In Situ Destruction of MCPD and Glycidyl Esters during Triglyceride Production

Transcription

1 In Situ Destruction of MCPD and Glycidyl Esters during Triglyceride Production Joseph ongione Jenifer Heydinger Galante Nothing contained herein grants or extends a license, express or implied, in connection with patents, issued or pending, of the manufacturer or others. The information contained herein is based on the manufacturer's own study and the works of others. The manufacturer makes no warranties, expressed or implied, as to the accuracy, completeness, or adequacy of the information contained herein. The manufacturer shall not be liable (regardless of fault) to the vendee's employees, or anyone for any direct, special or consequential damages arising out of or in connection with the accuracy, completeness, adequacy or furnishing of such information. 103rd ACS Annual Conference

2 utline Current State of Understanding History/Scope of undesired side products in food stream Proposed mechanisms of formation State of analytical technologies Elimination of Undesired Species History New MCT Process Mechanisms of MCPD removal Process flow diagram Data 103rd ACS Annual Conference

3 What are MCPDs? H H Cl H Cl Cl 3-monochloro-1,2-propanediol species (MCPDs) 103rd ACS Annual Conference

4 Glycidol and its esters H

5 Where are MCPDs found? Soy sauce Breads, donuts, chips, fries Coffee and creamers Cheese Cooked meats, salami, sausage *All refined vegetable oils including MCTs (medium chain triglycerides) *Infant formula ILSI summary report February rd ACS Annual Conference

6 Why do we care? 3-MCPD is carcinogenic, genotoxic Metabolic pathway for diesters uncertain World Health rganization (2001): TDI: 2 mg/kg of bodyweight for free 3-MCPD California Prop. 65 listing Detectable quantity Processing target - below detectable limits Joint FA/WH Expert Committee on Food Additives, rd ACS Annual Conference

7 MCPDs in Edible ils Palm oil > 4 ppm Soy, coconut ppm Infant formula ppm Commercial MCTs 2 ppm ppm ILSI summary report February rd ACS Annual Conference

8 Mechanisms of Formation Several mechanisms proposed Cyclic acyloxonium ion intermediate Water as leaving group Potential for several mechanisms Chloride source required Glycidol may be MPCD precursor Carcinogen, genotoxin 103rd ACS Annual Conference

9 Potential Mechanism of Formation MCPD Glycidyl esters -H + H H H H + H H + H -H 2 H H Cl H Hibbert, Greig, Can. J. esearch, (3): ; Svejkovska et al., Czech J. Food Sci., 2006, 24(4) Cl - 103rd ACS Annual Conference

10 Alternate Glycidyl Ester Formation Mechanism H - H H H Destaillats et al. (2012) Food Chem. 131: rd ACS Annual Conference

11 MCT Process aw Material Charging Esterification C Acid strip 245 C Neutralization Drying Filtration Deodorization Filter cake (carbon) Finished MCT 103rd ACS Annual Conference

12 MCTs Distinct from natural oils No bleaching step Forms during esterification and stripping Neutralization not a factor Use of carbon no effect emoved during deodorization, unlike other oils City vs. DI H 2 : No effect Temperature: ptimized for greatest MCPD removal 103rd ACS Annual Conference

13 Elimination of Impurities MCPD Species Deodorization Depends on ester chain length Physical means Bleaching clays Glycidyl Species Acid scavengers Sulfites Titration method for epoxides amli et al., J. Am. il Chem. Soc. (2011) 88: rd ACS Annual Conference

14 Impurity Destruction Mechanism xirane Species glycidyl ester M, H o C H diglyceride + M + H + M + - Carboxylate can be catalytic acidic destruction mechanism also possible M 103rd ACS Annual Conference

15 Impurity Destruction Mechanism rganohalo Species Cl monochloro propanediol diester o C M triglyceride + MCl - Cl M + equires stoichiometric carboxylate 103rd ACS Annual Conference

16 Current Analytical ptions GC/MS HPLC/MS No agreed-upon, official method edundant samples to multiple labs ACS Expert Panel convened 103rd ACS Annual Conference

17 Potential treatment points In situ processing Post esterification processing aw Material Charging Esterification C Acid strip 245 C Neutralization Dry Filtration Deodorization Filter cake (soap/carbon) Finished MCT Post deodorization processing 103rd ACS Annual Conference

18 Proof of Concept uns Description Moles Impurity added MCPD spiked in reaction mix Glycidyl butyrate spiked in MCT product Moles soap Molar ratio soap to impurity Final MCPD level (mg/kg) < 0.15 xirane species undetectable by GC after 1 hour 103rd ACS Annual Conference

19 Soap Concentration vs. Efficacy un A B C D Cation Na K Na None Millimoles soap Concentration of soap (mg/kg) Analysis results (mg/kg MCPDs) 8,960 1, < 0.15 < rd ACS Annual Conference

20 Pilot Plant in Situ Treatment un un 50 gallon reactor Cation K Concentration of soap (mg/kg) Analysis results (mg/kg MCPDs) 1,180 < rd ACS Annual Conference

21 Potential treatment points In situ processing Post esterification processing aw Material Charging Esterification C Acid strip 245 C Neutralization Dry Filtration Deodorization Filter cake (soap/carbon) Finished MCT Post deodorization processing 103rd ACS Annual Conference

22 Post esterification processing Undeodorized Plant Stream Undeodorized Plant Stream Hold temperature (C) Temperature profile 2 hr ramp, 2 hr hold 2 hr ramp, 2 hr hold Soap concentration (ppm) Initial MCPD level (mg/kg) Final MCPD level (mg/kg) 3,500 3, < rd ACS Annual Conference

23 Summary Eliminates both MCPDs and glycidyl species In situ or post production treatment Production scale since Feb Patent application published Mar rd ACS Annual Conference

24 Acknowledgements MCPD eduction Work Steve Clauss Pilot plant; Production obert iley - Production 103rd ACS Annual Conference