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Fats and oils formulating and processing for applications obrien

  1. 1. Fatsand Oils Formulating and Processing for Applications Third Edition
  2. 2. Fatsand Oils Formulating and Processing for Applications Richard D. O’Brien Third Edition
  3. 3. CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2009 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Printed in the United States of America on acid-free paper 10 9 8 7 6 5 4 3 2 1 International Standard Book Number-13: 978-1-4200-6166-6 (Hardcover) This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher can- not assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www.copy- right.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that pro- vides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data O’Brien, Richard D. Fat and oils : formulating and processing for applications / Richard D. O’Brien. -- 3rd ed. p. cm. Includes bibliographical references and index. ISBN-13: 978-1-4200-6166-6 ISBN-10: 1-4200-6166-6 1. Oils and fats, Edible. I. Title. TP670.O27 2009 664’.3--dc22 2008020476 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com
  4. 4. v Contents Third Edition Preface...............................................................................................xix 1Chapter Raw Materials.............................................................................................................1 1.1 Introduction......................................................................................................1 1.2 Sources of Fats and Oils..................................................................................2 1.3 Vegetable Oil Yields........................................................................................2 1.4 Availability of Fats and Oils............................................................................4 1.5 United States Utilization of Edible Fats and Oils............................................4 1.6 Characterization of Fats and Oils....................................................................7 1.7 Nonglyceride Components of Fats and Oils....................................................8 1.7.1 Phospholipids......................................................................................8 1.7.2 Tocopherols and Tocotrienols.............................................................9 1.7.3 Sequalene..........................................................................................10 1.7.4 Sterols...............................................................................................10 1.7.5 Pigments............................................................................................12 1.7.6 Pesticides...........................................................................................13 1.7.7 Trace Metals......................................................................................13 1.8 Genetically Modified Vegetable Oils.............................................................13 1.9 Soybean Oil....................................................................................................15 1.9.1 Soybean Oil Composition and Physical Properties.......................... 17 1.9.2 Genetically Modified Soybean Oil................................................... 18 1.10 Cottonseed Oil...............................................................................................19 1.10.1 Cottonseed Oil Composition and Physical Properties......................20 1.10.2 Genetically Modified Cottonseed Oil...............................................22 1.11 Peanut Oil.......................................................................................................22 1.11.1 Peanut Oil Composition and Physical Properties.............................23 1.11.2 Genetically Modified Peanut Oil......................................................25 1.12 Corn Oil.........................................................................................................25 1.12.1 Corn Oil Composition and Physical Properties................................26 1.12.2 Genetically Modified Corn Oil.........................................................28 1.13 Sunflower Oil.................................................................................................28 1.13.1 Sunflower Oil Composition and Physical Properties........................29 1.14 NuSun Sunflower Oil.....................................................................................30 1.14.1 NuSun Composition and Physical Properties................................... 31 1.15 High-Oleic Sunflower Oil..............................................................................32 1.15.1 High-Oleic Sunflower Oil Physical Properties and Composition...............................................................................32 1.16 Safflower Oil..................................................................................................33 1.16.1 Safflower Oil Composition and Physical Properties.........................33
  5. 5. vi Contents 1.17 High-Oleic Safflower Oil...............................................................................35 1.17.1 High-Oleic Safflower Oil Composition and Physical Characteristics..................................................................................35 1.18 Canola Oil......................................................................................................37 1.18.1 Canola Oil Composition and Physical Properties.............................37 1.18.2 Genetically Modified Canola Oil......................................................39 1.19 Olive Oil.........................................................................................................40 1.19.1 Olive Oil Composition and Physical Properties............................... 41 1.20 Palm Oil.........................................................................................................43 1.20.1 Palm Oil Composition and Physical Properties................................43 1.20.2 Genetically Modified Palm Oil.........................................................47 1.21 Coconut Oil....................................................................................................48 1.21.1 Coconut Oil Composition and Physical Properties...........................48 1.22 Palm Kernel Oil.............................................................................................50 1.22.1 Palm Kernel Oil Composition and Physical Properties.................... 51 1.23 Lard................................................................................................................52 1.23.1 Lard Physical Properties and Composition.......................................53 1.24 Tallow.............................................................................................................55 1.24.1 Tallow Physical Properties and Composition...................................56 1.25 Milk Fat..........................................................................................................58 1.25.1 Milk Fat Physical Properties and Composition................................58 1.26 Menhaden Oil.................................................................................................60 1.27 Single Cell Oils..............................................................................................64 1.27.1 Microalgae Oils................................................................................64 1.27.2 Fungal Oil.........................................................................................65 References............................................................................................................66 2Chapter Fats and Oils Processing...........................................................................................73 2.1 Introduction....................................................................................................73 2.2 Fats and Oils Recovery.................................................................................. 