Counter current dry fractional crystallization

Abstract: The invention relates to a method for dry fractionation of fatty substances by a counter current dry fractionation operation, comprising at least two dry fractional crystallization treatments; - a first dry fractional crystallization treatment comprising the steps of: 1a) dry fractionating by crystallization the fatty substances into a higher melting first stearin fraction and a lower melting first olein fraction; 1b) separating the first stearin fraction from the first olein fraction by membrane filter pressing; and 1c) feeding the separated first olein fraction to a second dry fractional recrystallization treatment; and - a second dry fractional crystallization treatment comprising the steps of: 2a) dry fractionating by crystallization the first olein fraction into a higher melting second stearin fraction and a lower melting second olein fraction; 2b) separating the second stearin fraction from the second olein fraction by membrane filter pressing; and 2c) feeding the separated second stearin fraction to the first dry fractional crystallization treatment.

Description: The present invention relates to a method for dry fractional crystallization of fatty substances, including fats and glyceride oils. In particular, the invention relates to the separation of fatty substances in a multi-stage dry fractional crystallization process, in which a high melting fraction obtained in a dry fractional crystallization treatment is recycled to an earlier dry fractional crystallization treatment. Natural glyceride oils and fats comprise a great many different triglycerides, the physical properties of which to a large extent are determined by the chain lengths and the degrees of unsaturation of the fatty acid moieties. To make natural glyceride oils and fats more suitable for particular applications it is often required to separate them into fractions characterized by fatty acid glyceride distributions which are more homogeneous with respect to the melting behaviour. For instance, fat blends suitable for producing margarines having a relatively high ratio of polyunsaturated to saturated fatty acids comprise triglycerides with a specific M₃/H₂M ratio (M means saturated C₁₂-C₁₄ fatty acid residue, H means saturated or mono-trans C₁₆ or more fatty acid residue), imparting margerines good organoleptic properties and suitable consistency at a temperature within the range of 15-25°C (see European patent application 89,082). In the book "Bailey's Industrial Oil and Fat Products" Volume 3, page 5-37 (1985) commercial dry fractionation processes are disclosed in which the oil is cooled to a temperature at which only a higher melting triglyceride fraction crystallizes, followed by separation of the crystallized solids and the liquid fraction, e.g. by filtration or centrifugation. A multi-stage counter current solvent fractionation process is disclosed in US 2,147,222, in which process a solid phase obtained in a crystallization treatment is passed to the next separation treatment, from which the liquid phase is passed to the former crystallization treatment. This transport of intermediate products is indicated by the term "counter current". Although solvent fractionation processes involve relatively high capital costs, up to now counter current dry fractionation has not been used on an industrial scale, because conventional separation techniques, such as filtration and centrifugation, possess relatively low separation efficiencies. A high separation efficiency is required to warrant an effective dry fractionation, because the amounts of the mutually counter current fractions determine the properties and the amounts of the products obtained in the dry fractionation. Finally, counter current dry fractionation is a process more difficult to control because of its complexity. The present invention is based on the finding that counter current dry fractionation is feasible on an industrial scale when membrane filter presses are used in the separation operation, resulting in much higher separation efficiencies. Although the separation of dry crystallized fatty materials using a membrane filter press was disclosed more than ten years ago (H. Hinnekens, "Le fractionnement des corps gras sans solvant", chapter 9 in Symposium International - La filtration dans le raffinage, le fractionnement des corps gras, 1976), it was not recognized up to now that using membrane filter presses, counter current dry fractional crystallization is feasible on an industrial scale. It has now been found that using a membrane filter press in a multi-stage counter current dry fractionation method, stearin fractions, olein fractions and/or mid fractions may be obtained in a higher yield and improved quality, and that oils having a relatively high solids content on fractionation may be fractionated, which oils due to these solids were difficult to fractionate in a conventional manner. Accordingly, the present invention provides a method for dry fractionation of fatty substances by a counter current dry fractionation operation, comprising at least two dry fractional crystallization treatments; a first dry fractional crystallization treatment comprising the steps of: 1a) dry fractionating by crystallization the fatty substances into a higher melting first stearin fraction and a lower melting first olein fraction; 1b) separating the first stearin fraction from the first olein fraction by membrane filter pressing; and 1c) feeding the separated first olein fraction to a second dry fractional recrystallization treatment; and a second dry fractional crystallization treatment comprising the steps of: 2a) dry fractionating by crystallization the first olein fraction into a higher melting second stearin fraction and a lower melting second olein fraction; 2b) separating the second stearin fraction from the second olein fraction by membrane filter pressing; and 2c) feeding the separated second stearin fraction to the first dry fractional crystallization treatment. According to the method of the present invention the olein fraction obtained after dry fractional crystallization of the starting fatty material and separation by membrane filter pressing is subjected to a similar dry fractional crystallization treatment at a lower crystallization temperature and the stearin fraction obtained is recycled to the first dry fractional crystallization treatment and mixed with the starting fatty material. If the first olein fraction subjected to the second dry fractional crystallization treatment according to the invention comprises a relatively high solids content, it is preferred that the second olein fraction is at least partly recycled and mixed with the first olein fraction to be dry fractionated in the second dry fractional crystallization treatment whereby the first olein fraction is diluted, preferably the recycling ratio for the olein fraction is about 10-60%, more preferably 25-50%. The method for counter current dry fractionation according to the invention may be used in the topping or bottoming section of a multi-stage dry fractionation process in which mid fractions are produced. When mid fractions are to be produced it is preferred that the olein fraction used as a feed for the dry fractional crystallization treatment that provides the mid fraction, is subjected to a second counter current dry fractional operation comprising at least two dry fractional crystallization treatments: a third dry fractional crystallization treatment comprising the steps of: 3a) dry fractionating by crystallization the second olein fraction into a higher melting third stearin fraction and a lower melting third olein fraction; 3b) separating the third stearin fraction from the third olein fraction by membrane filter pressing; and 3c) feeding the separated third olein fraction to fourth dry fractional crystallization treatment; and a fourth dry fractional crystallization treatment comprising the steps of: 4a) dry fractionating by crystallization the third olein fraction into a higher melting fourth stearin fraction and a lower melting fourth olein fraction; 4b) separating the fourth stearin fraction from the fourth olein fraction by membrane filter pressing; and 4c) feeding the separated fourth stearin fraction to the third dry fractional crystallization treatment. An optimal multi-stage counter current dry fractionation method is obtained if the separation efficiency by membrane filter pressing is higher than 0.4, preferably the separation efficiency is higher than about 0.5, most preferred as high as possible (0.5-0.85). The multi-stage dry fractionation method according to the invention is applicable to both batch and continuous methods of crystallization. The process is suitable for the dry fractionation of all semi-solid fatty substances from which a significant solid fraction has to be separated. It is particularly suitably applied to the fractionation of semi-solid glyceride oils and fats of vegetable, animal or marine origin, such as palm oil, palm kernel oil, tallow, butter fats, fish oils and mixtures thereof. These oils and fats may be partially hardened, pre-fractionated and/or inter-esterified. The method according to the invention is advantageously suitable for the production of hardstocks as starting materials for the production of margerines and spreads having an increased ratio of poly-unsaturated fatty acids to saturated fatty acids, and superior organoleptic properties. The counter current dry fractionation method according to the invention will be illustrated hereafter in comparison to dry fractionation processes according to the prior art. The various processes are shown in the annexed single drawing, in which each box refers to a dry fractional crystallization treatment comprising dry fractionation in a crystallizer and separation of the stearin fraction from the olein fraction using a membrane filter press. It is possible to carry out the multi-stage process of dry fractional crystallization in one crystallizer and with several storage tanks in which the olein and stearin fractions are temporarily stored, in a batchwise embodiment. Methods A and B are not according to the invention, because of the absence of a counter current recycling of the stearin fraction obtained in the second dry fractional crystallization treatment. Methods C, D and E are according to the invention and in methods D and E there is a partial recycling of the second olein fraction. Process E is specifically designed for the production of mid fraction. Experiment 1 Neutralized and bleached palm oil having the following composition: S₃: 9.0%; S₂O: 41.0%; remainder: 50.0%, was heated to 70°C to achieve complete liquidity (S means stearic acid residue, O means oleic acid residue). Subsequently, the liquid palm oil was dry fractionated in crystallization methods A, B, C, and D of which the process conditions and the composition and yield of the olein fraction and of the stearin fraction obtained in the first dry fractional crystallization treatment are summarized in table I. Table I clearly shows that in the olein fraction obtained in the methods C and D according to the invention the S₂O content increases and the S₃ content remains constant, whereas the olein yield increases notably. These olein fractions according to the invention are very suitable for use in margerines, because the increased S₂O content at a constant S₃ content imparts superior organoleptic properties and hardness at room temperature to the margerine. The stearin fraction obtained in methods C and D according to the invention shows an increased S₃ content and a lower S₂O content. This stearin fraction is suitable as a raw material for triglyceride mixtures rich in palmitic moieties. A comparison of methods C and D shows that by recycling the second olein fraction a feedstock with a relatively high solids content may be dry fractionated in a counter current process. Experiment 2 A hardstock comprising a mixture of partly hardened and inter-esterified palm oil and palm kernel oil was neutralized and bleached and heated to complete liquidity. The hardstock comprised 18.3% H₃ and 38.6% H₂M. This hardstock was dry fractionated under such conditions, that the H₂M content was as high as possible in order to improve the structure of the margerine. The process conditions and composition of the olein and stearin fractions obtained, and the stearin yield, are reviewed in table II for the prior art methods A and B and method C according to the invention. Table II clearly shows that method C according to the invention provides an olein fraction having the highest H₂M content, and is very suitable for use in the production of margerine hardstock. Experiment 3 A similar hardstock as used in experiment 2 was used. This hardstock comprised 17% H₃ and 40% H₂M. This hardstock was dry fractionated such that the H₃ content is about 12%, and the H₂M content was as high as possible. Accordingly, a mid fraction was obtained imparting superior properties to the margerines and spreads comprising it. The process conditions and composition of the olein and stearin fractions are reviewed in table III for the counter current dry fractional crystallization method E according to the invention. The mid fraction yield of process E (olein III) is 38%. It is noted that a fractionation similar to the method B is not feasible under experimental conditions, because in the second fractionation treatment about 28% of solids formed during crystallization should be separated. Such a separation of this type of fractions appears to be impossible at a sufficient separation efficiency. Experiment 4 A similar hardstock as used in experiment 2 was used. This hardstock comprised 15.8% H₃ and 39.6% H₂M. This hardstock was dry fractionated such that the H₃ content was about 24% and the H₂M content was as high as possible. Accordingly, a stearin was obtained imparting superior properties to the margarines and spreads comprising it. The process conditions and composition of the olein and stearin fractions are reviewed