Real Time and In Situ Monitoring of the Crystallization of Palm Oil-based Products using Focused Beam Reflectance Measurement (FBRM) Elina Hishamuddin Malaysian Palm Oil Board, Malaysia
OVERVIEW Introduction Palm oil Palm oil fractionation Focused beam reflectance measurement (FBRM) Materials and Methods Crystallization experiments Compositional analyses Results and Discussion Palm Oil Crystallization - Crystals population Palm Oil Melting Melting mechanisms Palm Olein Crystallization - Crystal size distribution & Crystallisation mechanisms Palm Olein Blend with Legume Seed Oil effect of blending on crystallization mechanism Conclusions 2
PALM OIL Palm oil largest produced vegetable oil in the world, >59.5 million tonnes in 214. (Source: Oil World Annual 214) Palm oil mainly consists of a multicomponent mixture of: Triacylglycerols (TAGs): 94% Diacylglycerols, monoacylglycerols and free fatty acids: 6%. Serves as feedstock for a variety of industries, i.e. food, oleochemicals, biofuels etc. Palm-based food products range from cooking oils, salad oils to margarines and shortenings and confectionery fats. 3
PALM OIL FRACTIONATION Dry fractionation : controlled partial crystallisation of oil from the melt and filtration of crystallized slurry Crystallisation : driven by differences in the melting points of the TAGs & operating temperature Quality of subproducts depend on the operating conditions during the crystallization stage and crystal characteristics such as size, numbers and shape have a profound effect on the filtration stage. Palm Oil Palm Olein Super Olein Palm Mid Fraction Palm Stearin Soft Stearin Super Stearin 4
MOTIVATION Most crystallization studies are performed on static systems Differential Scanning Calorimetry (DSC), polarized light microscopy (PLM), X-ray diffraction (XRD) etc. Static systems do not accurately reflect the actual industrial process. Dynamic systems are less studied due to fewer available monitoring devices. Particle characteristic studies image analysis, laser particle counters, particle size analyzers. Most require sampling the material and in some cases dilution -> changes material in study Focused beam reflectance measurement (FBRM) non-destructive technique capable of monitoring particle characteristics on-line in real time. 5
FOCUSED BEAM REFLECTANCE MEASUREMENT (FBRM) In-situ measuring device Real time tracking of particle size, population and events. No sampling or dilution required Particle size range :.8 1 µm Particle size in chord length Measurement depends on crystal orientation Source : Mettler Toledo 6
CRYSTALLIZATION METHODS Material : 7 ml oil FBRM 1 L Mettler Toledo LabMax Automatic Lab Reactor with LASENTEC FBRM Model D6L Agitation speed: 5 rpm Isothermal Crystallization time: Palm oil : 2 hours Palm olein : 6 hours Blended oil : 5 hours Morphological analysis by polarised light microscope 7
COMPOSITIONAL ANALYSES Fatty acids composition Triacylglycerols composition ISO 558:199 AOCS Method Ce 5c-89 GC-FID Conditions HPLC-RID Conditions Column : DB-23, 6m L x.25 Column : Purospher RP-18, 4.6 mm i.d., film thickness.25 µm mm i.d. x 25 mm L, 5 µm particles, 2 connected in series Oven T : 185 C Column & detector T : 35 C Injector & detector T : 24 C Acetone:Acetonitrile = 63.5:36.5 Carrier gas : He @.8 ml/min Flowrate : 1 ml/min Split ratio 1:1 GC-FID HPLC-RID 8
PALM OIL CRYSTALLIZATION 9
PALM OIL CRYSTALLIZATION Crystal population of palm oil crystallized at 32 C 45 Total particles 7 4 35 6 3 5 25 4 2 3 15 2 Oil temperature 1 Filter cake yield 1 5 Total particles (cts/s) Oil temperature (oc) / Filter cake yield (%) 8 1 2 3 Time (min) Hishamuddin et al. (211), J. Cryst. Growth, 335, 172-18 1
PALM OIL MELTING Melting mechanism of pre-crystallized palm oil from 24 to 46 C Melting Deagglomeration 8 12 Toil 6 1 Fine particles.8-5.5 mm 8 5 44 C 4 6 3 C 3 36 C 24 C 4 2 2 1 Coarse particles >88 mm 1 2 3 4 5 6 Time (min) Hishamuddin et al. (211), J. Cryst. Growth, 335, 172-18 11 Particle counts (Cts/s) Temperature ( C) 7
PALM OLEIN CRYSTALLIZATION 12
PALM OLEIN CRYSTALLIZATION Crystal population of palm olein crystallized at 9, 13 and 15 C 7 Agglomeration Total Counts (#/s) 6 9 C 5 4 13 C 3 Primary Nucleation 2 Secondary Nucleation 1 15 C 5 1 15 2 25 3 35 Isothermal hold time (min) Hishamuddin et al. (211), Eur. J. Lipid Sci., 113(S1): 1-46 13
PALM OLEIN CRYSTALLIZATION Crystal size distribution of palm olein crystallized at 9, 13 and 15 C 35 9 C Count/Channel (#) 3 25 13 C 2 15 1 5 15 C 1 1 1 1 Chord Length (µm) Hishamuddin (214). Palm Oil Dev., 61, 12-13 & 21-25. 14
PALM OLEIN CRYSTALLIZATION Fatty acid composition of palm olein crystallized at 9, 13 and 15 C PUFA 42.5 39.4 4 MUFA IV 64 47.2 5 Percentage (%) SFA 65 45.3 43.3 44.9 63 62 61 3 6 2 59 13.3 12.1 11.8 Iodine Value (IV) 6 58 1 57 56 9 11 Temperature ( C) IV : Iodine value PUFA : polyunsaturated fatty acids 13 SFA : saturated fatty acids MUFA : monounsaturated fatty acids 15
PALM OLEIN CRYSTALLIZATION Major triacylglycerol groups of palm olein crystallized at 9, 13 and 15 C 6 SUS SUU UUU 5 Percentage (%) 4 3 2 1 9 SUS : monounsaturated 13 Temperature ( C) SUU : diunsaturated 15 UUU : triunsaturated 16
OIL BLEND CRYSTALLIZATION 17
OIL BLEND CRYSTALLIZATION Crystals population of palm olein blended with winged bean seed oil at 13 C 9 Palm Olein 8 Total counts (#) 7 2.5% WBSO 6 5% WBSO 5 Secondary nucleation 4 3 2 Primary nucleation 1 5 1 15 2 Time (min) 25 3 35 18
OIL BLEND CRYSTALLIZATION Crystal size distribution of palm olein blended with winged bean seed oil at 13 C 35 Palm Olein 2.5% WBSO 5% WBSO Count/Channel (#) 3 25 2 15 1 5 1 1 1 Chord Length (µm) 1 19
OIL BLEND CRYSTALLIZATION Fatty acid composition of palm olein blended with winged bean seed oil at 13 C Fatty acid Palm Olein WBSO 2.5% WBSO in palm olein 5% WBSO in palm olein C16: 39.74 5.59 31.77 31.21 C18: 4.3 3.9 3.95 3.95 C18:1 42.53 31.88 45.6 45.27 C18:2 11.21 37.13 15.74 16.27 C18:3.22 1.37.48.51 C2:.43 1.3.34.35 C2:1-3.41.25.32 C22: - 11.9.35.61 C24: - 2.52 - - 56.63 95.5 67.72 68.42 Iodine value 2
CONCLUSIONS FBRM is a useful tool to characterize crystallization of palm oil-based products and oils and fats systems, in general. FBRM provides valuable information such as population, size distribution and mechanisms of particle formation/disappearance. In situ and real time data representative of actual process conditions. By complementing FBRM data with an imaging technique and compositional analysis, more information on crystallization behavior can be deciphered. Utilization of FBRM enables proper control and optimization of crystallization conditions to ensure production of optimum crystal characteristics. 21
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