74 2.2.1 Oilseed Extraction............................................................................ 74 2.2.1.1 Expeller or Screw Press Extraction...................................76 2.2.1.2 Prepress Solvent Extraction...............................................77 2.2.1.3 Direct Solvent Extraction..................................................77 2.2.2 Oil-Bearing Fruit Extraction.............................................................78 2.2.2.1 Olive Oil Extraction..........................................................78 2.2.2.2 Palm Oil Extraction...........................................................78 2.2.3 Animal Fat Recovery........................................................................79 2.2.3.1 Wet Rendering...................................................................79 2.2.3.2 Dry Rendering...................................................................79 2.3 Refining Systems............................................................................................80 2.4 Physical Refining...........................................................................................80
  6. 6. Contents vii 2.5 Refining Pretreatment....................................................................................83 2.5.1 Water Degumming............................................................................84 2.5.2 Acid Degumming.............................................................................85 2.5.3 Dry Degumming...............................................................................86 2.5.4 Enzymatic Degumming....................................................................86 2.5.5 Modified Acid Degumming..............................................................87 2.5.6 Membrane Filter Degumming..........................................................87 2.6 Chemical Refining.........................................................................................88 2.6.1 Short-Mix Caustic Refining..............................................................92 2.6.2 Miscella Refining..............................................................................92 2.6.3 Batch Caustic Refining.....................................................................95 2.6.3.1 Dry-Method Batch Refining..............................................95 2.6.3.2 Wet-Method Batch Refining..............................................96 2.6.4 Silica Refining...................................................................................96 2.6.5 Refining Efficiency...........................................................................97 2.6.6 Refining Byproducts.........................................................................98 2.6.6.1 Soapstock Processing........................................................98 2.6.6.2 Hydrated Gums Processing.............................................100 2.7 Prebleaching.................................................................................................100 2.7.1 Procedure........................................................................................ 101 2.7.1.1 Batch Atmospheric.......................................................... 101 2.7.1.2 Batch Vacuum................................................................. 101 2.7.1.3 Continuous Vacuum........................................................ 101 2.7.2 Bleaching Agents............................................................................ 103 2.7.2.1 Natural Bleaching Earth.................................................. 103 2.7.2.2 Activated Bleaching Earth.............................................. 103 2.7.2.3 Reuse Spent Bleaching Earth..........................................104 2.7.2.4 Activated Carbon.............................................................104 2.7.2.5 Silica Adsorbent.............................................................. 105 2.7.3 Bleaching Earth Dosage................................................................. 105 2.7.4 Temperature....................................................................................106 2.7.5 Time................................................................................................107 2.7.6 Moisture..........................................................................................107 2.7.7 Filtration..........................................................................................108 2.7.8 Bleaching Byproduct......................................................................109 2.8 Hydrogenation.............................................................................................. 110 2.8.1 Operating Variables........................................................................ 113 2.8.1.1 Temperature..................................................................... 113 2.8.1.2 Pressure........................................................................... 113 2.8.1.3 Agitation.......................................................................... 114 2.8.1.4 Catalyst Level.................................................................. 114 2.8.1.5 Catalyst Type................................................................... 114 2.8.1.6 Catalyst Poisons.............................................................. 115
  7. 7. viii Contents 2.8.1.7 Catalyst Reuse................................................................. 116 2.8.1.8 Source Oils...................................................................... 116 2.8.2 Hydrogenation Systems................................................................... 116 2.8.3 Hydrogenation Control.................................................................... 118 2.8.4 Hydrogenated Basestock System.................................................... 119 2.9 Interesterification.........................................................................................122 2.9.1 Chemical Rearrangement Catalyst.................................................124 2.9.2 Endpoint Control.............................................................................126 2.9.2.1 Melting Point...................................................................126 2.9.2.2 Fiber Optic Spectrometer Monitoring.............................126 2.9.2.3 Solids Fat Index...............................................................127 2.9.2.4 Differential Scanning Calorimetry.................................127 2.9.2.5 Glyceride Compositional Analysis..................................128 2.9.3 Random Chemical Interesterification Processes............................128 2.9.4 Directed Chemical Interesterification Process...............................130 2.9.5 Enzymatic Interesterification.......................................................... 131 2.9.6 Interesterified Fats and Oils Applications...................................... 132 2.10 Winterization................................................................................................ 133 2.10.1 Classical Winterization Process..................................................... 133 2.10.2 Winterization Principle...................................................................134 2.10.2.1 Source Oil Composition.................................................. 135 2.10.2.2 Cooling Rate.................................................................... 135 2.10.2.3 Crystallization Temperature............................................ 135 2.10.2.4 Agitation Rate................................................................. 135 2.10.2.5 Crystallization Time........................................................136 2.10.3 Solvent Winterization.....................................................................136 2.10.4 Winterization Process Control Procedures..................................... 137 2.10.5 Winterization Applications.............................................................138 2.11 Dewaxing..................................................................................................... 139 2.11.1 Dewaxing Process Control............................................................. 140 2.11.2 Dewaxing Applications................................................................... 140 2.12 Fractionation................................................................................................ 140 2.12.1 Dry Crystal Fractionation............................................................... 142 2.12.2 Detergent Fractionation.................................................................. 142 2.12.3 Solvent Fractionation...................................................................... 143 2.13 Postbleaching...............................................................................................144 2.14 Cholesterol Stripping Process...................................................................... 145 2.15 Esterification or Alcoholysis........................................................................ 146 2.15.1 Mono- and Diglycerides................................................................. 146 2.15.1.1 Monoglyceride Derivatives............................................. 148 2.15.2 Polyglycerol Ester...........................................................................150 2.15.3 Propylene Glycol Monoester........................................................... 152 2.16 Blending....................................................................................................... 152 2.17 Deodorization............................................................................................... 153 2.17.1 Operating Variables........................................................................154
  8. 8. Contents ix 2.17.1.1 Vacuum............................................................................154 2.17.1.2 Temperature.....................................................................154 2.17.1.3 Stripping Steam............................................................... 155 2.17.1.4 Retention Time................................................................156 2.17.2 Deodorization Systems...................................................................156 2.17.2.1 Batch................................................................................156 2.17.2.2 Semicontinuous Deodorization....................................... 157 2.17.2.3 Continuous Deodorization.............................................. 158 2.17.3 Deodorizer Heating Systems.......................................................... 159 2.17.4 Deodorization Process Control.......................................................160 2.17.5 Deodorizer Distillated.................................................................... 161 2.18 Finished Fats and Oils Handling.................................................................164 2.18.1 Protection against Oxidative Deterioration....................................164 2.18.1.1 Nitrogen Blanketing........................................................164 2.18.1.2 Temperature Control....................................................... 165 2.18.1.3 Light Control................................................................... 166 2.18.1.4 Storage Time................................................................... 166 2.18.1.5 Antioxidant Addition....................................................... 166 2.18.1.6 Synergistic Antioxidant Mixtures................................... 168 2.18.2 Protection against Contamination.................................................. 169 2.19 Plasticization................................................................................................ 170 2.19.1 Plasticity of Edible Fats and Oils.................................................... 170 2.19.1.1 Product Composition....................................................... 170 2.19.1.2 Crystal Size..................................................................... 171 2.19.1.3 Supercooling.................................................................... 171 2.19.1.4 Mechanical Working....................................................... 172 2.19.1.5 Gas Incorporation............................................................ 172 2.19.2 Solidification Apparatus Evolutions............................................... 172 2.19.3 Shortening Plasticization Process................................................... 174 2.19.4 Liquid Shortening Crystallization.................................................. 176 2.19.5 Margarine Plasticization Process.................................................... 177 2.19.5.1 Stick Margarine............................................................... 180 2.19.5.2 Soft-Tub Margarine......................................................... 180 2.19.5.3 Whipped-Tub Margarine................................................. 181 2.19.5.4 Liquid Margarine............................................................ 181 2.19.5.5 Industrial Margarines...................................................... 182 2.19.6 Tempering....................................................................................... 182 2.19.6.1 Quick Tempering............................................................. 183 2.20 Flaking......................................................................................................... 185 2.20.1 Chill Rolls....................................................................................... 186 2.20.2 Flake Crystallization....................................................................... 186 2.20.3 Flaking Conditions......................................................................... 186 2.21 Powdered and Beaded Fats.......................................................................... 187 2.21.1 Spray Cooling................................................................................. 188
  9. 9. x Contents 2.21.2 Flake Grinding................................................................................ 188 2.21.3 Spray Flaking and Grinding........................................................... 188 2.22 Salad and Cooking Oils Packaging.............................................................. 189 2.23 Bulk Oil Shipments...................................................................................... 189 2.23.1 Contamination................................................................................190 2.23.2 Overheating.....................................................................................190 2.23.3 Air Exposure...................................................................................190 References.......................................................................................................... 191 3Chapter Fats and Oils Analysis............................................................................................197 3.1 Introduction..................................................................................................197 3.2 Nonfatty Impurities...................................................................................... 198 3.2.1 Moisture Analysis........................................................................... 198 3.2.1.1 Hot Plate Method............................................................ 198 3.2.1.2 Air Oven Method............................................................199 3.2.1.3 Vacuum Oven Method.....................................................199 3.2.1.4 Karl Fisher Method.........................................................199 3.2.1.5 Skillet Moisture...............................................................199 3.2.2 Impurities Analysis.........................................................................200 3.2.2.1 Insoluble Impurities.........................................................200 3.2.2.2 Filterable Impurities (Standard Disk Method)................200 3.2.2.3 Turbidimeter Impurities..................................................200 3.2.3 Trace Metals Analysis.....................................................................201 3.2.4 Soap Analysis..................................................................................201 3.3 Melting, Solidification, and Consistency.....................................................201 3.3.1 Melting Point Analysis....................................................................202 3.3.1.1 Capillary Melting Point...................................................202 3.3.1.2 Softening Point................................................................202 3.3.1.3 Slipping Point..................................................................202 3.3.1.4 Wiley Melting Point........................................................203 3.3.1.5 Mettler Dropping Point...................................................203 3.3.2 Solid–Liquid Relationships.............................................................203 3.3.2.1 Solids Fat Index...............................................................204 3.3.2.2 Solids Fat Content...........................................................204 3.3.2.3 Differential Scanning Calorimetry Fat Solids Content............................................................................206 3.3.3 Solidification Analysis....................................................................207 3.3.3.1 Titer.................................................................................207 3.3.3.2 Quick Titer......................................................................207 3.3.3.3 Congeal Point..................................................................207 3.3.3.4 Cloud Point......................................................................208 3.3.3.5 Cold Test..........................................................................208 3.3.3.6 Chill Test.........................................................................208
  10. 10. Contents xi 3.3.4 Consistency Analysis......................................................................208 3.3.4.1 Consistency Ratings........................................................209 3.3.4.2 Penetrations.....................................................................209 3.4 Composition Analysis.................................................................................. 210 3.4.1 Saponification Value....................................................................... 211 3.4.2 Iodine Value.................................................................................... 211 3.4.3 Refractive Index.............................................................................. 212 3.4.4 Fatty Acid Composition.................................................................. 213 3.4.5 Calculated Iodine Value.................................................................. 214 3.4.6 Glyceride Structure......................................................................... 215 3.4.7 Emulsifier Analysis......................................................................... 215 3.4.8 Antioxidant Analysis...................................................................... 216 3.4.9 Tocopherol Analysis....................................................................... 216 3.5 Flavor, Rancidity, and Stability.................................................................... 217 3.5.1 Flavor Analysis............................................................................... 217 3.5.1.1 Sensory Evaluations........................................................ 218 3.5.1.2 Volatile Flavor Analysis.................................................. 219 3.5.2 Rancidity Analysis.......................................................................... 219 3.5.2.1 Peroxide Value................................................................. 219 3.5.2.2 Anisidine Value...............................................................220 3.5.2.3 Free Fatty Acid and Acid Value......................................220 3.5.2.4 Smoke Point..................................................................... 221 3.5.3 Stability Analysis............................................................................ 221 3.5.3.1 Active Oxygen Method...................................................222 3.5.3.2 Oil Stability Index...........................................................223 3.5.3.3 Schaal Oven Test.............................................................223 3.5.3.4 Pastry Flavor Test............................................................224 3.6 Color and Appearance.................................................................................224 3.6.1 Color................................................................................................225 3.6.1.1 Wesson Color Method.....................................................225 3.6.1.2 Lovibond (British Standard)...........................................225 3.6.1.3 Spectrophotometric Color Method for Oils....................226 3.6.1.4 Automatic Tintometers....................................................226 3.6.1.5 FAC (Fatty Acid Committee) Method.............................226 3.6.1.6 Gardner Color..................................................................227 3.6.1.7 Chlorophyll......................................................................227 3.6.1.8 Coloring Agents Determination......................................227 3.6.2 Appearance.....................................................................................227 3.6.2.1 Product Appearance Ratings...........................................227 3.7 Refining and Bleaching................................................................................228 3.7.1 Refining Loss..................................................................................228 3.7.2 Neutral Oil and Loss.......................................................................229 3.7.3 Bleaching Analysis.........................................................................229 3.8 Performance Testing....................................................................................229 3.8.1 Creaming Volume...........................................................................230
  11. 11. xii Contents 3.8.2 Pound Cake Test............................................................................. 231 3.8.3 Icing Volume................................................................................... 231 3.8.4 White Layer Cakes..........................................................................232 3.8.5 Crème Filling Test..........................................................................232 3.8.6 Cake Mix Evaluation......................................................................233 3.8.7 Puff Pastry Testing..........................................................................233 3.8.8 Restaurant Deep-Fat Frying Evaluation.........................................233 3.8.9 Ice Cream Bar Coating Evaluation.................................................234 3.9 Nonstandardized Methods...........................................................................234 References..........................................................................................................260 4Chapter Fats and Oils Formulation......................................................................................263 4.1 Introduction..................................................................................................263 4.2 Oils and Fats Characteristics.......................................................................265 4.2.1 Saturated Fatty Acids......................................................................265 4.2.1.1 Short-Chain Fatty Acids..................................................267 4.2.1.2 Medium-Chain Fatty Acids.............................................267 4.2.1.3 Long-Chain Fatty Acids..................................................268 4.2.2 Unsaturated Fatty Acids.................................................................269 4.2.2.1 Monounsaturated Fatty Acids.........................................269 4.2.2.2 Polyunsaturated Fatty Acids...........................................270 4.2.3 Isomerized Fatty Acids...................................................................273 4.2.3.1 Positional Isomers...........................................................273 4.2.3.2 Trans Fatty Acids............................................................273 4.2.3.3 Conjugated Linoleic Fatty Acid (CLA)........................... 274 4.3 Palatability................................................................................................... 275 4.3.1 Oxidation........................................................................................276 4.3.1.1 Flavor Reversion..............................................................280 4.3.1.2 Antioxidants....................................................................281 4.3.2 Hydrolysis.......................................................................................283 4.3.3 Mouth Feel......................................................................................283 4.4 Physical Characteristics...............................................................................285 4.4.1 Fat Crystal Habit.............................................................................285 4.4.2 Fat Plasticity....................................................................................288 4.4.3 Solid–Liquid Relationships.............................................................289 4.4.3.1 Hydrogenation.................................................................289 4.4.3.2 Random Interesterification.............................................. 291 4.4.3.3 Directed Interesterification.............................................295 4.4.3.4 Fractionation....................................................................295 4.5 Nutritional Considerations...........................................................................297 4.5.1 Nutritional Facts Panel....................................................................298 4.5.2 Health Claims.................................................................................299 4.5.3 2005 Dietary Guidelines for Americans.........................................300
  12. 12. Contents xiii 4.5.4 Package Ingredient Statement.........................................................300 4.6 Basestock System.........................................................................................301 4.7 Solids–Liquids Characteristics....................................................................302 4.7.1 Wide Plastic-Range Fats and Oils Products...................................305 4.7.2 Steep Solid Fat Index Slopes...........................................................308 4.7.3 Liquid Opaque or Pumpable Products............................................ 311 4.8 Emulsification.............................................................................................. 312 4.8.1 Mono- and Diglycerides................................................................. 314 4.8.2 Propylene Glycol Esters.................................................................. 316 4.8.3 Sorbitan Esters................................................................................ 317 4.8.4 Polysorbate Fatty Acid Esters......................................................... 317 4.8.5 Polyglycerol Esters.......................................................................... 318 4.8.6 Lactated Esters................................................................................ 318 4.8.7 Lecithin........................................................................................... 319 4.8.8 Emulsifier Selection Methods.........................................................320 4.8.8.1 Hydrophilic/Lipophilic Balance System.........................320 4.8.8.2 Emulsifier Functionality Traits........................................323 4.8.8.3 Emulsifier Selection Procedure.......................................324 4.9 Product Development...................................................................................325 4.9.1 Application Product Development..................................................325 4.9.2 Analytical Development.................................................................327 4.9.2.1 Solids Fat Index Calculations..........................................327 4.9.3 Triglyceride Replication..................................................................328 4.10 Source Oils and Fats Interchangeability...................................................... 333 4.11 Reduced Trans Fatty Acid Formulation.......................................................334 4.12 Essential Fatty Acid Fortification................................................................ 337 4.12.1 Essential Fatty Acid Sources.......................................................... 337 4.12.2 Omega-3 Fortified Products............................................................338 References.......................................................................................................... 339 5Chapter Shortening Types....................................................................................................347 5.1 Introduction..................................................................................................347 5.1.1 Historical Background....................................................................347 5.1.2 Source Oils...................................................................................... 351 5.1.3 Shortening Product Forms.............................................................. 355 5.2 Plasticized Shortening Applications............................................................ 355 5.3 Liquid Shortening Applications................................................................... 357 5.4 Flakes, Chips, and Powdered Shortening Applications............................... 358 References.......................................................................................................... 359 6Chapter Baking Shortenings................................................................................................. 361 6.1 Introduction.................................................................................................. 361
  13. 13. xiv Contents 6.2 All-Purpose Shortenings..............................................................................363 6.3 Emulsified All-Purpose Shortening.............................................................368 6.4 Retail Cake Mix Shortenings.......................................................................370 6.5 Specialty Bakery Cake Shortenings............................................................373 6.6 Liquid Cake Shortening............................................................................... 374 6.7 Icing and Filling Shortenings....................................................................... 376 6.8 Icing Stabilizers...........................................................................................378 6.9 Bread Shortening.........................................................................................379 6.10 Liquid Bread Shortenings............................................................................ 381 6.11 Sweet Yeast-Raised Dough Shortenings......................................................383 6.12 Cookie Shortenings......................................................................................384 6.13 Cookie Filler Shortenings............................................................................384 6.14 Pie Crust Shortenings...................................................................................386 6.15 Biscuit Shortenings......................................................................................387 6.16 Danish Pastry Roll-In Shortenings..............................................................389 6.17 Puff Paste Roll-In Shortening......................................................................392 6.18 Shortening Chips..........................................................................................394 6.19 Cracker Shortenings.....................................................................................395 References..........................................................................................................396 7Chapter Frying Shortenings.................................................................................................399 7.1 Introduction..................................................................................................399 7.2 Frying Shortening Additives........................................................................402 7.3 Selection of Frying Shortening....................................................................404 7.3.1 Product Characteristics...................................................................405 7.3.2 Frying Life......................................................................................405 7.3.3 Shelf Life........................................................................................406 7.4 Foodservice Deep-Fat Frying Shortening Applications..............................407 7.4.1 Foodservice All-Purpose Shortening.............................................409 7.4.2 Animal–Vegetable Blended Frying Shortening.............................. 410 7.4.3 Heavy-Duty Vegetable Frying Shortenings.................................... 410 7.4.4 Liquid Frying Shortenings.............................................................. 411 7.4.5 Trait-Enhanced Vegetable Oils....................................................... 412 7.5 Foodservice Pan and Grill Shortenings....................................................... 414 7.6 Bakery Frying Shortening Applications...................................................... 416 7.6.1 Cake Donut Shortenings................................................................. 417 7.6.2 Yeast-Raised Fried Products........................................................... 419 7.6.3 Fried-Pie Shortenings..................................................................... 419 7.7 Snack Frying Shortening Applications........................................................420 7.7.1 Nut Meats Oil Roasting..................................................................422 References..........................................................................................................422
  14. 14. Contents xv 8Chapter Dairy Analog Shortenings......................................................................................425 8.1 Introduction..................................................................................................425 8.2 Nondairy Creamer.......................................................................................426 8.3 Whipped Topping.........................................................................................429 8.4 Cheese Analog............................................................................................. 431 8.5 Frozen Dessert or Mellorine........................................................................ 432 8.6 Sour Cream Analog and Dip Bases............................................................. 433 8.7 Fluid Milk Analogs......................................................................................434 8.8 Sweetened Condensed Milk Analogs..........................................................434 References..........................................................................................................436 9Chapter Household Shortenings........................................................................................... 437 9.1 Introduction.................................................................................................. 437 9.2 Household Shortening Development............................................................ 437 9.3 Household Shortening Product Requirements............................................. 439 9.4 Household Shortening Formulation.............................................................440 9.5 Household Shortening Plasticization...........................................................444 9.6 Household Shortening Packaging................................................................444 References..........................................................................................................445 1Chapter 0 Margarine................................................................................................................447 10.1 Introduction..................................................................................................447 10.2 Margarine Development...............................................................................447 10.3 Margarine Formulation................................................................................ 453 10.3.1 Milk Products or Protein................................................................ 453 10.3.2 Emulsifiers......................................................................................454 10.3.3 Flavoring Materials.........................................................................454 10.3.4 Preservatives................................................................................... 455 10.3.5 Vitamins and Color......................................................................... 455 10.3.6 Supplements for Health Claims......................................................456 10.3.7 Margarine Oils and Fats.................................................................456 10.4 Low-Fat Margarine or Spread...................................................................... 457 10.5 Consumer Margarine Oil Formulations....................................................... 459 10.5.1 Margarine Oil Formulations with Hydrogenated Oils.................... 459 10.5.2 Margarine Oil Formulation with Interesterified Oils..................... 461 10.5.3 Margarine Oil Formulation with Fractionated Oils........................464 10.5.4 Margarine Oil Formulation with Unmodified Oils........................464
  15. 15. xvi Contents 10.6 Industrial Margarine Formulations..............................................................465 10.7 Margarine and Spread Preparation..............................................................466 10.7.1 Stick Margarine or Spread..............................................................467 10.7.2 Soft Tub Margarine or Spread........................................................468 10.7.3 Whipped Tub Margarine or Spread................................................469 10.7.4 Liquid Margarine............................................................................469 10.7.5 Industrial Margarines or Spreads...................................................469 References.......................................................................................................... 470 1Chapter 1 Liquid Oils.............................................................................................................. 473 11.1 Introduction.................................................................................................. 473 11.2 Development of Liquid Oils......................................................................... 474 11.3 Cooking and Salad Oil Sources................................................................... 476 11.4 Retail Consumer Oils................................................................................... 479 11.5 Industrial Salad Oil Applications................................................................. 481 11.6 Mayonnaise..................................................................................................482 11.6.1 Mayonnaise Ingredients..................................................................483 11.6.1.1 Salad Oil..........................................................................483 11.6.1.2 Vinegar............................................................................485 11.6.1.3 Eggs.................................................................................485 11.6.1.4 Flavoring Ingredients......................................................485 11.6.2 Mayonnaise Processing...................................................................486 11.7 Spoonable Salad Dressing............................................................................487 11.8 Pourable Salad Dressings.............................................................................488 11.8.1 French Dressing..............................................................................489 11.9 High-Stability Oils.......................................................................................490 11.9.1 Processed High-Stability Oils........................................................490 11.9.2 Plant Breeding................................................................................490 11.9.3 High-Stability Oil Applications...................................................... 491 References..........................................................................................................492 1Chapter 2 Quality Management..............................................................................................495 12.1 Introduction..................................................................................................495 12.2 Operating Standards....................................................................................496 12.3 Specifications...............................................................................................496 12.3.1 Specifications Format.....................................................................497 12.3.2 Ingredient Specifications................................................................499 12.3.2.1 Ingredient Specifications Format.................................... 501 12.3.3 Packaging Specifications................................................................502 12.3.3.1 Packaging Specifications Format....................................503 12.3.4 Product Specifications....................................................................504 12.3.4.1 Product Specifications Format........................................505
  16. 16. Contents xvii 12.3.5 Customer Instruction Specifications...............................................506 12.3.5.1 Customer Instruction Specifications Format...................506 12.3.6 Summary Specifications.................................................................508 12.3.6.1 Summary Specifications Format.....................................508 12.4 Procedures....................................................................................................509 12.4.1 Procedures Format..........................................................................509 12.4.2 Quality Procedures.........................................................................509 12.4.2.1 Complaint Handling Procedure...................................... 510 12.4.2.2 Product Recall Procedure................................................ 511 12.4.2.3 Product Identification Procedures................................... 513 12.4.2.4 Specification Change Requisition................................... 515 12.4.2.5 New Product Approval Procedure.................................. 517 12.4.2.6 Weight Control Program................................................. 518 12.4.2.7 Quality Cost System........................................................ 518 12.4.2.8 Label Approval Procedure..............................................520 12.5 Methods........................................................................................................ 521 12.5.1 Methods Format..............................................................................522 12.6 Process Control Overview...........................................................................524 12.7 Crude Fats and Oils Process Control...........................................................526 12.8 Refining Process Control.............................................................................527 12.9 Prebleaching Process Control......................................................................530 12.10 Modification Processes................................................................................ 532 12.10.1 Hydrogenation Process Control...................................................... 533 12.10.2 Interesterification Process Control.................................................. 535 12.10.2.1 Random Interesterification Using Chemical Catalyst..... 536 12.10.2.2 Random Interesterification Using Enzyme Catalyst....... 538 12.10.3 Fractionation Process Control......................................................... 539 12.10.3.1 Winterization Process Control........................................540 12.10.3.2 Dewaxing Process Control..............................................540 12.11 Postbleach Process Control..........................................................................542 12.12 Blending Process Control.............................................................................544 12.13 Deodorization Process Control....................................................................544 12.14 Bulk Shipment Process Control...................................................................546 12.15 Plasticized Shortening Packaging Process Control.....................................547 12.16 Liquid Shortening Packaging Process Control............................................550 12.17 Liquid Oils Packaging Process Control....................................................... 552 12.18 Shortening Flake Process Control Standards..............................................554 12.19 Margarine and Spread Process Control Standards......................................556 References.......................................................................................................... 559 1Chapter 3 Troubleshooting...................................................................................................... 561 13.1 Introduction.................................................................................................. 561 13.2 Process Troubleshooting..............................................................................563
  17. 17. xviii Contents 13.2.1 Vegetable Oil Extraction.................................................................563 13.2.2 Meat Fat Rendering.........................................................................566 13.2.3 Crude Oil Storage...........................................................................566 13.2.4 Degumming.................................................................................... 570 13.2.5 Caustic Oil Refining: Primary Centrifuge...................................... 571 13.2.6 Oil Refining: Water Wash............................................................... 574 13.2.7 Oil Refining: Vacuum Drying......................................................... 575 13.2.8 Prebleaching.................................................................................... 575 13.2.9 Hydrogenation................................................................................. 578 13.2.10 Interesterification............................................................................580 13.2.11 Postbleaching.................................................................................. 581 13.2.12 Winterization..................................................................................582 13.2.13 Dewaxing........................................................................................584 13.2.14 Esterification...................................................................................585 13.2.15 Blending..........................................................................................588 13.2.16 Deodorization.................................................................................589 13.2.17 Antioxidant Addition......................................................................598 13.2.18 Bulk Railroad Car or Truck Loading.............................................600 13.2.19 Oil Filling and Packaging...............................................................603 13.2.20 Packaged Liquid Oils: Storage and Transportation........................604 13.2.21 Shortening Packaging.....................................................................605 13.2.22 Liquid Opaque Shortenings............................................................ 611 13.2.23 Shortening Flakes........................................................................... 614 13.2.24 Packaged Shortening: Storage and Transportation......................... 621 13.2.25 Quality Control Laboratory............................................................622 13.2.26 Edible Fats and Oils: Organoleptic Evaluations.............................624 13.2.27 Edible Fats and Oils Formulation...................................................627 13.2.28 Edible Fats and Oils: Processed Oil Storage..................................629 13.3 Shortening Applications...............................................................................629 13.3.1 Baking Shortening..........................................................................629 13.3.2 Frying Shortenings.........................................................................633 13.4 Margarine and Spread Products...................................................................644 13.5 Quality Management....................................................................................649 References..........................................................................................................656 Index.......................................................................................................................659
  18. 18. xix Third Edition Preface The objective of this edition remains the same as the two previous editions — to provide a practical reference for fats and oils processing and formulation for effec- tive food processor, foodservice, and household applications. It is designed to be an information source for personnel and students of fats and oils processing as well as the personnel of the user industries. Most of the additions for this edition are related to nutrition. Dietary recommendations for fat and fatty acids continue to evolve as a better understanding of the role of dietary lipids in human health is gained. Processing and formulation techniques are reviewed to help determine how to achieve the most favorable nutritional characteristics while maintaining function- ality for the various food applications. This book was designed to delve into the technical aspects that control the functional characteristics of fats and oils products, how these characteristics can be purified and/or modified to perform as needed, and the processing control nec- essary to produce these characteristics on a continuing uniform basis at the most economical cost. Applications development and quality management begin when the customer’s requirements are identified and continue through product design, sales, manufacturing, product costing, delivery, and service. A thorough understanding of the functions and properties of the various fats and oils products is the basic key to formulating for the desired attributes. Chapters dealing with the raw materials or source oils and fats, process performance and availability, evaluation techniques, formulation attributes, historic changes, and food applications were designed to pro- vide the elements of formulation. Control of oil processing requires consideration of the problems associated with the properties of the raw materials and each process as well as the real and potential customer problems with the ingredients use. A qual- ity management chapter was included to help establish when a system is in or out of control, and a troubleshooting chapter was included to help identify solutions to problems or at least stimulate the thought process for solving the problem. Fats and oils user industries have a vested interest in the development, pro- cessing, and quality control for shortening, margarine, and liquid oil products. The properties of the fat and oil ingredients are key elements in the performance and nutritional characteristics of most prepared food products. Fats and oils products for general use, specific applications, processes, nutritional contributions, and other functionalities have been successful due to the cooperative development efforts between fats and oil processors and food processors. Therefore, this text focuses on the formulation of fats and oils ingredients for food applications for food processor, foodservice, and household use. Information and materials for this book have been gathered over the past 45 years from patents, trade journals, personal experience, and exposure to many of the industry’s recognized leaders and other individuals who have taken a genuine pride in their work and the product produced.
  19. 19. 1 1Chapter Raw Materials 1.1  Introduction Fats and oils are the raw materials for liquid oils, shortenings, margarines, and other specialty or tailored products that are functional ingredients in food products prepared by food processors, restaurants, and in the home. Fats and oils have been used for food and a variety of other applications since prehistoric times, as they were easily isolated from their source. For example, fatty tissues from animals lib- erate free-floating fats on being boiled, whereas oil can be pressed from olives and oilseeds. Fats and oils found utility because of their unique properties. These ingre- dients were found to add flavor, lubricity, texture, and satiety to foods. They have also been found to have a major role in human nutrition. Fats and oils are the highest energy source of the three basic foods (carbohydrates, proteins, and fats), carriers for oil soluble vitamins, and many contain fatty acids essential for health that are not manufactured by the human body. Fats and oils occur naturally in a wide range of sources, with each source pro- viding a separate and distinctive material. Hundreds of seeds and fruits contain oil, all animals produce fat, and marine sources also provide oils; however, only a few of these sources are of economic importance. All edible fats and oils are water- insoluble substances that consist predominantly of glyceryl esters of fatty acids, or triglycerides, with some nonglyceridic materials present in small or trace quantities. The terms fats and oils are used interchangeably, and the choice of terms is usually based on the physical state of the material at ambient temperature and tradition. Generally, fats appear solid at ambient temperatures and oils appear liquid. In the final analysis, it is the chemical composition that defines the characteristics of the individual fat or oil, which, in turn, determines the suitability of this ingredient in various processes and applications.
  20. 20. 2 Fats and Oils: Formulating and Processing for Applications 1.2  Sources of Fats and Oils Humans have survived as hunters and gatherers for a majority of their known existence on Earth. It was only during the past 10,000 years that they learned to domesticate plants and animals. During this period, the evolution of cultivated plants has been shaped to the needs of modern humans. Today’s agricultural crops are man- kind’s creation. Humans cannot survive without them, nor can the crops that have been developed survive without our care. The combined largest source of vegetable oils is the seeds of annual plants grown in relatively temperate climates. Most of these annual plants not only are cultivated as a source of oil, but are also utilized as protein-rich foods. A second source of vegetable oil is oil-bearing trees. