Developments in Edible Oil Refining for the Production of High Quality Food Oils
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1 1 101 st ACS Annual Meeting Phoenix, Arizona Developments in Edible il Refining for the Production of High Quality Food ils Wim De Greyt Desmet Ballestra Group, Zaventem, Belgium
2 101 st ACS Annual Meeting WRLD VEGETABLE IL PRDUCTIN Total : 140 Mio Ton % Palm Soybean Rapeseed Sunflower Palm Kernel Cottonseed Coconut live Corn thers
3 101 st ACS Annual Meeting VEGETABLE ILS : GENERAL CMPSITIN Acylglycerols (92-95%) -Mainly Triacylglycerols -Some Di- and Monoacylglycerols FFA (0.3-5%) Minor components (0.3-2%) - Tocopherols, Sterols, Pigments, - Contaminants, Impurities,. Phospholipids (<3%) -Hydratable PL -Non-hydratable PL
4 101 st ACS Annual Meeting VEGETABLE ILS : MINR CMPNENTS Valuable Minor Components Side Reaction Products Tocopherols, Sterols,. - Desired in the refined oil - Good nutritional properties - To be retained during refining MINR CMPNENTS Contaminants Pesticides, PAH, Dioxins, Trans FA, polymers, (3-MCPD esters), - Formed during refining - Bad nutritional properties -Unwanted - Present in crude oils - Carcinogenic/Toxic - To be removed during refining
5 101 st ACS Annual Meeting Phoenix, Arizona REFINED IL QUALITY PARAMETERS rganoleptic quality /stability Nutritional Quality -Bland taste, no odor -Light color (brilliant) -High thermal stability -High oxidative stability -Long shelf life IL QUALITY - High tocopherol content -No trans FA - No contaminants - No side-reaction products -(Fatty acid composition) Standard Quality Parameters New Quality Parameters ptimized Edible il Processing required to meet new oil Quality Parameters
6 101 st ACS Annual Meeting REFINERS CHALLENGE EFFICIENCY REFINING PRCESS CNDITINS SUSTAINABILITY QUALITY
7 101 st ACS Annual Meeting EDIBLE IL REFINING : PRCESS PTINS Crude il Water degumming Gums Chemical refining WDG il Physical refining Soapstock Alkali Neutralisation Acid Gums Acid degumming Bleaching Spent bleaching earth Bleaching Deodorization Deodorizer Distillate Physical deacidification Deodorization Fully Refined il
8 101 st ACS Annual Meeting CNTAMINANT REMVAL DURING IL PRCESSING Adsorption on specific adsorbens (active carbon) Heavy Polycyclic Aromatic Hydrocarbons (PAH) Dioxins and furans from Fish ils Dioxin-like PCB (non-ortho PCB) Deodorization/Steam Stripping Pesticides (herbicides,insecticides,fungicides,.) Light PAH (e.g. from coconut oil) rtho-pcb (non dioxin-like PCB)
9 101 st ACS Annual Meeting Combiclean process meets refiners challenge Vacuum unit Removal of contaminants Active carbon Silica Bleaching earth Degummed oil Pre filtration final filtration cleaning Silica + Prebleaching 2 Spent bleach earth acid bleacher Sparge steam Spent bleach earth Leaf filters Filter press Spent carbon Polish filters bleaching Bleached oil To deodorisation
10 101 st ACS Annual Meeting TFA formation during soybean oil deodorization 5 4,5 4 TFA max. 1.0% 270 C %TFA 3,5 3 2,5 2 1,5 1 0,5 260 C 250 C 230 C Time (minutes) 200 C 210 C 220 C 230 C 240 C 250 C 260 C 270 C REDUCING HEAT LAD AND KEEPING STRIPPING EFFICIENCY HIGH
11 101 st ACS Annual Meeting LWER HEAT LAD DUAL TEMPERATURE 841 Vacuum Plant Scrubber to 841 vacuum plant 823 HP Heating Steam 878AG Distillate Collection P850/81AG Distillate Storage 881AG Distillate Cooler P878AG 822TS Steam Stripper Low pressure short pack to 841 vacuum plant RB il Feed Steam Deaerator Steam Steam 880A1/ Deodorizer Steam 890 HP Steam generator Single or Dual Temp 880A2 Steam Cooling Water 810 il Deaeration 808 Splash il Recovery P880A2 881A il/il Heat Exchanger 881B Final il Cooler 816A Polishing Filters P801
12 101 st ACS Annual Meeting IMPRVED VACUUM SYSTEMS CHILLED BARMETRIC WATER ICE CNDENSING * Lower pressure in the deodorizer - Lower motive steam consumption * Less odor emissions
13 101 st ACS Annual Meeting NEW CHALLENGE : 3-MCPD / GLYCIDL ESTERS MCPD ESTERS H R R R H R Cl 3-MCPD mono-(sn1) ester Cl 3-MCPD mono-(sn2) ester Cl 3-MCPD di-ester GLYCIDL ESTERS H H H 2 C C CH 2 H 2 C C CH 2 H CR Free glycidol Glycidol-ester