in table IV for the prior art method B and method C according to the invention. Table IV clearly shows that method C according to the invention provides a stearin fraction having a higher H₂M content, and is very suitable for use in the production of margarine hardstock. Conditions + Composition Dry fractional crystallization process A B C D T I (°C) 24.5 38 38 38 T II (°C) -- 24.5 24.5 24.5 SE I 0.5 0.5 0.5 0.5 SE II -- 0.5 0.5 0.5 SPC I 12.8 5.7 8.5 8.5 SPC II -- 7.1 7.4 6.6 Olein S₃ 0.9 0.9 0.9 0.9 S₂O 42.1 42.3 43.6 43.6 yield (%) 74.5 76.1 80.7 80.7 Stearin S₃ 33.0 35.0 43.7 43.7 S₂O 37.5 36.5 29.6 29.7 (SE means separation efficiency SPC means solid particles content). Conditions + Composition Dry fractional crystallization process A B C T I (°C) 41.6 43.3 43.4 T II (°C) -- 41.4 40.5 SE I 0.5 0.5 0.5 SE II -- 0.5 0.5 SPC I 15.7 8.6 12 SPC II -- 8.6 12 Olein H₃/H₂M 10.0/39.4 9.2/39.7 6.9/40.6 Stearin H₃/H₂M 36.6/37.0 37.8/36.6 42.4/34.7 yield (%) 31.5 31.5 31.5 Conditions + Composition Dry fractional cystallization process E T₁ (°C) 45 T₂ (°C) 41 T₃ (°C) 36 T₄ (°C) 32.5 SE I 0.5 SE II 0.5 SE III 0.52 SE IV 0.52 SPC I 11 SPC II 11 SPC III 18 SPC IV 18 Olein I 12/43 Olein II 7/42 Olein III 3/40 Olein IV 2/30 Stearin I 47/36 Stearin II 31/48 Stearin III 12/55 Stearin IV 4/48 Conditions + Composition Dry fractional crystallization process B C T I (°C) 38 37 T II (°C) 33 32 SE I 0.5 0.5 SE II 0.5 0.5 SPC I 19.5 19.5 SPC II 19.5 19.5 Olein H₃/H₂M 24/44 24/48 yield (%) 63 64

Claims: Method for dry fractionation of fatty substances by a counter current dry fractionation operation, comprising at least two dry fractional crystallization treatments; a first dry fractional crystallization treatment comprising the steps of: 1a) dry fractionating by crystallization the fatty substances into a higher melting first stearin fraction and a lower melting first olein fraction; 1b) separating the first stearin fraction from the first olein fraction by membrane filter pressing; and 1c) feeding the separated first olein fraction to a second dry fractional recrystallization treatment; and a second dry fractional crystallization treatment comprising the steps of: 2a) dry fractionating by crystallization the first olein fraction into a higher melting second stearin fraction and a lower melting second olein fraction; 2b) separating the second stearin fraction from the second olein fraction by membrane filter pressing; and 2c) feeding the separated second stearin fraction to the first dry fractional crystallization treatment. Method as claimed in claim 1, wherein the second olein fraction is partly recycled and mixed with the first olein fraction to be dry fractionated in the second dry fractional crystallization treatment. Method as claimed in claim 1 or 2, wherein the second olein fraction obtained is subjected to a second counter current dry fractional operation comprising at least two dry fractional crystallization treatments: a third dry fractional crystallization treatment comprising the steps of: 3a) dry fractionating by crystallization the second olein fraction into a higher melting third stearin fraction and a lower melting third olein fraction; 3b) separating the third stearin fraction from the third olein fraction by membrane filter pressing; and 3c) feeding the separated third olein fraction to fourth dry fractional crystallization treatment; and a fourth dry fractional crystallization treatment comprising the steps of: 4a) dry fractionating by crystallization the third olein fraction into a higher melting fourth stearin fraction and a lower melting fourth olein fraction; 4b) separating the fourth stearin fraction from the fourth olein fraction by membrane filter pressing; and 4c) feeding the separated fourth stearin fraction to the third dry fractional crystallization treatment. Method as claimed in claim 3, wherein the fourth olein fraction is partly recycled and mixed with the third olein fraction to be dry fractionated in the fourth dry fractionation treatment. Method as claimed in claim 1-4, wherein the separation efficiency by membrane filter pressing is higher than 0.4. Method as claimed in claim 5, wherein the separation efficiency by membrane filter pressing is higher than 0.5. Method as claimed in claim 1-6, wherein the recycling ratio for the olein fraction is about 10-60%. Method as claimed in claim 7, wherein the recycling ratio of the olein fraction is about 25-50%.

Inventors: KEULEMANS CORNELIS NICOLAAS MA, VAN DEN OEVER CHRISTIAAN EVERT, KEULEMANS, CORNELIS NICOLAAS MARIA, VAN DEN OEVER, CHRISTIAAN EVERT
Applicants: UNILEVER NV, UNILEVER PLC, UNILEVER N.V.
Application year: 1990
Main classification: C11B7
IPC codes: C11B7