Process for collecting minor components with short path evaporator and using enzyme

Abstract

The present invention relates to a process for obtaining minor components from vegetable oils, wherein the minor components of interest are squalene, tocopherols, and optionally tocotrienols, wherein the vegetable oil include palm oil, palm olein, palm mid-fraction or mixtures thereof. The process is comprising, an enzymatic condensation of a feed stream in presence of a lipase followed by a fractionation in short path evaporator. The feed stream may be a condensate stream from a deodorization step.

Description

PT-2254-WO-PCTPROCESS FOR COLLECTING MINOR COMPONENTS WITH SHORT PATH EVAPORATOR AND USING ENZYMECROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of European Application No.24213748.7, filed November 18, 2024, which is incorporated by reference herein in its entirety.FIELD OF THE INVENTION

[0002] The present invention relates to a process for obtaining minor components from vegetable oils. The minor components of interest are squalene, tocopherols, and optionally tocotrienols.BACKGROUND OF THE INVENTION

[0003] Squalene is a widely distributed natural triterpene, and it is a minor component of high commercial value worldwide because it has nutritional, pharmaceutical, medicinal, and cosmetic applications, due to its different biological properties. The main source of extraction has been shark liver oil. Secondary sources are mainly vegetable oils, although a limited one, as they allow low productive yields. Due to the diversity of applications that squalene presents and its growing demand, there is an increasing interest in identifying sustainable sources of extraction and obtaining a certain concentration / purity.

[0004] Tocopherols and tocotrienols are both part of the vitamin E family and a have a wide range of beneficial applications. The most common application is the use for their anti-oxidative properties.

[0005] Squalene, tocopherols and / or tocotrienols are present in a variety of vegetable oils. Isolation of minor components from various vegetable oils and by-products of refining of vegetable oils is less efficient as minor components are present in low concentrations. There are several processes available to concentrate and purify these minor components, but they involve solvents and / or chemicals, or chromatographic separation methods.

[0006] There is a need for a suitable process to isolate these minor components in higher purify and / or yield, higher quality; for a simple process, preferably without involving solventsPT-2254-WO-PCTand / or chemicals.

[0007] The present invention provides for such a process.SUMMARY OF THE INVENTION

[0008] The present invention relates to a process for obtaining minor components from vegetable oils, the process is comprising:a) Enzymatic condensation of a feed stream in presence of a lipase for obtaining an enzymatic treated feed stream;b) Fractionation of the enzymatic treated feed stream into a distillate and a residue and the fractionation is taking place in a short path evaporator;c) Collecting the distillate and / or the residue; andWherein the feed stream of step a) is comprising triglycerides, diglycerides, monoglycerides, free fatty acids, tocopherols, squalene and optionally tocotrienols; andWherein free fatty acids are present in the feed stream in an amount of 5 to 65 wt.%; tocopherols are present in the feed stream in an amount of 0.1 to 5.0 wt.% of the feed stream, and squalene is present in an amount of 0.1 to 4.0 wt.% of the feed stream, whereinthe vegetable oil includes palm oil, palm olein, palm mid-fraction or mixtures thereof.DETAILED DESCRIPTION

[0009] The present invention relates to a process for obtaining minor components from vegetable oils, the process is comprising:a) Enzymatic condensation of a feed stream in presence of a lipase for obtaining an enzymatic treated feed stream;b) Fractionation of the enzymatic treated feed stream into a distillate and a residue and the fractionation is taking place in a short path evaporator;c) Collecting the distillate and / or the residue; andWherein the feed stream of step a) is comprising triglycerides, diglycerides, monoglycerides, free fatty acids, tocopherols, squalene and optionally tocotrienols; andPT-2254-WO-PCTWherein free fatty acids are present in the feed stream in an amount of 5 to 65 wt.%; tocopherols, are present in the feed stream in an amount of 0.1 to 5.0 wt.% of the feed stream, and squalene is present in an amount of 0.1 to 4.0 wt.% of the feed stream, wherein the vegetable oil include palm oil, palm olein, palm mid-fraction or mixtures thereof.Vegetable Oils

[0010] The primary components of most unrefined vegetable oils are comprising triglycerides (TAG), diglycerides (DAG), monoglycerides (MAG), free fatty acids (FFA), minor components and the like.

[0011] In the present invention, the vegetable oil includes palm oil, palm olein, palm midfraction or mixtures thereof.

[0012] Unrefined vegetable oils often contain varying amounts of other components (beyond the tnglycerides, diglycerides, monoglycerides), too. Some of these components are desirable components of the oil, e g., squalene, tocopherols, and / or tocotrienols, phytosterols (free and esterified), and the like.

[0013] Vegetable oil impurities (including free fatty acids) are typically removed in the refining process, in different steps, particularly degumming, alkali treatment, bleaching, and / or deodorization.

[0014] In the deodorization step, remaining volatile impurities are removed to yield a deodorized vegetable oil having the desired final characteristics. The volatile impurities removed in the deodorization process commonly include free fatty acids (FFA), aldehydes, ketones, alcohols, and other hydrocarbon impurities.