14 101 st ACS Annual Meeting CCURRENCE IN REFINED FD ILS MCPD-ester content in various vegetable oils (source : FEDIL) IL N Samples Average content 3-MCPD ester Max. level of 3-MCPD ester Rapeseed il mg/kg 1.5 mg/kg Sunflower il mg/kg 5.7 mg/kg Corn il mg/kg 7.0 mg/kg Palm il mg/kg 13 mg/kg * Reported data vary widely (due to applied method?) * Most used (DGF) method not generally accepted * Mechanism of formation not fully understood * Very difficult to develop an efficient mitigation strategy
15 MECHANISM F FRMATIN : HYPTHESIS MNGLYCERIDES AS PRECURSR 101 st ACS Annual Meeting CH H H H H 2 CH H - H 2 CH Cl C R 2 MAG C R 2 Cl C R 2 Glycidol ester Nucleophilic substitution Cl CH H C R 2 Source : R. Verhé, Dept. rganic Chemistry, UGent, (2010) 3-MCPD mono-ester
16 MECHANISM F FRMATIN : HYPTHESIS DIGLYCERIDES AS PRECURSR 101 st ACS Annual Meeting CH 2 H CH C CH 2 C DAG R 1 R 2 CH 2 H 2 H CH C CH 2 C R 1 R 2 Nucleophilic substitution Cl CH 2 Cl CH C CH 2 C R 1 R 2 3-MCPD di-ester + H 2 CH Cl H DAG C CH C C R > 240 C CH Source : R. Verhé, Dept. rganic Chemistry, UGent, (2010) Cl H C Radicalar mechanism R CH C R Glycidol-esters
17 101 st ACS Annual Meeting Phoenix, Arizona Mono- and diglycerides and 3-MCPD ester formation MCPD ester content (mg/kg) ,2 0,4 0,6 0,8 1 1,2 Palm il, deodorized at 260 C Monoglyceride-content (%) 3-MCDP ester content (mg/kg) Diglyceride content (%) Palm il, deodorized at 260 C * Low DAG content will result in low 3-MCPD/glycidol-ester content * If DAG > 4%, then 3-MCPD/glycidol ester content is mostly > 5 ppm * No apparent correlation between MAG and 3-MCPD/glycidol ester formation Source :Karel Hrncirik (Unilever,2009) and Bertrand Matthaus (MRI, 2009)
18 101 st ACS Annual Meeting 3-MCPD ester (ppm) EFFECT F TEMPERATURE 3-MCPD esters : 1 hr; : 2 hr : 4 hr 3,5 3 2,5 2 1,5 1 0, Temperature ( C) Glycidol esters Gly cidol esters (p p m ) : 1 hr; : 2 hr : 4 hr Temperature ( C) Source : Bertrand Matthaus (MRI, 2009) Temperature more important parameter than time At t > 240 C, mainly glycidol-esters are formed (exponential increase) Formation of 3-MCPD esters is relatively independent of temperature (2-4 ppm)
19 101 st ACS Annual Meeting MITIGATIN STRATEGY Current statement of BfR (German Federal Institute for Risk Assessment) Alternative techniques have to be developed that guarantee the production of refined food oils with reduced or no 3-MCPD esters (and related compounds) Today s informal position of FEDIL Information so far obtained is insufficient to optimize the refining process for the mitigation (reduction/removal) of 3-MCPD esters and related compounds while maintaining the quality and food safety of the refined oil/fat
20 MITIGATIN STRATEGY 101 st ACS Annual Meeting 3-MCPD esters -Require acidic conditions and presence of chloride -Can be formed during acid degumming and bleaching -Washing may remove chlorides from crude oil -Systematic monitoring of chlorides in all processing aids Glycidol esters -Can be formed from MAG via nucleophilic substitution (in absence of Cl - ) -Formation from DAG possible via radicalair reaction at T > 240 C -Most likely to be formed during deodorization at high temp. (physical refining) -Dual temperature deodorization concept may give lower levels
21 101 st ACS Annual Meeting CNCLUSIN Vegetable il Refining can be optimized to meet new oil quality standards - Activated carbon process for removal of heavy contaminants - ptimized steam distillation/deodorization for removal of light contaminants minimal trans formation - ther refiners challenges (efficiency, environmental impact) are also met 3-MCPD and glycidol esters - Still some knowledge gaps makes good mitigation strategy difficult - Need for a more reliable and accurate analytical methodology - Better understanding of mechanisms of formation during food processing in general and oil refining in particular required
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