

During frying, changes in physical and chemical properties take place in the oil, which are a consequence of the chemical reactions of the oil itself and the reaction of the oil with water and oxygen at elevated temperature, which results in a different chemical composition compared to vegetable oils.

At present, there are essentially two main routes for the production of renewable biofuel from lipids; these are: transesterification to produce biodiesel (fatty acid methyl esters) or hydroprocessing to produce renewable diesel (hydrocarbons).

The version of the European standard EN 14214: 2012 and the subsequent EN 14214: 2014 concerning the requirements and test methods of fatty acid methyl esters (FAME) raised the problem of low-temperature properties of diesel fuel mixtures related to the quality of FAME used as a component and found that there is a negative effect of monoacylglycerols and glucosides sterols, which are present in FAME, on the low temperature properties of the fuel. Accordingly, a temporary effective way to solve this problem is to introduce requirements regarding the Cold Filter Blocking Point (CFPP) and cloud point.

As mentioned above, low temperature properties are one of the important quality parameters of the FAME fuel component.

Known ester fuels according to PL 163001 have certain limitations and imperfections, e.g. unfavorable temperatures of blocking the cold filter and pouring point, which limits the scope of their use at sub-zero temperatures.

Authors Mohanan A, Bouzidi L, Li SJ, Narine SS. in the article “Mitigating crystallization of saturated fames in biodiesel: 1. Lowering crystallization temperatures via addition of metathesized soybean oil” Energy 2016; 96: pp. 335-45, show that FAMEs have higher cloud and freezing points than petroleum fuel, which results in their limited use at low temperatures. In relation with

Therefore, the use of biodiesel is usually limited to blending with petroleum diesel, typically containing 20% by weight of biodiesel (B20) or less.

Sierra-Cantor JF, Guerrero-Fajardo CA authors of the article: “Methods for improving the cold flow properties of biodiesel with high saturated fatty acids content: A review”; Renew Sustain Energy Rev. 2017; 72: pp. 774-90, report that the freezing point of various FAMEs is usually between 263 K (-10 ^e C) and 298 K (+ 25 ° C), and they are higher compared to 246 K (- 25 ° C) to 258 K (-15 ^e C) for diesel fuel derived from crude oil.

According to the authors of the articles: "Biodiesel fuels" Prog. Energy Combust. Sci. 2017; 58: pp. 36-59 and “Methods for improving the cold flow properties of biodiesel with high saturated fatty acids content: A review”; Renew Sustain Energy Rev. 2017; 72: pp.774-900 and “Thermodynamic selection o effective additives to improve the cloud point of biodiesel fuels”; Fuel 2016; 171: pp. 94-100, the cloud point of biofuels (CP) is often considered the most important parameter influencing the quality of biofuels at low temperatures.

According to the author of Harrow G. in the article: "E85 and biodiesel deployment"; National Renewable Energy Laboratory; 2007, at the cloud point, "solid wax" crystals are formed that are at least 0.5 µm in diameter, making the fuel solution opaque and cloudy. Thus, CP is the temperature at which engine problems begin to occur due to the formation of solids in biofuels.

In the article by the authors Patrick A. Leggieri, Michael Senra, Lindsay Soh "Cloud point and crystallization in fatty acid ethyl ester biodiesel mixtures with and without additives" Fuel 222 (2018); pp. 243-249 states that biofuels, composed of saturated fatty acid alkyl esters (FAAEs), have relatively high cloud points (CPs) that limit their commercial use.

Arjun B. Chhetri et al. In the article "Waste Cooking Oil as an Alternate Feedstock for Biodiesel Production" state that the fatty acid content of glycerides is a major indicator of the properties of biodiesel. The amount and type of fatty acid content in biodiesel are the main factors that determine the viscosity of biodiesel. Fatty acid chains, especially saturated fatty acid chains, play an important role in determining the low temperature properties of biodiesel. In the article by Hilber, T .; Mittelbach, M .; Schmidt, E. "Animal fats perform well in biodiesel" describe the relationship between the change in the low temperature properties of biodiesel and the content of saturated fatty acids. It follows that as the content of saturated fatty acids increases, the Cold Filter Plugging Point (CFPP) of biodiesel is at a higher temperature. The CFPP of animal fats occurs approximately between 12 ° C - 1 ° C. When the biodiesel is derived from rapeseed oil, the CFPP is in the range of about -7 ° C to -12 ° C. Likewise, the CFPP of cooking oil waste, which has an average of 10% saturated fatty acids, is contained in the boundary between CFPP, a biofuel obtained from rapeseed oil and animal fat. In the performed tests, the content of saturated fatty acids in waste cooking oil was about 8%, which corresponds to a CFPP value of about -10 ° C.

There are a number of inventions dealing with the improvement of the properties of low-temperature vegetable oils. Some descriptions of such technological solutions are presented below.

The patent application US 2,982,692 describes the concept of a process whereby enzymes contained in yeast and fermentation products are used to alter some of the unsaturated bonds of lower alcohols in the wax of a vegetable oil. Such a reaction can change the crystal structure of the wax components and the higher molecular weight compounds then make the crystals denser and heavier. The process of dewaxing an oil containing waxy components, including the addition of live yeast and carbohydrate as a medium that the yeast will accept as food, allows for the physical separation of at least a portion of the wax from the vegetable oil. The method of physically removing the wax includes leaving the produced wax until it sinks down and then decanting the oil from above it.

US3943155 discloses a method in which crude vegetable oils are simultaneously refined and dewaxed by cooling the vegetable oils to a temperature sufficient to crystallize the vegetable waxes and separate them from the desired glyceride oils. The cooled oil is gently shaken then pre-cooled aqueous alkaline refining agent is added and mixed with the oil to form an emulsion of hydrophilic and wax components; phosphoric acid solution is then added to break this emulsion into a two-phase system, allowing the oil phase to be separated from the water phase.

PL 241 184 B1

Application US 3,994,943 describes a method whereby crude vegetable oil is dewaxed by mixing with a mixture of surfactants containing an aqueous solution of less than 100 ppm of an alkyl sulfosuccinate ester, e.g. such as sodium dioctyl sulfosuccinate and 0.01 to 0.5% fatty acid sulfate. , e.g. such as sodium lauryl sulfate. By mixing the two-phase oil-water system, an emulsion is formed, which is then centrifuged and washed to separate the wax-containing water phase from the oil. The oil can be degummed simultaneously by adding a phosphate compound to the treated mixture.

The application US 4,545,940 broadly describes the problem of the quality of vegetable oils for food purposes. Raw vegetable oil contains wax, phospholipids, free fatty acids, pigments, water and other trace compounds. The wax makes the oil cloudy and degrades its taste; phospholipids also cloud the oil, degrade its taste and produce an undesirable odor; free fatty acids degrade the taste of the oil and create an undesirable odor; pigments cause an undesirable appearance, and water accelerates the oxidation of the oil, which in turn lowers its taste and produces an undesirable odor. Therefore, when making edible vegetable oil, these substances must be removed. Conventional methods consist of many steps and suffer from many disadvantages; in addition, the most troublesome stage is dewaxing the vegetable oil. Therefore, it was required to simplify the steps of refining the vegetable oil. According to this invention, a method of effectively removing wax from vegetable oil has been developed using a porous membrane with specific surface properties as a filter medium, as a result of which wax and phospholipids, free fatty acids, water and natural impurities such as sulfur compounds, peptides are removed from the crude vegetable oil. , pigments, aldehydes and ketones. In addition, the filter medium, a porous membrane with specific surface properties, also removes most of the foreign substances introduced during the oil extraction or refining process, such as alkalis, acids, metal ions and fine inorganic and organic particles.

The invention of US patent application 4,981,620 includes a combined process of bleaching and dewaxing vegetable oils that eliminates the filtration step that essentially follows the bleaching operation in which the used bleaching clay cake is removed. Basically, the present invention provides a process for refining crude vegetable oils by pre-degumming the oil or alternatively by alkaline refining and subsequent bleaching, cooling and keeping the oil low while mixing, followed by cold separation, e.g. filtering used bleaching clay, other contaminants and constituents. with high melting point.

Patent application WO 03/049832 A1 covers a method of purifying a lipid composition mainly containing neutral lipid components, the composition comprising at least one of 10 long chain polyunsaturated fatty acids (LCPUFA) and at least one other compound. The process involves contacting the lipid composition with a polar solvent, and the solvent is selected such that the other compound is less soluble in the solvent than the LCPUFA. Polar solvents selected from acetone, isopropyl alcohol, methanol, ethanol, ethyl acetate and mixtures thereof were used in the invention. An advantage of the process of this invention is that fewer desired LCPUFAs are lost than similar methods used hitherto, e.g. the embodiment of the present invention (i.e. extraction with hexane followed by freezing with acetone) only causes a loss of 7% to about 10% of the starting extracted lipid.

Patent application WO 2006/004454 A1 relates to the technology of dewaxing vegetable oils by freezing or cooling. The method of removing wax from vegetable oils includes cooling the vegetable oil with the addition of filter aid powders, auxiliary action of the oil at low temperature, separating used filter powder from wax-containing residues from refined vegetable oil, and regenerating the separated used filter powder.

The used filter powder is mixed with the additionally introduced fat product to a pasty consistency, said paste is heated with stirring to the melting point of all the wax components, and the resulting mixture is separated by centrifugation to obtain a regenerated dry filter powder and a wax-containing fat product. The regenerated filter powder can be recycled many times as an auxiliary filter powder in successive operating cycles involving the wintering of new portions of vegetable oil, in which the used filter powder is regenerated after each operating cycle.

PL 241 184 B1

Patent application WO 2006/096872 A2 discloses a method of treating a crude oil stream containing sunflower oil, sunflower wax and water, comprising adjusting the pH of the feed stream to form a lipophilic phase and an aqueous phase, the phases being separated to form a lipophilic stream and an aqueous stream. Also disclosed are methods of treating a lipophilic stream containing sunflower wax and sunflower oil to produce a solid wax and an oil containing extract or solution comprising:

- extraction of the lipophilic stream with an organic solvent;

- adjusting the content of the organic solvent and the crystallizing wax and adjusting the temperature of the lipophilic stream and the crystallizing wax accordingly;

- application of membrane dewaxing;

- the organic solvent may be hexane or an organic solvent selected from the group consisting of ethanol and hydrocarbons from 4 to 8 carbon atoms.

The application US 4,200,509 shows that natural vegetable seed oils are composed not only of oily components but also, usually, low percentages of natural phosphatides, vegetable waxes, pigments and many other compounds. The oil components, namely the glyceride esters of long-chain fatty acids of the saturated and unsaturated type, constitute the largest fraction of vegetable oils. Such materials largely determine the properties of the oil, including one of the undesirable phenomena, which is clouding of vegetable oils.

Application US 4,200,509 describes a method of dewaxing a refined vegetable oil by cooling a refined vegetable oil at a temperature low enough for the waxes to start crystallizing, when the wax crystals are large enough to be electrostatically separated, they are removed by dielectrophoretic filtration, thus passing through cooled oil through the electrostatic precipitator at an appropriate flow rate sufficient to capture the crystallized waxes in the electrostatic precipitator, this allows obtaining a vegetable oil with excellent transparency at low temperature.

The essence of the present invention is to subject fats, which are vegetable oils, hydrogenated vegetable oils, animal fats, used frying oils, to the process of solvent separation into filtrate - modified fat and sludge based on the principles of the solvent dewaxing process, which process is normally used for dewaxing oils and de-oiling of slackers of hydrocarbon compounds.

An important element of this classic process for hydrocarbon feedstocks is the short filtration time of several seconds to about 30 seconds; moreover, shorter filtration time allows to achieve a lower temperature gradient of dewaxing, that is to obtain a better selectivity of the process. In addition, similar quality parameters of fats and hydrocarbon feeds, such as viscosity, density, flash point, distillation range allow directly, without the need for modernization, to process fats in a solvent dewaxing installation.

The subject process makes it possible to obtain a modified fat as a filtrate, characterized by improved low-temperature properties.

The solvents used for the solvent separation of the fats must not be, as research has shown, halogen compounds such as mixtures of dichloroethane with methylene chloride in various proportions, 1,2-dichloropropane with methylene chloride in various proportions, or 1,2-dichloropropane alone. Surprisingly, it was found that halogenated solvents show a lower selectivity of the process and, which is significant, the filtration times range from more than 3 minutes to more than 5 minutes, which disqualifies the practical use of these solvents in industrial processes.

The essence of the invention is to subject the process of solvent separation into filtrate and sludge of the raw material consisting mainly of acyl glycerol esters, commonly called glycerides. These raw materials contain chemical compounds other than charges consisting of various groups of hydrocarbon compounds in the classic dewaxing process, and charges which are mixtures of fatty acid methyl esters.

Surprisingly, it turns out that the application of the solvent separation process into filtrate and sediment for fats, which are vegetable oils, hydrogenated vegetable oils, animal fats, and used frying oils, maintains the selectivity of the process while obtaining short filtration times, which is desirable in industrial processes and allows to reduce cloud point, pour point and pour point, which has the effect of improving the low-temperature properties of the obtained product, including rheological properties at low temperatures.

PL 241 184 B1

The method of producing a modified fat, according to the invention, consists in that the raw fat is vegetable oil or hydrogenated vegetable oil or animal fat or used cooking oil, with a cloud point equal to or higher than -11 ° C, a pour point equal or / or higher than -18 ° C and a freezing point equal to or / and higher than -21 ° C, is subjected to a solvent separation process into a filtrate - modified fat and sediment, the main component of which is solid glycerides, including a crystallization step and a filtration step, with the step of to crystallize, the raw material is subjected to the first dilution with a solvent containing 5% - 100% (m / m) methyl isobutyl ketone and 95% - 0% (m / m) methyl ethyl ketone, respectively, to obtain a mixture of raw material and solvent, which is then cooled at a controlled rate with simultaneous feeding cooled solvent in 1-6 portions - successive dilutions, at the cooling rate in the range res 0.10-5.0 ° C / min., until the temperature is reached from -15 to -30 ° C, the ratio of the total amount of solvent to the raw material is in the range from 1.5: 1 to 7.5: 1 (m / m), and the size of the unit dilutions expressed in the mass ratio of the solvent to the raw material is from 0.2: 1 to 4: l (m / m), then in the temperature range from -15 to -30 ° C, the the separated precipitate, which is washed with a cold solvent of the same composition as the solvent used in the crystallization step, used in an amount from 0.1: 1 to 2: 1 (m / m), expressed in the mass ratio of the solvent to the raw material, and then from the filtrate solution the solvent is distilled off to obtain the final product, which is a filtrate - a modified fat with reduced: cloud point by 4-33 ° C, pour point by 4-31 ° C and pour point by 3-30 ° C, in relation to the values of these temperatures before subjecting the raw material to the process of solvent separation into filtrate and sediment.

Preferably, a crystallization modifier is additionally added to the raw material, which contains as active ingredient polymethyl methacrylates in an amount from 50 to 5000 ppm (mg / kg), most preferably in an amount of 800-1200 ppm. '

Glycerides are polymorphic substances and, in addition, they tend to form much smaller crystals, creating spaces between the crystals in which the filtrate solution is trapped, which negatively affects the process of separating the filtrate solution from the sediment. The introduction of crystallization modifiers significantly improves the filtration processes. In the present invention, polymer substances of a similar type to those used in the solvent dewaxing process are used, influencing the crystallization process by promoting the formation of large cubic crystals. Crystallization modifiers improve the speed and efficiency of the filtration process, influencing the structure of the formed sediment layer on the filter. Properly selected and used crystallization modifiers - chemical compounds specially developed for this purpose improve the efficiency and effectiveness of the entire dewaxing process. The crystallization modifiers used in solvent dewaxing processes are largely based on polyalkyl methacrylates (PAMA).

Preferably the solvent used in the crystallization step and the filtration step comprises 40% - 60% (m / m) methyl isobutyl ketone and 60% - 40% (m / m) methyl ethyl ketone, respectively.

Preferably, the mixture in the crystallization step is cooled at a rate of 0.4-1.5 ° C / min. to a temperature value of -22 to -28 ° C.

Preferably, the ratio of the total amount of solvent to raw material is in the range from 2.4: 1 to 4.5: 1 (m / m).

Preferably the number of dilutions in the crystallization step is from 2 to 3.

Preferably, the separated esters are filtered off in the temperature range from -22 to -28 ° C and washed with a cold solvent used in an amount of 0.2: 1 to 1: 1.2 (m / m).

Preferably, in the crystallization step, the temperature of the solvent at the point of injection into the mixture is equal to or differs by maximum ± 3 ° C from the temperature of the mixture being cooled. This is to prevent disturbance of the ester crystallization process in the mixture.

Preferably, in the crystallization step, the first portion of the solvent is introduced into the feed at a temperature at which the feed is a crystal-free homogeneous liquid phase, most preferably in the range of 45-60 ° C.

The modified fat produced by the method according to the invention is characterized by improved low-temperature properties, i.e. the cloud point lowered by 4-33 ° C, the pour point lowered by 4-31 ° C and the pour point lowered by 3-30 ° C, in relation to these values. temperatures before subjecting the fat to a solvent separation process. The modified fat according to the invention can be used as a biodegradable base oil,

PL 241 184 Β1 for the production of lubricants, when the cloud point is lower than -10 ° C, the pour point is below -14 ° C and the pour point is below -16 ° C, and as a raw material, with a cloud point lower than -3 ° C, below -4 ° C pour point and below -5 ° C freezing point, for the production of FAMA biofuel, which can be used as an independent fuel or as a fuel component.

The method according to the invention, consisting in the use of the solvent separation process into filtrate and sludge for raw materials of natural origin, which are vegetable oils, hydrogenated vegetable oils, animal fats, used cooking oils, gives the advantage of obtaining a product characterized by improved low-temperature properties, i.e. reduced by a few to about 33 degrees Celsius with cloud, flow and solidification temperatures compared to the temperatures of the raw material used in the solvent separation process into filtrate and sediment, which will translate into improvement of low-temperature properties, including theological properties at low temperatures of the base oil and ultimately produced in the process of transesterification of esters methyl fatty acids (FAMA).

The subject matter of the invention is elucidated in the following non-limiting examples of its protection.

Example 1

Rapeseed oil with the quality parameters presented in Table 1 (marked as FAT 1).

Table 1 Rapeseed oil test results (FAT 1)

No. Marked property Unit FAT 1 Test method 1 Kinematic viscosity at 40 ° C mm ² / s 35.88 PN-EN ISO 3104 2 Kinematic viscosity at IOOC mm ² / s 9.09 PN-EN ISO 3104 3 Viscosity index - 198 PN-ISO 2909: 09 4 Cloud point ° c -11 PN ISO 3016 5 Pour point ° c -18 PN ISO 3016 6 Temperature of solidification ° c -21 ASTM D 7346 7 Flash point, Cleveland open cup ° c 324 ISO 2592 8 Acid number mg KOH / g 0.13 9 Iodine number gJ / 100g 116 PN-EN 14111: 2004 10 Density at 15 ° C g / cm ³ 0.920 PN-EN ISO 12185 11 Phosphorus content ppm 12 PN-ISO 10540- 3: 2005

PL 241 184 Β1

Table 1.1 Result of studies on fatty acid profiles in rapeseed oil, labeled FAT 1

Unit FAT 1 Component: <C12 unidentified - C12: 0 - C12 irid - <C14 irid - 04: 0 % (m / m) - 04 abs - 06: 0 % (m / m) 4.2 06: 1 % (m / m) 0.2 06 abs % (m / m) 0.3 08: 0 % (m / m) 1.6 08: 1 % (m / m) 63.7 08: 2 19.1 08 abs - 08: 3 8.1 C20: 0 0.5 C20: l % (m / m) 1.3 C20 abs % (m / m) 0.2 C22: 0 0.3 C22 irid 0.3 C22: l % (m / m) - C24: 0 0.1 C24: l 0.1 Higher non-id - SUM 100

A sample of rapeseed oil (FAT 1) in the amount of 300 g was subjected to a solvent separation process into filtrate and sediment, using a mixture of methylisobutyl ketone (MIBK) and methyl ethyl ketone (MEK) solvents.

The crystallization of hydrocarbons in the laboratory was carried out by the gradual cooling of the mixture of the raw material and the solvent contained in the crystallizer. The crystallizer was placed in a cooling bath, equipped with a cooling cycle programmer, allowing to set the final crystallization temperature and the appropriate cooling rate in subsequent stages of the process. The cryostat was connected to a filter fitting equipped with a jacket in which the cooling agent was circulated.

The crystallization process was carried out by the dilution method, by adding successive portions of the cooled solvent to the cooled mixture of the raw material with the solvent, at appropriate moments in the cooling cycle.

In the crystallization process, continuous mixing of the crystallizer content was applied using a stirrer with an anchor tip, with the mixing speed adjusted to the increasing viscosity of the mixture.

After the final crystallization temperature was reached in a vacuum cleaner, the separated precipitate, the main component of which was solid glycerides, containing the occluded solvent, was filtered off from the filtrate solution. The filtrate solution was collected in the receiver. The filtered precipitate was washed with a portion of cold solvent. The sediment collected from the nibbling and the filtrate solution were subjected to

PL 241 184 Β1 the solvent regeneration process, obtaining the final product, which is a filtrate-modified fat. The solvent regeneration operation was carried out by distillation with nitrogen stripping.

Table 2 presents: technological parameters of the solvent separation process into filtrate and sludge, mass balance and properties of the obtained filtrate - modified rapeseed oil fat.

Table 2 Technological parameters, mass balance and properties of the obtained modified fat filtrate from the raw material, rapeseed oil (FAT 1)

Sample no PR 01 Technological parameters of the solvent separation process MIBK-MEK solvent, mass ratio 70:30 Crystallization / filtration temperature, ° C -28 Total ratio of solvent to raw material, (m / m) 1.8: 1 Dilution I. temperature 60 ° C, (m / m) 0.8: 1 Dilution II, tcmp 20 ° C, (m / m) 0.4: 1 Dilution III, temperature 4 ° C. (m / m) - Dilution IV, temp. -1 ° C, (m / m) 0.4: 1 Washing at filtering temperature, (m / m) 0.2: 1 Mass balance of solvent separation processes Filtrate efficiency, ° / djn / m) - 92.5 Sludge yield,% (m / m) 4.3 Losses,% (m / m) 3.2 Filter time, seconds 26 Properties of the filtrate Kinematic viscosity at 40 ° C, mm ² / s 35.99 Cloud point, ° C -15 Pour point, C. -23 Solidification point, ° C -24

Example 2

A sample of rapeseed oil (designated FAT 1) in the amount of 300 g was subjected to the solvent separation process into filtrate and sediment, with a mixture of methylisobutyl ketone (MIBK) and methyl ethyl ketone (MEK) solvents according to the procedure described in example 1, with the difference that prior to crystallization into the raw material the crystallization modifier was added in an amount of 1000 ppm.

Table 3 presents: technological parameters of the solvent separation process into filtrate and sludge, mass balance and properties of the obtained filtrate - modified rapeseed oil fat.

PL 241 184 Β1

Table 3 Technological parameters, mass balance and properties of the obtained modified fat filtrate from the raw material, rapeseed oil (FAT 1)

Sample no PR 02 Crystallization modifier Viscoplex 9-327 Technological parameters of the solvent separation process MIBK-MEK solvent, mass ratio 50:50 Crystallization / filtration temperature, ° C -28 Total ratio of solvent to raw material, (m / m) 2.8: 1 Dilution 1, temp. 60 ° C, (m / m) 1.4: 1 Dilution II, temperature 20 ° C, (m / m) 0.6: 1 Dilution III, temperature 4 ° C, (m / m) - Dilution IV, temp. -1 ° C, (m / m) 0.6: 1 Washing at filtering temperature, (m / m) 0.2: 1 Mass balance of solvent separation processes Filtrate efficiency, ° Ajm / m) 91.2 Sludge yield,% (m / m) 4.7 Losses,% (m / m) 4.1 Filter time, seconds 21 Properties of the filtrate Kinematic viscosity at 40 ° C, mm% 36.04 Cloud point, ° C -17 Pour point, ° C -24 Solidification point ° C -25

PL 241 184 Β1

Table 3.1 Result of the study of fatty acid profiles in the modified fat filtrate, marked (142 / ol)

Unit Filtrate Evidence Number (142 / ol) Component: <CI2 abs % (m / m) - C12: 0 - C12 irid - <C14 irid - C14: 0 - C14 irid - C16: 0 4.0 C16: l 0.2 C16 irid 0.2 C18: 0 1.3 C18: l 64.1 C18: 2 19.3 C18 irid - C18: 3 % (m / m) 8.3 C20: 0 % (m / m) 0.4 C20: l % (m / m) 1.3 C20 abs % (m / m) OJ C22: 0 0.3 C22 irid % (m / m) 0.3 C22: l % (m / m) - C24: 0 0.1 C24: l % (mm) 0.1 Higher non-id - SUM 100

PL 241 184 Β1

Table 3.2 Result of the acid profile tests in the sediment marked (142 / ol)

Unit Precipitate Evidence Number (142 / g) Component: <C12 abs - C12: 0 - C12 irid - <C14 irid - C14: 0 - C14 irid % (m / m) - C16: 0 4.9 C16: l - C16 irid 0.2 C18: 0 % (m ^/ m) 18.7 C18: l % (m / m) 4.6 C18: 2 % (m / m) - C18 irid % (m / m) 0.1 C18: 3 % (m / m) 0.1 C20: 0 % (m / m) 26.4 C20: l - C20 abs % (m / m) 1.8 C22: 0 26.0 C22 irid % (m / m) - C22: l % (m / m) 2.9 C24: 0 % (m / m) 4.9 C24: l - Higher non-id 2.0 SUM 100

Example 3

A sample of rapeseed oil (designated FAT 1) in the amount of 300 g was subjected to the process of solvent separation into filtrate and sediment with a mixture of methylisobutyl ketone (MIBK) and methyl ethyl ketone (MEK) solvents according to the procedure described in Example 1.

Table 4 presents: technological parameters of the solvent separation process into filtrate and sludge, mass balance and properties of the obtained filtrate - modified rapeseed oil fat.

PL 241 184 Β1

Table 4 Technological parameters, mass balance and properties of the obtained modified fat filtrate from the raw material, rapeseed oil (FAT 1)

Sample no PR 03 Technological parameters of the solvent separation process Solvent MIBK-MEK. mass ratio 30:70 Crystallization / filtration temperature, ° C -thirty Total ratio of solvent to raw material, (m / m) 6.0: 1 Dilution I, temperature 60 ° C, (m / m) 2.4: 1 Dilution II, temperature 20 ° C, (m / m) 1.0: 1 Dilution III. temperature 4 ° C, (m / m) 1.0: 1 Dilution IV, temp. -1 ° C, (m / m) 0.8: 1 Washing at filtering temperature, (m / m) 0.8: 1 Mass balance of solvent separation processes Filtrate efficiency,% (m / m) 90.7 Sludge yield,% (m / m) 5.5 Losses, ^o A {m / m) 3.8 Filter time, seconds 29 Properties of the filtrate Kinematic viscosity at 40 ° C, mm ² / s 35.98 Cloud point, ° C -17 Pour point, ° C -24 Solidification point, ° C -26

Example 4

A sample of rapeseed oil (designated FAT 1) in the amount of 300 g was subjected to the process of solvent separation into filtrate and sediment with a mixture of methylisobutyl ketone (MIBK) and methyl ethyl ketone (MEK) solvents according to the procedure described in Example 1.

Table 5 presents: technological parameters of the solvent separation process into filtrate and sludge, mass balance and properties of the obtained filtrate - modified rapeseed oil fat.

PL 241 184 Β1

Table 5 Technological parameters, mass balance and properties of the obtained filtrate - modified fat from the raw material, rapeseed oil (FAT 1)

Sample no PR 04 Technological parameters of the solvent separation process Solvent M1BK-MEK, mass ratio 90:10 Crystallization / filtration temperature, ° C -thirty Total ratio of solvent to raw material, (m / m) 2.8: 1 Dilution I, temperature 60 ° C, (m / m) 1.4: 1 Dilution II, temperature 20 ° C, (Wm) 0.6: 1 Dilution III, temperature 4 ° C, (m / m) - Dilution IV, temp. -1 ° C, (m / m) 0.6: 1 Washing at filtering temperature, (m / m) 0.2: 1 Mass balance of the solvent separation process Filtrate efficiency,% (wLm) 92.8 Sludge yield,% (m / m) 3.7 Losses,% (m / m) 3.5 Filter time, seconds 24 Properties of the filtrate Kinematic viscosity at 40 ° C, mm ^! / s 36.02 Cloud point, ° C -15 Pour point, ° C -24 Solidification point, ° C -26

Example 5

A sample of rapeseed oil (designated FAT 1) in the amount of 300 g was subjected to the process of solvent separation into filtrate and sediment, with methylisobutyl ketone (MIBK) solvent according to the procedure described in Example 1, with the difference that before crystallization, a crystallization modifier in the amount of 1000 was added to the raw material. ppm.

Table 6 presents: technological parameters of the solvent separation process into filtrate and sludge, mass balance and properties of the obtained filtrate - modified rapeseed oil fat.

PL 241 184 Β1

T a b e I a 6 Technological parameters, mass balance and properties of the obtained modified fat filtrate from the raw material, rapeseed oil (FAT 1)

Sample no PR 05 Crystallization modifier Viscoplex 9-327 Technological parameters of the solvent separation process MIBK solvent, mass ratio - Crystallization / filtration temperature, ° C -28 Total ratio of solvent to raw material, (m / m) 2.8: 1 Dilution I, tcmp. 60 ° C, (m / m) 1.4: 1 Dilution II, temperature 20 ° C, (m / m) 0.6: 1 Dilution III, temperature 4 ° C, (m / m) - Dilution IV, temp. -1 ° C, (m / m) 0.6: 1 Washing at filtering temperature, (m / m) 0.2: 1 Mass balance of solvent separation processes Filtrate efficiency,% (m / m) 91.8 Sludge yield,% (m / m) 4.3 Losses,% (/ w / m) 3.9 Filter time, seconds 25 Properties of the filtrate Kinematic viscosity at 40 ° C, mm% 36.01 Cloud point, ° C -17 Pour point, ° C -23 Solidification point ° C -25

Example 6

A sample of rapeseed oil (designated as FAT 1) in the amount of 300 g was subjected to the process of solvent separation into filtrate and precipitate with a mixture of dichloroethane (DI) and methylene chloride (ME) solvents according to the procedure described in Example 1.

Table 7 presents: technological parameters of the solvent separation process into filtrate and sludge, mass balance and properties of the obtained filtrate - modified rapeseed oil fat.

PL 241 184 Β1

Table? Technological parameters, mass balance and properties of the obtained modified fat filtrate from the raw material, rapeseed oil (FAT 1)

Sample no PR 06 Technological parameters of the solvent separation process Solvent DI-ME, wt. 2.8: 1 Crystallization / filtration temperature, ° C 1.4: 1 Total ratio of solvent to raw material, (m / m) 0.6: 1 Dilution I, temperature 60 ° C, (m / m) - Dilution II, tcmp 20 ° C, (m / m) 0.6: 1 Dilution III, temperature 4 ° C, (m / m) 0.2: 1 Dilution IV, temp. -1 ° C, (m / m) 2.8: 1 Washing at filtering temperature, (m / m) 1.4: 1 Mass balance of solvent separation processes Filtrate efficiency,% (m / m) 92.3 Sludge yield,% (m / m) 3.8 Losses,% (m / m) 3.9 Filter time, seconds 182 Properties of the filtrate Kinematic viscosity at 40 ° C, mnr / s 35.98 Cloud point, ° C -12 Pour point, ° C -18 Solidification point, ° C -21

Example 7

Sunflower oil with the quality parameters presented in Table 8 (marked as FAT 2).

PL 241 184 Β1

Table 8 Results of tests of sunflower oil (marked as FAT 2).

No. Marked property Unit FAT 2 Test method 1 Kinematic viscosity at 40 ° C mm ² / s 39.84 PN-EN ISO 3104 2 Kinematic viscosity at 100 ° C mm ² / s 8.50 PN-EN ISO 3104 3 Viscosity index - 202 PN-ISO 2909: 09 4 Cloud point ° c -4 PN ISO 3016 5 Pour point ° c -16 PN ISO 3016 6 Temperature of solidification ° c -18 ASTM D 7346 7 Flash point, in an open cup of Clcycland ° c 39.19 ISO 2592 8 Acid number mg KOH / g 0.15 9 Iodine number gJ / 100g 112 PN-EN 14111: 2004 10 Density at 15 ° C g / cm ³ 0.914 PN-EN ISO 12185 11 Phosphorus content ppm - PN-ISO 10540- 3: 2005

A sample of sunflower oil (FAT 2) in the amount of 300 g was subjected to the process of solvent separation into filtrate and sediment, using a mixture of methylisobutyl ketone (MIBK) and methyl ethyl ketone (MEK) solvents.

The crystallization of hydrocarbons in the laboratory was carried out by the gradual cooling of the mixture of the raw material and the solvent contained in the crystallizer. The crystallizer was placed in a cooling bath, equipped with a cooling cycle programmer, allowing to set the final crystallization temperature and the appropriate cooling rate in subsequent stages of the process. The cryostat was connected to a filtration jacket equipped with a jacket in which the coolant circulates.

The crystallization process was carried out by the dilution method, by adding successive portions of the cooled solvent to the cooled mixture of the raw material with the solvent, at appropriate moments in the cooling cycle.

In the crystallization process, continuous mixing of the crystallizer content was applied using a stirrer with an anchor tip, with the mixing speed adjusted to the increasing viscosity of the mixture.

After the final crystallization temperature was reached in a vacuum cleaner, the separated precipitate, the main component of which was solid glycerides, containing the occluded solvent, was filtered off from the filtrate solution. The filtrate solution was collected in the receiver. The filtered precipitate was washed with a portion of cold solvent. The sediment collected from the nibs and the filtrate solution were subjected to the solvent regeneration process, obtaining the final product, which is the filtrate - modified fat. The solvent regeneration operation was carried out by distillation with nitrogen stripping.

Table 9 presents: technological parameters of the solvent separation process into filtrate and sludge, mass balance and properties of the obtained filtrate - modified rapeseed oil fat.

PL 241 184 Β1

Table 9 Technological parameters, mass balance and properties of the obtained modified fat filtrate from the raw material, sunflower oil (FAT 2)

Sample no PR 07 Technological parameters of the solvent separation process MIBK-MEK solvent, mass ratio 60:40 Crystallization / filtration temperature, ° C -28 Total ratio of solvent to raw material, (m / m) 2.8: 1 Dilution I, tcmp. 60 ° C, (m / m) 1.4: 1 Dilution II, temperature 20 ° C, (m / m) 0.6: 1 Dilution 111, temp. 4 ° C, (m / m) - Dilution IV, temperature -11 ° C, (m / m) 0.6: 1 Washing at filtering temperature, (m / m) 0.2: 1 Mass balance of solvent separation processes Filtrate efficiency,% (talk) 91.2 Sludge yield,% (m / m) 5.4 Losses,% (m / m) 4.4 Filter time, seconds 26 Properties of the filtrate Kinematic viscosity at 40 ° C, mm ² / s 40.11 Cloud point, ° C -14 Pour point, ° C -21 Solidification point ° C -24

Example 8

UCO post-frying vegetable oil with the quality parameters presented in Table 8 (marked as FAT 3).

PL 241 184 Β1

Table 10 Test results for used cooking oil, UCO (marked as FAT 3)

No. Marked property Unit FAT 3 Test method 1 Kinematic viscosity at 40 ° C mm ² / s 41.06 PN-EN ISO 3104 2 Cloud point ° c +12 PN ISO 3016 3 Pour point ° c -6 PN ISO 3016 4 Temperature of solidification ° c -7 ASTM D 7364

Table 10.1 Results of studies on fatty acid profiles in used cooking oil marked FAT 3

Unit FAT 3 Component: <C12 abs % (m / m) - C12: 0 % (m / m) 0.1 Cl2 absent % (m / m) - <C14 irid % (m / m) - C14: 0 % (m / m) 0.3 C14 irid - C16: 0 % (m / m) 11.0 C16: l % (m / m) 0.4 C16 irid % (m / m) 0.3 C18: 0 % (m / m) 3.6 C18: l % (m / m) 52.7 C18: 2 % (m / m) 26.1 C18 irid % (m / m) 0.1 C18: 3 % (m / m) 2.4 C20: 0 % (m / m) 0.4 C20: l % (m / m) 0.6 C20 abs % (m / m) - C22: O % (m / m) 0.5 C22 irid % (m / m) 0.1 C22: l % (m / m) 0.2 C24: 0 % (m / tn) 0.2 C24: l - Higher non-id % (m / 'm) 1.0 SUM % (m / m) 100.0

A sample of used cooking oil (marked FAT 3) in the amount of 300 g was subjected to the solvent separation process into filtrate and sediment, using a mixture of methylisobutyl ketone (MIBK) and methyl ethyl ketone (MEK) solvents.

The crystallization of hydrocarbons in the laboratory was carried out by the gradual cooling of the mixture of the raw material and the solvent contained in the crystallizer. The crystallizer was placed in a cooling bath, equipped with a cooling cycle programmer, allowing to set the final crystallization temperature and the appropriate cooling rate in subsequent stages of the process. The cryostat was connected to a filtration jacket equipped with a jacket in which the coolant circulates.

PL 241 184 Β1

The crystallization process was carried out by the dilution method, by adding successive portions of the cooled solvent to the cooled mixture of the raw material with the solvent, at appropriate moments in the cooling cycle.

In the crystallization process, continuous mixing of the crystallizer content was applied using a stirrer with an anchor tip, with the mixing speed adjusted to the increasing viscosity of the mixture.

After the final crystallization temperature was reached in a vacuum cleaner, the separated precipitate, the main component of which was solid glycerides, containing the occluded solvent, was filtered off from the filtrate solution. The filtrate solution was collected in the receiver. The filtered precipitate was washed with a portion of cold solvent. The sediment collected from the nibs and the filtrate solution were subjected to the solvent regeneration process, obtaining the final product, which is the filtrate - modified fat. The solvent regeneration operation was carried out by distillation with nitrogen stripping.

Table 11 presents: technological parameters of the solvent separation process into filtrate and sludge, mass balance and properties of the obtained used cooking oil filtrate - modified cooking oil fat.

Table 11 Technological parameters, mass balance and properties of the obtained filtrate, modified fat from the raw material, used cooking oil (FAT 3)

Sample no PR 08 Technological parameters of the solvent separation process MIBK-MEK solvent, mass ratio 80:20 Crystallization / filtration temperature, ° C -22 Total ratio of solvent to raw material, (m / m) 1.8: I Dilution I, temperature 60 ° C, (m / m) 0.8: 1 Dilution Π, temperature 20 ° C, (m / m) 0.4: 1 Dilution III, temperature 4 ° C, (m / m) - Dilution IV, temp. -1 ° C, (m / m) 0.4: 1 Washing at filtering temperature, (m / m) 0.2: 1 Mass balance of solvent separation processes Filtrate capacity, ° / o (m / m) 83.4 Sludge yield,% (w / m) 11.4 Losses,% (m / m) 5.2 Filter time, seconds 25 Properties of the filtrate Kinematic viscosity at 40 ° C, mm ² / s 41.31 Cloud point, ° C -7 Pour point, ° C -10 Solidification point, ° C -11

PL 241 184 Β1

Table 11.1 Result of studies on fatty acid profiles in the modified fat filtrate, marked (143 / ol)

Unit Filtrate Evidence Number 143 / ol Component: <C12 abs % (m / m) - C12: 0 % (m / m) 0.1 Cl2 absent % (m / m) - <C14 irid % (m / m) - C14: 0 % (m / m) 0.2 C14 irid % (m / m) - C16: 0 % (m / m) 8.7 C16: l 0.4 C16 irid % (m / m) 0.2 C18: 0 % (m / m) 2.7 C18: l % (m / m) 55.9 C18: 2 % (m / m) 27.6 C18 irid % (m / m) - C18: 3 % (m / m) 2.6 C20: 0 % (m / m) 0.3 C20: l % (m / m) 0.6 C20 abs % (m / m) - C22: O % (m / m) 0.4 C22 irid % (m / m) o, l C22: l % (m / m) 0.1 C24: O % (m / m) 0.1 C24: l % (m ^; m) - Higher non-id % (m / m) 1.0 SUM % (m / m) 100.0

PL 241 184 Β1

Table 11.2 The results of studies on fatty acid profiles in the sediment marked (143 / g)

Unit Precipitate Evidence Number 143 / g Component: <C12 abs % (m / m) - Ci2: 0 % (m / m) 0.2 C12 irid % (m / m) - <C14 irid % (m / m) - C14: 0 % (m / m) 1.1 C14 irid % (m / m) 0.2 C16: 0 % (in m) 43.4 C16: l % (m / m) 0.4 Cl6 abs % (m / m) 0.7 C18: 0 % (m / m) 15.6 C18: l % (m / m) 26.1 C18: 2 7.7 C18 irid % (m / m) 0.4 C18: 3 % (m / m) 0.8 C20: 0 % (m / m) 1.1 C20: l 0.3 C20 abs - C22: 0 1.2 C22 irid % (m / m) - C22: l 0.2 C24: 0 % (m / m) 0.5 C24: l % (m / m) - Higher non-id 1.0 SUM 100.0

Example 9

A sample of used cooking oil (designated FAT 3) in the amount of 300 g was subjected to the process of solvent separation into filtrate and sediment, with a mixture of methylisobutyl ketone (MIBK) and methyl ethyl ketone (MEK) solvents according to the procedure described in example 5, with the difference that before crystallization was added to the raw material crystallization modifier in an amount of 1000 ppm.

Table 12 presents: technological parameters of the solvent separation process into filtrate and sludge, mass balance and properties of the obtained filtrate - modified cooking oil fat.

PL 241 184 Β1

Table 12 Technological parameters, mass balance and properties of the obtained filtrate, modified fat from the raw material, used cooking oil (FAT 3)

Sample no PR 09 Crystallization modifier Viscoplex 9 - 327 Technological parameters of the solvent separation process Solvent MIBK-MEK. mass ratio 40:60 Crystallization / filtration temperature, ° C -28 Total ratio of solvent to raw material, (m / m) 2.8: 1 Dilution I, temperature 60 ° C, (m / m) 1.4: 1 Dilution II, temperature 20 ° C, (mm) 0.6: 1 Dilution III, temperature 4 ° C, (m / m) - Dilution IV, temp. -1 ° C, (m / m) 0.6: 1 Washing at filtering temperature, (m / m) 0.2: 1 Mass balance of solvent separation processes Filtrate efficiency,% (m / m) 84.7 Sludge yield,% (m / m) 10.4 Losses,% (m / m) 4.9 Filter time, seconds 22 Properties of the filtrate Kinematic viscosity at 40 ° C, mm ² / s 41.28 Cloud point, ° C -10 Pour point, ° C -15 Solidification point, ° C -16

Example 10

A sample of used cooking oil (designated FAT 3) in the amount of 300 g was subjected to the process of solvent separation into filtrate and sediment, with a mixture of methylisobutyl ketone (MIBK) and methyl ethyl ketone (MEK) solvents according to the procedure described in Example 5.

Table 13 presents: technological parameters of the solvent separation process into filtrate and sludge, mass balance and properties of the obtained filtrate - modified cooking oil fat.

PL 241 184 Β1

Table 13 Technological parameters, mass balance and properties of the obtained filtrate, modified fat from the raw material, used cooking oil (FAT 3)

Sample no PR 10 Technological parameters of the solvent separation process MIBK-MEK solvent, mass ratio 50:50 Crystallization / filtration temperature, ° C -29 Total ratio of solvent to raw material, (m / m) 5.5: 1 Dilution I, temperature 60 ° C, (m / m) 1.8: 1 Dilution II, temperature 20 ° C, (m / m) 1.2: 1 Dilution III, temperature 4 ° C, (m / m) 1.0: 1 Dilution IV, temp. -1 ° C, (m / m) 1.0: 1 Washing at filtering temperature, (m / m) 0.5: 1 Mass balance of solvent separation processes Filtrate efficiency,% (m / m) 82.9 Sludge yield,% (m / m) 11.5 Losses,% m / m) 5.6 Filter time, seconds 27 Properties of the filtrate Kinematic viscosity at 40 ° C, mm ² / s 41.37 Cloud point, ° C -10 Pour point, ° C -13 Solidification point, ° C -15

Example 11

A sample of used cooking oil (designated FAT 3) in the amount of 300 g was subjected to the solvent separation process into filtrate and sediment, with a mixture of 1,2-dichloropropane (PDC) and methylene chloride (ME) solvents according to the procedure described in example 5, with the difference that before crystallization, the crystallization modifier was added to the raw material in an amount of 1000 ppm. Table 14 presents: technological parameters of the solvent separation process into filtrate and sludge, mass balance and properties of the obtained filtrate - modified cooking oil fat.

PL 241 184 Β1

Table 14 Technological parameters, mass balance and properties of the obtained filtrate, modified fat from the raw material, used cooking oil (FAT 3)

Sample no PR 11 Crystallization modifier Vlscoplex 9-327 Technological parameters of the solvent separation process PDC-ME solvent, mass ratio 5.5: 1 Crystallization / filtration temperature, ° C 1.8: 1 Total ratio of solvent to raw material, (m / m) 1.2: 1 Dilution I, temperature 60 ° C, (m / m) 1.0: 1 Dilution II, temperature 20 ° C, (m / m) 1.0: 1 Dilution III, tcmp 4 ° C, (m / m) 0.5: 1 Dilution IV, temp. -1 ° C, (m / m) 5.5: 1 Washing at filtering temperature, (m / m) 1.8: 1 Mass balance of solvent separation processes Filtrate capacity, ° / o (m / m) 87.6 Sludge yield,% (m / m) 8.0 Losses,% (m / m) 4.4 Filter time, seconds 187 Properties of the filtrate Kinematic viscosity at 40 ° C, mm ² / s 41.36 Cloud point, ^D C -6 Pour point, ° C -7 Solidification point, ° C -8

Example 12

Animal fat (lard) with the quality parameters presented in Table 15 (marked as FAT 4).

Table 15 Animal fat test results (FAT 4)

No. Marked property Unit Fat Test method Evidence Number - 81 / B1 - 1 Kinematic viscosity at 40 ° C mm ² / s 38.04 PN-EN ISO 3104 2 Cloud point ° C +30 PN ISO 3016 3 Pour point ° C +27 PN ISO 3016 4 Temperature of solidification ° C +24 ASTM D 7364

PL 241 184 Β1

Table 15.1 Results of studies on fatty acid profiles in animal fat designated FAT 4

Unit FAT 4 Component: <C12 abs % (m / m) OJ C12: 0 % (m / m) - C12 irid % (m / m) oh <C14 irid % (m / m) - C14: 0 1.5 C14 irid % (m / m) - C16: 0 % (m / m) 27.8 C16: l % (m / m) 2.4 C16 irid % (m / m) 0.6 C18: 0 % (m / m) 17.2 C18: l % (m / m) 36.5 C18: 2 % (m / m) 10.8 C18 irid % (m / m) 0.6 C18: 3 % (m / m) 0.8 C20: 0 % (m / m) 0.2 C20: l % (m / m) 0.6 C20 abs % (m / m) 0.6 C22: 0 % (m / m) - C22 irid % (m / m) - C22: l % (m / m) oh C24: 0 % (m / m) oh C24: l - Higher non-id % (m / m) - SUM 100.0

A sample of animal fat - lard (marked as FAT 4) in the amount of 300 g was subjected to the process of solvent separation into filtrate and sediment, with a mixture of methylisobutyl ketone (MIBK) and methyl ethyl ketone (MEK) solvents.

The crystallization of hydrocarbons in the laboratory was carried out by the gradual cooling of the mixture of the raw material and the solvent contained in the crystallizer. The crystallizer was placed in a cooling bath, equipped with a cooling cycle programmer, allowing to set the final crystallization temperature and the appropriate cooling rate in subsequent stages of the process. The cryostat was connected to a filtration jacket equipped with a jacket in which the coolant circulates.

The crystallization process was carried out by the dilution method, by adding successive portions of the cooled solvent to the cooled mixture of the raw material with the solvent, at appropriate moments in the cooling cycle.

In the crystallization process, continuous mixing of the crystallizer content was applied using a stirrer with an anchor tip, with the mixing speed adjusted to the increasing viscosity of the mixture.

After the final crystallization temperature was reached in a vacuum cleaner, the separated precipitate, the main component of which was solid glycerides, containing the occluded solvent, was filtered off from the filtrate solution. The filtrate solution was collected in the receiver. The filtered precipitate was washed with a portion of cold solvent. The sediment collected from the nibbling and the filtrate solution were subjected to

PL 241 184 Β1 the solvent regeneration process, obtaining the final product, which is a filtrate - a modified fat. The solvent regeneration operation was carried out by distillation with nitrogen stripping.

Table 16 presents: technological parameters of the solvent separation process into filtrate and sludge, mass balance and properties of the obtained filtrate - modified fat from lard.

Table 16 Technological parameters, mass balance and properties of the obtained modified fat filtrate from raw material, lard (FAT 4)

Sample no PR 12 Technological parameters of the solvent separation process Solvent MIBK-MEK. mass ratio 60:40 Crystallization / filtration temperature. ° C -28 Total ratio of solvent to raw material, (m / m) 2.8: 1 Dilution 1, temp. 60 ° C, (m / m) 1.4: 1 Dilution 11, temperature 20 ° C, (m / m) 0.6: 1 Dilution III, temperature 4 ° C, (m / m) - Dilution IV, temp. -1 ° C, (m / m) 0.6: 1 Washing at filtering temperature, (m / m) 0.2: 1 Mass balance of solvent separation processes Filtrate efficiency,% (mm) 48.5 Sludge yield,% (m / m) 49.3 Losses,% (m / m) 2.2 Filter time, seconds 24 Properties of the filtrate Kinematic viscosity at 40 ° C, mm ² / s 38.30 Cloud point, ° C -3 Pour point, ° C -4 Solidification point, ° C -6

PL 241 184 Β1

Table 16.1 Results of studies on fatty acid profiles in the modified fat filtrate, marked (155 / ol)

Unit Filtrate Evidence Number 155 / ol Component: <C12 abs OJ C12: 0 % (m / m) OJ C12 irid - <C14 irid % (m / m) - C14: 0 % (m / m) 1.5 C14 irid % (m / m) - C16: 0 20.7 C16: l % (m / m) 3.4 C16 irid % (m / m) 0.6 € 18: 0 % (tn / m) 5.2 C18: l % (m / m) 49.6 C18: 2 % (m / m) 14.8 Cl8 irid % (m / m) 0.9 C18: 3 % (m / m) 1.2 C20: 0 % (m / m) 0.2 C20: l % (m / m) 0.9 C20 abs % (m / m) 0.7 C22: 0 % (m / m) - C22 irid % (m / m) - C22: l % (mm) oh C24: 0 % (m / m) - C24: l % (m / m) - Higher non-id % (m / m) - SUM % (m / m) 100.0

PL 241 184 Β1

Table 16.2 Test results for fatty acid profiles in sediment 155 / g

Unit Precipitate Evidence Number 155 / g Component: <C12 abs % (m / m) - C12: 0 % (m / m) - C12 irid % (m / m) - <C14 irid % (m / m) - C14: 0 % (m / m) 1.1 C14 irid % (m / m) - C16: 0 % (m / m) 34.3 C16: l % (m / m) 1.1 C16 irid % (m / m) 0.6 C18: 0 % (m / m) 30.6 C18: l 24.4 C18: 2 % (m / m) 5.9 C18 irid % (m / m) 0.5 C18: 3 % (m / m) 0.4 C20: 0 % (m / m) 0.3 C20: l % (m / m) 0.4 C20 abs 0.3 C22: 0 % (m / m) - C22 irid % (m / m) 0.1 C22: l % (m / m) - C24: 0 % (m / m) - C24: l % (m / m) - Higher non-id % (m / m) - SUM 100.0

Example 13

A sample of animal fat - lard (marked as FAT 4) in the amount of 300 g was subjected to the process of solvent separation into the filtrate and sediment with the solvent 1,2-dichloropropane (PDC) according to the procedure described in Example 12.

Table 17 presents: technological parameters of the solvent separation process into filtrate and sediment, mass balance and properties of the obtained filtrate - modified fat from lard.

PL 241 184 Β1

Table 17 Technological parameters, mass balance and properties of the obtained filtrate - modified raw fat, lard (FAT 4)

Sample no PR 13 Technological parameters of the solvent separation process PDC solvent, mass ratio - Crystallization / filtration temperature, ° C -28 Total ratio of solvent to raw material, (m / m) 2.8: 1 Dilution I, temperature 60 ° C, (m / m) 1.4: 1 Dilution II, temperature 20 ° C, (m / m) 0.6: 1 Dilution III, temperature 4 ° C, (m / m) - Dilution IV, temp. -1 ° C, (m / m) 0.6: 1 Washing at filtering temperature, (m / m) 0.2: 1 Mass balance of solvent separation processes Filtrate efficiency,% (mm) 47.3 Sludge capacity, // (mm) 49.1 Losses,% (m / w) 3.6 Filter time, seconds 324 Properties of the filtrate Kinematic viscosity at 40 ° C, mm ² / s 41.31 Cloud point, ° C -1 Pour point, ° C -2 Solidification point, ° C -4

Example 14

Hydrogenated rapeseed oil with the quality parameters presented in Table 18 (FAT 5).

Table 18 Test results for hydrogenated rapeseed oil (FAT 5)

No. Marked property Unit FAT 5 Test method 1 Kinematic viscosity at 40 ° C mm ² / s 43.13 PN-EN ISO 3104 2 Kinematic viscosity at 100 ° C mm ² / s 8.993 PN-EN ISO 3104 3 Cloud point ° C +6 PN ISO 3016 4 Pour point ° C 0 PN ISO 3016 5 Temperature of solidification; Temp, no flow. ° C -2 ASTM D 7346 6 Acid number mg KOH / g 0.05 7 Iodine number g J / 100g 88.4 PN-EN 14111: 2004 8 Density at 15 ° C g / cm ³ 0.9160 PN-EN ISO 12185

PL 241 184 Β1

Table 18.1 Results of studies on fatty acid profiles in hydrogenated rapeseed oil (labeled as FAT 5)

Unit FAT 5 Component: <C12 abs % (m / m) - C12: 0 % (m / m) - C12 irid % (m / m) - <C14 irid % (m / m) - C14: 0 % (m / m) 0.1 C14 irid % (m / m) - C16: 0 % (m / m) 5.7 C16: l % (m / m) 0.3 C16 irid % (m / m) 0.2 C18: 0 % (m / m) 2.4 C18: l % (m / m) 77.7 C18: 2 % (m / m) 4.4 C18 irid % (m / m) 5.3 C18: 3 % (m / m) 0.3 C20: 0 % (m / m) 0.6 C20: l % (m / m) 1.4 C20 abs % (m / m) 0.6 C22: 0 % (m / m) 0.3 C22 irid % (m / m) 0.1 C22: l % (m / m) 0.3 C24: 0 % (m / m) 0.1 C24: l % (m / m) 0.2 Higher non-id % (m / m) - SUM % (m / m) 100.0 Elaid acid content ynov (trans-9) - including trans-11 % (m / m) 15.8

A hydrogenated rapeseed oil sample (FAT 5) in the amount of 300 g was subjected to the process of solvent separation into filtrate and sediment, using a mixture of methylisobutyl ketone (MIBK) and methyl ethyl ketone (MEK) solvents.

The crystallization of hydrocarbons in the laboratory was carried out by the gradual cooling of the mixture of the raw material and the solvent contained in the crystallizer. The crystallizer was placed in a cooling bath, equipped with a cooling cycle programmer, allowing to set the final crystallization temperature and the appropriate cooling rate in subsequent stages of the process. The cryostat was connected to a filtration jacket equipped with a jacket in which the coolant circulates.

The crystallization process was carried out by the dilution method, by adding successive portions of the cooled solvent to the cooled mixture of the raw material with the solvent, at appropriate moments in the cooling cycle.

In the crystallization process, continuous mixing of the crystallizer content was applied using a stirrer with an anchor tip, with the mixing speed adjusted to the increasing viscosity of the mixture.

PL 241 184 Β1

After the final crystallization temperature was reached in a vacuum cleaner, the separated precipitate, the main component of which was solid glycerides, containing the occluded solvent, was filtered off from the filtrate solution. The filtrate solution was collected in the receiver. The filtered precipitate was washed with a portion of cold solvent. The sediment collected from the nibs and the filtrate solution were subjected to the solvent regeneration process, obtaining the final product, which is the filtrate - modified fat. The solvent regeneration operation was carried out by distillation with nitrogen stripping.

Table 19 presents: technological parameters of the solvent separation process into filtrate and sludge, mass balance and properties of the obtained filtrate - modified fat from hydrogenated rapeseed oil.

Table 19 Technological parameters, mass balance and properties of the obtained modified fat filtrate from the raw material, hydrogenated rapeseed oil (FAT 5)

Sample no PR 14 Technological parameters of the solvent separation process MIBK-MEK solvent, mass ratio 80:20 Crystallization / filtration temperature, ° C -25 Total ratio of solvent to raw material, (m / m) 4: 1 Dilution I, temperature 60 ° C, (m / m) 1: 1 Dilution II, temperature 20 ° C, (m / m) 2: 1 Dilution III, temperature 4 ° C, (m / m) 0.6: 1 Dilution IV, temp. -1 ° C, (m / m) - Washing at filtering temperature, (m / m) 0.4: 1 Mass balance of solvent separation processes Filtrate efficiency,% (m / m) 86.3 Sludge yield,% (m / m) 12.0 Losses, ° / <fm / m) 1.7 Filter time, seconds 24 Properties of the filtrate Kinematic viscosity at 40 ° C, mm ² / s 43.84 Cloud point, ° C -6 Pour point, ° C -8 Solidification point, ° C -9

PL 241 184 Β1

Table 19.1 Results of studies on fatty acid profiles in the modified fat filtrate marked (69 / ol)

Marked feature Unit Test result Fatty acid - 69 / ol C14: 0 0.1 C14 irid 0 C16: 0 3.8 C16: l 0.4 C16 irid 0.1 C18: 0 1.3 C18: l 80.3 C18: 2 4.4 C18 irid 5.7 C18: 3 0.4 C20: 0 0.4 C20: l 1.5 C20 abs 0.9 C22: 0 0.2 C22: l 0.3 C22 irid 0 C24: 0 0.1 C24: l 0.1 Sum 100

PL 241 184 Β1

Table 19.2 Test results for fatty acid profiles in sediment 69 / g

Marked feature Unit Test result Fatty acid - 69 / g C14: 0 7 / (m'm} 0.1 Cl 4 ind 0 C16: 0 9.7 C16: 1 0.3 C16 irid 0.2 C18: 0 5.2 C18: l 71 C18: 2 3.5 Cl 8 irid // (min) 4.4 C18: 3 0.2 C20: 0 1.2 C20: l 1.3 C20 abs % (m / m) 1.4 C22: 0 0.6 C22: l ^o / djn / m) 0.4 C22 irid % (m / m) 0.1 C24: 0 % (m / w) 0.2 C24: l % (m / m) 0.2 Sum % (m / m) 100

The above examples have proved that the invention is suitable for industrial application.

Claims (9)

Patent claims A method for producing a modified fat, characterized in that the raw fat, i.e. vegetable oils, hydrogenated vegetable oils, animal fats, used frying oils, with a cloud point equal to or higher than -11 ° C, a pour point equal to or higher than -18 ° C and a freezing point equal to or higher than -21 ° C, is subjected to the process of solvent separation into a filtrate, which is a modified fat and sediment, the main component of which is solid glycerides, including a crystallization step and a filtration step, while in the crystallization step the raw material is subjected to a first dilution with a solvent containing 5% - 100% (m / m) methyl isobutyl ketone and 95% - 0% (m / m) methyl ethyl ketone, respectively, to obtain a mixture of the raw material and solvent, which is then cooled at a controlled rate with the simultaneous introduction of a cooled solvent in 1 -6 portions - successive dilutions, with a cooling rate in the range of 0.10-5.0 ° C / min., until the temperature of -15 to -30 ° C is reached, the ratio of the total amount of solvent to the raw material is in the range of 1.5: 1 to 7.5: 1 (m / m), and the amount of unit dilutions expressed in the mass ratio of the solvent to the raw material is from 0.2: 1 to 4: 1 (m / m), then in the temperature range from -15 to -30 ° C, the separated precipitate is filtered off, which is washed with a cold solvent of the same composition as the solvent used in the crystallization step, used in the amount of 0.1: 1 to 2: 1 (m / m) expressed as the weight ratio of the solvent to the raw material, and then the solvent is distilled off from the filtrate solution to obtain the final product, filtrate PL 241 184 B1 - a modified fat with lower: cloud point by 4-33 ° C, pour point by 4-31 ° C and pour point by 3-30 ° C, in relation to the values of these temperatures before subjecting the raw material to the process of solvent separation into filtrate and sediment. 2. The method according to p. A method as claimed in claim 1, characterized in that the raw material is additionally fed with a crystallization modifier which contains as active substance polyalkyl methacrylates in an amount from 50 to 5000 ppm (mg / kg), preferably in an amount of 800-1200 ppm. 3. The method according to p. The process of claim 1 or 2, characterized in that the solvent used in the crystallization step and the filtration step contains 40 - 60% (m / m) methyl isobutyl ketone and 60 - 40% (m / m) methyl ketone, respectively. 4. The method according to p. A process as claimed in claim 1 or 2, characterized in that the mixture in the crystallization step is cooled at a rate of 0.4 - 1.5 ° C / min. to a temperature value of -22 to -28 ° C. 5. The method according to p. The process of claim 1 or 2, characterized in that the ratio of the total amount of solvent to raw material is in the range from 2.4: 1 to 4.5: 1 (m / m). 6. The method according to p. The process of claim 1 or 2, characterized in that the number of dilutions in the crystallization step is from 2 to 3. 7. The method according to p. The method of claim 1 or 2, characterized in that the separated precipitate is filtered off in the temperature range from -22 to -28 ° C and washed with a cold solvent used in the amount of 0.2: 1 to 1: 1.2 (m / m). 8. The method according to p. The method of claim 1 or 2, characterized in that in the crystallization step, the temperature of the solvent at the point of injection into the mixture is equal to or differs at most by ± 3 ° C from the temperature of the cooled mixture. 9. The method according to p. The method of claim 1 or 2, characterized in that in the crystallization step, the first portion of the solvent is introduced into the feed at a temperature at which the feed is a homogeneous liquid phase containing no crystals, preferably in the range of 45-60 ° C.