[0015] Deodorization is typically carried out at elevated temperatures and reduced pressure to better volatilize the FFAs and other impurities. The precise temperature and pressure may vary depending on the nature and quality of the oil being processed. The pressure, for instance, will preferably be no greater than 10 mbar but in certain occasions may benefit from a pressure below or equal to 5 mbar, e.g. 1 to 3 mbar. The temperature in the deodorizer may be varied as desired to optimize the yield and quality of the deodorized oil. At higher temperatures, reactions which may degrade the quality of the oil will proceed more quickly. For example, at higher temperatures, cis-fatty acids may be converted into their less desirable trans form.PT-2254-WO-PCT

[0016] Operating the deodorizer at lower temperatures may minimize the cis-to-trans conversion but will generally take longer or require more stripping medium or lower pressure to remove the requisite percentage of volatile impurities. As such, deodorization is typically performed at a temperature of the oil in a range of 180 to 270°C, with temperatures of about 220-260°C being useful for many oils. For cocoa butter-based oil, a deodorization temperature in a range of 130 to 220°C is advised. Typically, deodorization is thus occurring in a deodorizer whereby volatile components such as FFAs and other unwanted volatile components that may cause off-flavors in the oil, are removed. Deodorization may also result in the thermal degradation of components.

[0017] Unfortunately, some of the desirable components such as the minor components of the vegetable oil may be driven off with the volatile impurities during the deodorization process. As a consequence, the volatile stream exiting the deodorizer will include a substantial fraction but may also include a varying amount of desirable components.Minor Components

[0018] In an aspect of the invention, the minor components are tocopherols, tocotrienols, triterpenes (such as squalene, alfa-amyrin, beta-amyrin and the like), phytosterols (free sterols and sterol esters).

[0019] In another aspect of the invention, the minor components are squalene, tocopherols, tocotrienols and phytosterols.

[0020] In an aspect of the invention, the minor components are squalene, tocopherols and tocotrienols.

[0021] In an aspect of the invention, the minor components are squalene and tocopherols.Feed Stream

[0022] Feed stream is the starting material used for the enzymatic condensation step in presence of a lipase.

[0023] The feed stream is comprising triglycerides, diglycerides, monoglycerides, free fatty acids, tocopherols, squalene, and optionally tocotrienols and; and wherein free fatty acids are present in the feed stream in an amount of 5 to 65 wt.%; tocopherols are present in the feed stream in an amount of 0.1 to 5.0 wt.% of the feed stream, and squalene is present in an amount of 0.1 to 4.0 wt.% of the feed stream.PT-2254-WO-PCT

[0024] In an aspect of the invention, the feed stream is comprising the tocopherols in an amount of 0.1 to 3.0 wt.% of the feed stream.

[0025] In an aspect of the invention, the feed stream is comprising the squalene in an amount of 0.1 to 2.0 wt.% of the feed stream.

[0026] In an aspect of the invention, the feed stream is comprising phytosterols in an amount of 0.7 to 6.0 wt.% of the feed stream.

[0027] In an aspect of the invention, the feed stream is comprising triglycerides in an amount of 7 to 55 wt.% based on weight of the feed stream.

[0028] In an aspect of the invention, the feed stream is comprising diglycerides in an amount of 15 to 35 wt.% based on weight of the feed stream.

[0029] In an aspect of the invention, the feed stream is comprising monoglycerides in an amount of 1 to 4.5 wt.% based on w eight of the feed stream.

[0030] In an aspect of the invention, the feed stream is comprising tocotrienols in an amount of 0.1 to 2 wt.% of the feed stream.

[0031] In an aspect of the invention, the feed stream is sourced from vegetable oils that include palm oil or palm oil fractions, sunflower oil, rapeseed oil, soybean oil, rice bran oil, palm kernel oil, coconut oil, shea butter or mixtures thereof.

[0032] In an aspect of the invention, the feed stream is sourced from vegetable oil including palm oil, palm olein, palm mid-fraction or mixtures thereof.

[0033] In an aspect of the invention, the feed stream is a condensate stream of a deodorization step of a vegetable oil.

[0034] A deodorization step of a vegetable oil can be conducted such that a deodorized vegetable oil and a volatiles stream is obtained. A condensation stream can be obtained by partial and / or complete condensation of the volatiles stream. The condensation stream is cooled at a certain temperature, here referred to as the condenser temperature. The condensation stream comprises a portion of the glycerides and a majority of the volatile impurity fraction of the vegetable oil, as well as the minor components of interest. Such a condensate stream may be the feed stream of the present invention.

[0035] In an aspect of the invention, the condensate stream is obtained at a condenser temperature of from 100°C to 180°C, preferably from 140°C to 160°C.

[0036] In an aspect of the invention, the feed stream, preferably a condensate stream is comprising:PT-2254-WO-PCT- triglycerides in an amount of 7 to 55 wt.%, preferably from 20 to 40 wt.% based on weight of the feed stream,diglycerides in an amount of 15 to 35 wt. %, preferably from 20 to 32 wt. % based on weight of the feed stream,- monoglycerides in an amount of 1 to 4.5 wt.% preferably from 2.0 to 4.0 wt.% based on weight of the feed stream,free fatty acids in an amount of 5 to 65 wt.% based on weight of the feed stream; preferably from 15 to 35 wt.% based on weight of the feed stream,- tocopherols in an amount of 0.1 to 5.0 wt.% based on weight of the feed stream, preferably from 0.1 to 3.0 wt.% based on weight of the feed stream, andsqualene in an amount of 0.1 to 4.0 wt.% based on weight of the feed stream, preferably from 0.1 to 2.0 wt.% based on w eight of the feed stream.

[0037] In an aspect of the invention, the vegetable oils are selected from palm oil, palm olein, palm mid-fraction or mixtures thereof, and the feed stream, preferably a condensate stream is comprising:- triglycerides in an amount of 7 to 55 wt.%, preferably from 20 to 40 wt.% based on weight of the feed stream,diglycerides in an amount of 15 to 35 wt. %, preferably from 20 to 32 wt. % based on weight of the feed stream,- monoglycerides in an amount of 1 to 4.5 wt.% preferably from 2.4 to 4.0 wt.% based on weight of the feed stream.- free fatty acids in an amount of 5 to 65 wt.% based on weight of the feed stream; preferably from 15 to 35 wt.% based on weight of the feed stream,- tocopherols and tocotrienols in an amount of 0.1 to 3.0 wt.% based on weight of the feed stream; and- squalene in an amount of 0.1 to 2.0 wt.% based on weight of the feed stream.Enzymatic Condensation

[0038] The feed stream is enzymatically treated (= enzymatic condensation) in presence of a lipase.PT-2254-WO-PCT

[0039] In an aspect of the invention, an enzymatic condensation of the feed stream and glycerol is taking place in presence of a lipase.

[0040] The lipase may be used in solution or can be immobilized and as such have an impact on the purification of the reaction medium and stability of the enzyme.

[0041] Lipases are classified according to the sources from which they are obtained, such as microorganism (fungi or bacteria), animal and plant. Most lipases applied are derived from fungal or bacterial sources. Some of the most widely used fungal lipases are derived from various species within genera such as Candida, Yarrowia, Aspergillus and Penicillium, while bacterial lipases often come from Pseudomonas sp., Bacillus sp., Staphylococcus sp., Burkholderia sp. and many others. Bacterial lipases and esterases have been classified into eight families (and several subfamilies) based on sequence homology and biological properties. Lipases from animal origin have been originated from various organs and tissues of several mammalian species, among which the pancreatic lipases are the most thoroughly studied. Plant lipases have not received the same attention as those from other sources, but oilseed lipases have been of greatest interest among the plant lipases. An non-exhaustive, non-limiting list of suitable lipases includes, lipase derived from Candida cylindracea, Candida lipolytica, Candida rugosa, Candida antarctica, Candida utilis, Chromobacterium viscosum, Geotrichum viscosum, Geotrichum candidum, Mucor javanicus, Mucor miehei, Porcine pancreas. Pseudomonas species, specifically Pseudomonas fluorescens, Pseudomonas cepacia, Pseudomonas pseudoalkaligenes, Pseudomonas alkaligenes, Thermomyces species, Rhizopus arrhizus, Rhizopus delemar, Rhizopus niveus, Rhizopus oryzae, Rhizopus javanicus, Aspergillus niger, Penicillium roquefortii, Penicillium camembertii or an esterase derived from Bacillus species, specifically Bacillus thermoglucosidasius; Mucor miehei, Horse liver, Saccharomyces cerevisiae. Pigs liver or combinations thereof.

[0042] In an aspect of the invention, the lipase is added in an amount of 1 to 3 wt.% based upon the weight of the feed stream.

[0043] The enzymatic treatment is conducted at a temperature of 60 to 75°C. preferably at a temperature of 68 to 72°C.

[0044] The product obtained after the enzymatic treatment is the enzymatic treated feed stream.

[0045] In an aspect of the invention, the enzymatic treated feed stream is comprising:i. Triglycerides in an amount of 50 to 90 wt.% based on weight of the enzymatic treated feed stream;PT-2254-WO-PCTii. Free fatty acids in an amount of 1 to 10 wt.% based on weight of the enzymatic treated feed stream;iii. Tocopherols in an amount of 0.1 to 5.0 wt.% based on weight of the enzy matic treated feed stream; andiv. Squalene in an amount of 0.1 to 4.0 wt.% based on weight of the enzymatic treated feed stream.

[0046] In an aspect of the invention, the enzy matic treated feed stream is comprising:i. Triglycerides in an amount of 50 to 90 wt.% based on weight of the enzymatic treated feed stream;ii. Free fatty acids in an amount of 1 to 10 wt.% based on weight of the enzymatic treated feed stream;iii. Tocopherols in an amount of 0.1 to 3.0 wt.% based on weight of the enzymatic treated feed stream; andiv. Squalene in an amount of 0.1 to 2.0 wt.% based on weight of the enzymatic treated feed stream.

[0047] In an aspect of the invention, the vegetable oils are selected from palm oil, palm olein, palm mid-fraction or mixtures thereof and the enzymatic treated feed stream is comprising:i. Triglycerides in an amount of 50 to 90 wt.% based on weight of the enzymatic treated feed stream;ii. Free fatty acids in an amount of 1 to 10 wt.% based on weight of the enzymatic treated feed stream;iii. Tocopherols and tocotrienols in an amount of 0.1 to 3.0 wt.% based on weight of the enzymatic treated feed stream; andiv. Squalene in an amount of 0.1 to 2.0 wt.% based on weight of the enzymatic treated feed stream.

[0048] In an aspect of the invention, the enzymatic treated feed stream is comprising phytosterols in an amount of 0.7 to 6.0 wt.% of the feed stream.Fractionation

[0049] The enzymatic treated feed stream is fractionated in a short path evaporator (SPE).PT-2254-WO-PCT

[0050] In an aspect of the invention, the fractionation of step b) is conducted in a short path evaporation at a temperature of from 180°C to 240°C, preferably at a temperature of from 190°C to 230°C, more preferably at a temperature of from 200°C to 220°C or from 210°C to 215°C.

[0051] Short-path evaporation, also called short-path distillation or molecular distillation, is a distillation technique that involves the distillate travelling a short distance, often only a few centimetres, and it is normally done at reduced pressure. With short path distillation, a decrease of boiling temperature is obtained by reducing the operating pressure. It is a continuous process with very short residence time. This technique is often used for compounds which are unstable at high temperatures or to purify small amounts of compounds. The advantage is that the heating temperature can be considerably lower (at reduced pressure) than the boiling point of the liquid at standard pressure. Additionally, short-path evaporation allows working at very low pressure.

[0052] Different types of short-path evaporation apparatus can be used that are well known to the skilled person. Examples are, but are not limited to, falling film, centrifugal, or wiped film evaporation apparatus. Preferably the short-path evaporation of the current process is performed in a wiped film evaporation apparatus.

[0053] The short-path evaporation in step b) of the process according to the invention is performed at a pressure below 1 mbar. preferably below 0.1 mbar, more preferably below 0.01 mbar, most preferably below 0.005 mbar.

[0054] The short-path evaporation is further performed at specific conditions of temperature and feed rate per unit area of evaporator surface of the shorth-path evaporation equipment.

[0055] The “feed rate per unit area of evaporator surface of the shorth-path evaporation equipment”, also called “specific throughput” or “specific feed rate”, expressed in kg / h per m2, is defined as the flow of oil, expressed in kg / h, per unit area of evaporator surface of the short-path evaporation equipment, expressed in m2The feed rate per unit area of evaporator surface of the shorth-path evaporation equipment in the process of the current invention is applicable to any short-path equipment, including industrial short-path evaporation equipment independent of the dimensions of the equipment. Preferably stainless steel short-path evaporation equipment is used in the current invention.

[0056] In an aspect of the invention, the short path evaporator is operated with a feed rate (flow rate) (kilogram per hour) per unit area of evaporator surface of the shorth-path evaporationPT-2254-WO-PCTequipment in a range of from 10 to 200 kilogram per hour per square meter (kg / h per m2). preferably from 12 to 150 kilogram per hour per square meter (kg / h per m2), more preferably in a range of from 15 to 100 kilogram per hour per square meter (kg / h per m2), even more preferably in a range of from 17 to 80 kilogram per hour per square meter (kg / h per m2), most preferably in a range of from 20 to 50 kilogram per hour per square meter (kg / h per m2)

[0057] The fractionation of the enzymatic treated feed stream provides a distillate and a residue.

[0058] In an aspect of the invention, the distillate collected in step c) is comprising i. Tocopherols in an amount of 4 to 25 wt.% based on weight of the distillate; and ii. Squalene in an amount of 8 to 15 wt.% based on weight of the distillate.

[0059] In an aspect of the invention, the distillate collected in step c) is further comprising i. Triglycerides in an amount of less than 5 wt.% based upon the weight of the distillate;ii. Free fatty acids in an amount of 35 to 80 wt.% based on weight of the distillate.

[0060] In an aspect of the invention, the distillate collected in step c) is comprising i. Triglycerides in an amount of less than 5 wt.% based upon the weight of the distillate;ii. Diglycerides in an amount of 0.4 to 10 wt.% wt.% based on weight of the distillate:iii. Monoglycerides in an amount of 1 to 7 wt.% wt.% based on weight of the distillate;iv. Free fatty acids in an amount of 35 to 80 wt.% based on weight of the distillate;v. Tocopherols in an amount of 4 to 25 wt.% based on weight of the distillate;andvi. Squalene in an amount of 8 to 15 wt.% based on weight of the distillate;

[0061] In an aspect of the invention, the vegetable oils are selected from palm oil, palm olein, palm mid-fraction or mixtures thereof and the distillate collected in step c) is comprising:PT-2254-WO-PCTiii. Tocopherols and tocotrienols in an amount of 4 to 25 wt.% based on weight of the distillate;iv. Squalene in an amount of 8 to 15 wt.% based on weight of the distillate;

[0062] In an aspect of the invention, the vegetable oils are selected from palm oil, palm olein, palm mid-fraction or mixtures thereof and the distillate collected in step c) is further comprising:i. Triglycerides in an amount of less than 5 wt.% based upon the weight of the distillate;ii. Free fatty acids in an amount of 35 to 80 wt.% based on weight of the distillate.

[0063] In an aspect of the invention, the vegetable oils are selected from palm oil, palm olein, palm mid-fraction or mixtures thereof and the distillate collected in step c) is comprising:i. Triglycerides in an amount of less than 5 wt.% based upon the weight of the distillate;ii. Diglycerides in an amount of 0.4 to 10 wt.% wt.% based on weight of the distillate:iii. Monoglycerides in an amount of 1 to 7 wt.% wt.% based on weight of the distillate;iv. Free fatty acids in an amount of 35 to 80 wt.% based on weight of the distillate:v. Tocopherols and tocotrienols in an amount of 4 to 25 wt.% based on weight of the distillate; andvi. Squalene in an amount of 8 to 15 wt.% based on weight of the distillate;

[0064] In an aspect of the invention, the distillate collected in step c) is comprising phytosterols in an amount of 1 to 10 wt.% based on weight of the distillate.

[0065] In an aspect of the invention, the distillate is obtained in an amount of 3 to 15 wt.%, preferably 3.5 to 10 wt.% of the weight of the enzymatic treated feed stream.

[0066] In the fractionation of step b) beyond the distillate that can be collected, also a residue is obtained.PT-2254-WO-PCT

[0067] In an aspect of the invention, the residue collected in step c) is comprisingi. Tocopherols in an amount of 0.2 to 3.0 wt.% based on weight of the residue; ii. Squalene in an amount of below 1.5 wt.% based on weight of the residue.

[0068] In an aspect of the invention, the residue collected in step c) is further comprising i. Triglycerides in an amount of 60 to 80 wt.% based upon the weight of the residue;ii. Diglycerides in an amount of 5 to 15 wt.% based on weight of the residue.

[0069] In an aspect of the invention, the residue is obtained in an amount of 85 to 97 wt.% of the weight of the enzymatic treated feed stream.

[0070] In an aspect of the invention, the vegetable oils are selected from palm oil, palm olein, palm mid-fraction or mixtures thereof and the residue collected in step c) is comprising i. Tocopherols and tocotrienols in an amount of 0.2 to 3.0 wt.% based on weight of the residue;ii. Squalene in an amount of below 1.5 wt.% based on weight of the residue.

[0071] In an aspect of the invention, the vegetable oils are selected from palm oil, palm olein, palm mid-fraction or mixtures thereof and the residue collected in step c) is further comprisingiii. Triglycerides in an amount of 60 to 80 wt.% based upon the weight of the residue;iv. Diglycerides in an amount of 5 to 15 wt.% based on weight of the residue.

[0072] In an aspect of the invention, it relates to a process for obtaining minor components from vegetable oils, and the process is comprising:a) Enzymatic condensation of a feed stream in presence of a lipase for obtaining an enzy matic treated feed stream;b) Fractionation of the enzymatic treated feed stream into a distillate and a residue and the fractionation is taking place in a short path evaporator at a temperature of from 180 up to 240°C;PT-2254-WO-PCTc) Collecting the distillate;d) Collecting the residue; andWherein the feed stream of step a) is comprising triglycerides, diglycerides, monoglycerides, free fatty acids, tocopherols, squalene and optionally tocotrienols; andWherein free fatty acids are present in the feed stream in an amount of 5 to 65 wt.%; tocopherols are present in the feed stream in an amount of 0.1 to 5.0 wt.% of the feed stream, and squalene is present in an amount of 0.1 to 4.0 wt.% of the feed stream.

[0073] In an aspect of the invention, it relates to a process for obtaining minor components from vegetable oils, and the process is comprising:a) Enzymatic condensation of a feed stream and glycerol in presence of a lipase for obtaining an enzymatic treated feed stream;b) Fractionation of the enzymatic treated feed stream into a distillate and a residue and the fractionation is taking place in a short path evaporator at a temperature of from 180 up to 240°C:c) Collecting the distillate;d) Collecting the residue; andWherein the feed stream of step a) is comprising triglycerides, diglycerides, monoglycerides, free fatty acids, tocopherols, squalene and optionally tocotrienols; andWherein free fatty acids are present in the feed stream in an amount of 5 to 65 wt.%; tocopherols are present in the feed stream in an amount of 0.1 to 3.0 wt.% of the feed stream, and squalene is present in an amount of 0.1 to 2.0 wt.% of the feed stream.

[0074] In an aspect of the invention, it relates to a process for obtaining minor components from vegetable oils selected from palm oil, palm olein, palm mid-fraction or mixtures thereof, and the process is comprising:a) Enzymatic condensation of a feed stream in presence of a lipase for obtaining an enzymatic treated feed stream;PT-2254-WO-PCTb) Fractionation of the enzymatic treated feed stream into a distillate and a residue and the fractionation is taking place in a short path evaporator at a temperature of from 180 up to 240°C;c) Collecting the distillate;d) Collecting the residue; andWherein the feed stream of step a) is comprising triglycerides, diglycerides, monoglycerides, free fatty acids, squalene, tocopherols and tocotrienols; and Wherein free fatty acids are present in the feed stream in an amount of 5 to 65 wt%; tocopherols and tocotrienols are present in the feed stream in an amount of 0.1 to 3.0 wt.% of the feed stream, and squalene is present in an amount of 0.1 to 2.0 wt.% of the feed stream.

[0075] In an aspect of the invention, it relates to a process wherein the process is comprising the following steps:a) Enzymatic condensation of a feed stream in presence of a lipase for obtaining an enzymatic treated feed stream;b) Fractionation of the enzymatic treated feed stream into a distillate and a residue and the fractionation is taking place in a short path evaporator at a temperature of from 180 up to 240°C;c) Collecting the distillated) Collecting the residue;e) Recycling of the residue collected in step d) into a deodorization step of vegetable oil;andWherein the feed stream of step a) is comprising triglycerides, diglycerides, monoglycerides, free fatty acids, tocopherols, squalene and optionally tocotrienols; andWherein free fatty acids are present in the feed stream in an amount of 5 to 65 wt.%; tocopherols are present in the feed stream in an amount of 0.1 to 5.0 wt.% of the feed stream, and squalene is present in an amount of 0.1 to 4.0 wt.% of the feed stream, and whereinthe vegetable oil includes palm oil, palm olein, palm mid-fraction or mixtures thereof.PT-2254-WO-PCT

[0076] In an aspect of the invention, it relates to a process wherein the process is comprising the following steps:a) Enzymatic condensation of a feed stream in presence of a lipase for obtaining an enzymatic treated feed stream;b) Fractionation of the enzymatic treated feed stream into a distillate and a residue and the fractionation is taking place in a short path evaporator at a temperature of from 180 up to 240°C;c) Collecting the distillated) Collecting the residue;e) Recycling of the residue collected in step d) into a deodorization step of vegetable oil;andWherein the feed stream of step a) is comprising triglycerides, diglycerides, monoglycerides, free fatty acids, tocopherols, squalene and optionally tocotrienols; andWherein free fatty acids are present in the feed stream in an amount of 5 to 65 wt.%; tocopherols are present in the feed stream in an amount of 0.1 to 5.0 wt.% of the feed stream, and squalene is present in an amount of 0.1 to 4.0 wt.% of the feed stream, wherein the feed stream is a condensate stream of a deodorization step of a vegetable oil; andwherein the vegetable oil includes palm oil, palm olein, palm mid-fraction or mixtures thereof.

[0077] The advantages of the present invention are amongst others:Isolation of minor components from various streams is difficult as they are present in low concentrations; but the process of the present invention allows the concentration of the minor components without using solvents and / or chromatographic separation methods; - The enzymatic treatment allowed to obtain a stream with a significant reduction of the content of free fatty acids, while the amount of minor components remained (quasi) unchanged;There is no need to add glycerol in the enzy matic condensation step- Avoiding long heat treatments and thus reduce breakdown of the heat-sensitive minor components;PT-2254-WO-PCT- Provision of distillates with high value due to the high amount of minor components, that can have multiple applications;- Pre-enriches minor components, which helps further process capabilities to operate at higher throughput / higher capacity;- Use of short path evaporator allows a smooth / mild process;- Upgrade the value of existing condensation stream obtained in deodorization process of edible oils;The residue amounts for at least 70 to 95% by weight of the feed stream.- The residue can be re-cycled back into the overall process of deodorization of vegetable oil.

[0078] The present invention is illustrated by the following examples.EXAMPLESAnalytical MethodsLipid Profile by GC / FID

[0079] Lipid Profile analysis was used to determine the lipid composition of the samples ((monoglycerides, diglycerides, triglycerides, free fatty acids, glycerol, phytosterols (free and esterified sterols, including ferulates), squalene, hydrocarbons)), within a single analysis. Quantitation of each class of compounds used multi-level calibration curves with an appropriate standard. The sample size was approximately 100 mg. An internal standard (IS) of heptadecanyl stearate (HDS) was used at 10 mg. Samples were silylated with N, O,-bis-(trimethylsilyl) trifluoroacetoamide (BSTFA) with 1% trimethylchlorosilane and pyridine. The trimethylsilane (TMS) ethers were analyzed by cool on-column (COC) gas chromatography (GC) with a non-polar column stationary phase (15 m x 0.25 mm x 0.10 mm df, DB™-5HT) coupled to a flame ionization detector (FID). The temperature program was 110°C (0.2 min) to 140°C at 30°C / min to 340°C at 10°C / min (13.8 min). Hydrogen was the carrier gas, and inlet pressure was 6.7 psi at 110°C in the constant flow mode. The detector temperature was 370°C. The FID air flow rate was 450 mL / min, the FID hydrogen flow rate was 40 mL / min and the makeup gas flow was 40 mL / min. Samples were analyzed a single time.PT-2254-WO-PCTAnalysis of Total and Isomeric Tocopherols / Tocotrienols by Liquid Chromatography with Fluorescence Detection (LC / FLD). Total and isomeric tocopherol / tocotrienol concentrations in the samples were determined by LC / FLD. A five-point calibration curve was created using an established tocopherol mix that contained a-Tocopherol. b-Tocopherol. g-Tocopherol, and d-Tocopherol; the tocotrienol isomers referenced their corresponding tocopherol calibration curve. Oil samples were prepared at 200 mg / mL (2 g in a 10 mL volumetric and diluted to volume with / 7-hexane) and distillate preparations ranged from 1 to 100 mg / mL oil depending on tocopherol and tocotrienol concentration. Chromatography was performed on a 250 mm x 4.6 mm LiChrospher® 60 (5mm particle size) HPLC column using a mobile phase of 99% / ?-Hexane with 1% Isopropyl Alcohol running under isocratic conditions (flow rate at 1.0 mL / min) with a 10 mL injection volume. The fluorescence detector was set to run an excitation wavelength of 290 nm and collect the emission at a wavelength of 330 nm. The calibration curves were linear through zero.Example 1

[0080] The condensate stream obtained from palm oil common refining process was used as a feed stream. The refining process of the palm oil included a deodorization performed at 265°C.

[0081] The feed stream can be obtained at different condenser temperature settings. The corresponding compositions can be seen below in Table 1 and Table 2.Table 1: Minor Components in Feed StreamTotalTotal TotalCondenser Tocopherol Total Tocopherol Tocotrienol Squalenetemperature s and phytosterolss s [wt.%]settings (°C) tocotrienols '[wt %][wt %] [wt %][wt.%]120 0.30 0.84 1.14 1.56 3.25130 0.16 0.73 0.89 1.16 4.32140 0.27 0.72 0.99 1.02 5.16150 0.46 1.76 2.22 1.34 2.68160 0.37 1.26 1.63 0.69 1.47170 0.27 0.92 1.19 0.49 1.40PT-2254-WO-PCT180 0.16 0.61 0.77 0.35 1.38Table 2: Glycerides Composition of Feed StreamCondenserTAG DAG MAG FFAtemperature[wt.%] [wt.%] [wt.%] [wt.%]settings (°C)120 12.12 18.96 2.71 54.95130 20.99 21.48 2.68 42.44140 24.51 24.97 2.69 33.31150 25.01 28.81 3.76 20.72160 38.97 29.61 2.32 16.04170 44.46 30.23 1.94 10.68180 48.87 30.85 1.55 7.15Enzymatic condensation of the feed stream

[0082] The feed stream had a starting FFA content of 20.7% (see table 2, condensation at 150°C).

[0083] The enzyme Lipozyme 435 was used for the enzymatic condensation reaction. The feed stream (36.2 kg) was heated to 70°C under vacuum (1-2 mbar) to reduce moisture. The dosage of 2% Lipozyme 435 was added to the feed stream and allowed to react for 20 and 22 hours, respectively. The free fatty acids content was reduced to 4 wt.%.

[0084] The enzymatic treatment had relatively no impact on the amount of squalene, tocopherols, and / or tocotrienols.

[0085] The corresponding composition can be seen below in Table 3 and Table 4.Table 3: Minor components in Enzymatic Treated Feed StreamTotalTotal Total Total Tocopherols Squalene Tocopherols tocotrienols phytosterols +tocotrienols [wt %][wt %] [wt %] [wt %][wt %]Enzymatic treated0.53 1.96 2.51 1.57 5.45feed streamTable 4: Glycerides Composition of Enzymatic Treated Feed StreamPT-2254-WO-PCTTotal TotalTotal TAG Total MAGDAG [wt FFA [wt[wt %] [wt %]%] %]Enzymatictreated feed 63.10 8.71 0.20 4.08streamFractionation - Short Path Evaporation (SPE) of the enzymatic treated feed stream

[0086] Short-Path Evaporation (SPE) Unit KDL-5 from UK was used for the short path evaporation tests. The KDL-5 unit has an evaporator surface of 0.048 m2. The enzymatic treated feed stream was fractionated on the SPE to obtain a distillate and residue.

[0087] For the tests, the pressure and flow rate were kept relatively constant (see process conditions in Table 5) while evaporator temperature was changed (example to 180°C, 220°C or 240°C).Table 5: Process settings for SPE testsTest-condition Unit Test 180°C Test 200°C Test 220°C Test 240°C Temperatures bathfeed (°C) 80 80 80 80 evaporator (°C) 180 200 220 240 residue (°C) 80 100 120 140 condenser (°C) 70 70 70 70 Flow-rate per (kg / h per29 29 29 29 evaporation surface area m2)Vacuum systempressure (mbar) 2.0*10-3 2.1*10-3 2.1*10-3 2.0*10-3 Wiper Systemrollers / blockwiper type rollers rollers rollers rollers srotation speed (rpm) 366 366 366 366

[0088] The mass balances and compositions of the obtained distillates and residues, including content of free fatty acids, tocopherol, tocotrienols, phytosterols, and squalene, after SPE treatment at different temperatures, can be seen in Table 6, 7 & 8.Table 6: Mass balance fractionation SPEPT-2254-WO-PCTMass balance,wt.%SPE@ 180°CDistillate 5.40Residue 94.60SPE@ 200°CDistillate 7.30Residue 92.70SPE@ 220°CDistillate 8.80Residue 91.20SPE@240°CDistillate 11.00Residue 89.00Table 7: Minor Components of the distillates and residues fractionation SPETotalTotal Total Tocopherols Total Squalene Tocopherols tocotrienols and phytosterols [wt %][wt %] [wt %] Tocotrienols [wt %][wt %]SPE@180°CDistillate 1.38 4.09 5.49 12.56 2.00 Residue ND 0.78 0.78 0.67 5.82 SPE@ 200°CDistillate 2.66 7.31 9.97 12.69 4.01 Residue 0.36 1.39 1.75 0.31 5.63 SPE@ 220°CDistillate 4.23 13.63 17.86 12.26 6.86 Residue 0.21 0.79 1.01 0.16 5.38 SPE@240°CDistillate 4.43 15.12 19.54 10.47 7.87 Residue 0.09 0.34 0.43 0.07 5.38ND=not detectedTable 8: Glyceride Compositions of the distillates and residues fractionation SPETotal TAG Total DAG Total MAG Total FFA[wt %] [wt %] [wt %] [wt %]PT-2254-WO-PCTSPE@180°CDistillate ND 0.61 2.19 75.20 Residue 67.21 9.48 0.22 0.38SPE@ 200°CDistillate 0.16 1.02 3.67 59.58 Residue 69.28 9.08 0.10 0.05SPE@ 220°CDistillate ND 2.40 3.55 49.84 Residue 69.85 9.32 0.05 0.01SPE@ 240°CDistillate ND 8.42 3.08 39.96 Residue 72.44 8.89 0.01 0.04ND=not detected

Claims

PT-2254-WO-PCTCLAIMS1. A process for obtaining minor components from vegetable oils, the process is comprising:a) Enzymatic condensation of a feed stream in presence of a lipase for obtaining an enzymatic treated feed stream;b) Fractionation of the enzymatic treated feed stream into a distillate and a residue and the fractionation is taking place in a short path evaporator;c) Collecting the distillate and / or the residue; andWherein the feed stream of step a) is comprising triglycerides, diglycerides, monoglycerides, free fatty acids, tocopherols, squalene and optionally tocotrienols; andWherein free fatty acids are present in the feed stream in an amount of 5 to 65 wt.%; tocopherols are present in the feed stream in an amount of 0.1 to 5.0 wt.% of the feed stream, and squalene is present in an amount of 0.1 to 4.0 wt.% of the feed stream, and whereinthe vegetable oil includes palm oil, palm olein, palm mid-fraction or mixtures thereof.

2. The process according to claim 1 wherein the feed stream is comprising:a) Triglycerides in an amount of 7 to 55 wt.% based on weight of the feed stream.

3. The process according to claim 1 or 2 wherein the feed stream is further comprising: a) Diglycerides in an amount of 15 to 35 wt.% based on weight of the feed stream; b) Monoglycerides in an amount of 1 to 4.5 wt.% based on weight of the feed stream.

4. The process according to anyone of the preceding claims wherein the enzy matic treated feed stream is comprising:a) Triglycerides in an amount of 50 to 90 wt.% based on weight of the enzymatic treated feed stream;b) Free fatty acids in an amount of 1 to 10 wt.% based on weight of the enzy matic treated feed stream;c) Tocopherols in an amount of 0.1 to 3.0 wt.% based on weight of the enzymatic treated feed stream; andPT-2254-WO-PCTd) Squalene in an amount of 0.1 to 2.0 wt.% based on weight of the enzymatic treated feed stream.

5. The process according to anyone of the preceding claims wherein the fractionation of step b) is conducted in a short path evaporation at a temperature of from 180°C to 240°C.

6. The process according to anyone of the preceding claims wherein the distillate collected in step c) is comprisinga) Tocopherols, and optionally tocotrienols in an amount of 4 to 25 wt.% based on weight of the distillate; andb) Squalene in an amount of 8 to 15 wt.% based on weight of the distillate.

7. The process according to anyone of the preceding claims wherein the residue of step b) is comprisinga) Tocopherols, and optionally tocotrienols in an amount of 0.2 to 3 wt.% based on weight of the residue; andb) Squalene in an amount of below 1.5 wt.% based on weight of the residue.

8. The process according to anyone of the preceding claims wherein the residue collected in step c) is further comprisinga) Triglycerides in an amount of 60 to 80 wt.% based upon the weight of the residue; b) Diglycerides in an amount of 5 to 15 wt.% based on weight of the residue.

9. The process according to anyone of the preceding claims wherein the feed stream is a condensate stream of a deodorization step of a vegetable oil.

10. The process according to claim 9 wherein the condensate stream is obtained at a condenser temperature of from 100°C to 180°C.

11. The process according to anyone of the preceding claims wherein the residue is collected.

12. The process according to anyone of the preceding claims wherein the process is comprising the following steps:PT-2254-WO-PCTa) Enzymatic condensation of a feed stream in presence of a lipase for obtaining an enzymatic treated feed stream;b) Fractionation of the enzymatic treated feed stream into a distillate and a residue and the fractionation is taking place in a short path evaporator at a temperature of from 180 up to 240°C;c) Collecting the distillate;d) Collecting the residue; andWherein the feed stream of step a) is comprising triglycerides, diglycerides, monoglycerides, free fatty acids, tocopherols, squalene and optionally tocotrienols; andWherein free fatty acids are present in the feed stream in an amount of 5 to 65 wt.%; tocopherols are present in the feed stream in an amount of 0.1 to 3.0 wt.% of the feed stream, and squalene is present in an amount of 0.1 to 2.0 wt.% of the feed stream and whereinthe vegetable oil includes palm oil, palm olein, palm mid-fraction or mixtures thereof.

13. The process according to anyone of the preceding claims wherein the process is comprising the following steps;a) Enzymatic condensation of a feed stream in presence of a lipase for obtaining an enzymatic treated feed stream;b) Fractionation of the enzymatic treated feed stream into a distillate and a residue and the fractionation is taking place in a short path evaporator at a temperature of from 180 up to 240°C;c) Collecting the distillated) Collecting the residue;e) Recycling of the residue collected in step d) into a deodorization step of vegetable oil;andWherein the feed stream of step a) is comprising triglycerides, diglycerides, monoglycerides, free fatty acids, tocopherols, squalene and optionally tocotrienols; andPT-2254-WO-PCTWherein free fatty acids are present in the feed stream in an amount of 5 to 65 wt.%; tocopherols are present in the feed stream in an amount of 0.1 to 5.0 wt.% of the feed stream, and squalene is present in an amount of 0.1 to 4.0 wt.% of the feed stream, and wherein the vegetable oil include palm oil, palm olein, palm mid-fraction or mixtures thereof.

14. The process according to anyone of the preceding claims wherein the process is comprising the following steps:a) Enzymatic condensation of a feed stream in presence of a lipase for obtaining an enzymatic treated feed stream;b) Fractionation of the enzymatic treated feed stream into a distillate and a residue and the fractionation is taking place in a short path evaporator at a temperature of from 180 up to 240°C;c) Collecting the distillated) Collecting the residue;e) Recycling of the residue collected in step d) into a deodorization step of vegetable oil;andWherein the feed stream of step a) is comprising triglycerides, diglycerides, monoglycerides, free fatty acids, tocopherols, squalene and optionally tocotrienols; andWherein free fatty acids are present in the feed stream in an amount of 5 to 65 wt.%; tocopherols are present in the feed stream in an amount of 0.1 to 5.0 wt.% of the feed stream, and squalene is present in an amount of 0.1 to 4.0 wt.% of the feed stream, wherein the feed stream is a condensate stream of a deodorization step of a vegetable oil; andwherein the vegetable oil includes palm oil, palm olein, palm mid-fraction or mixtures thereof

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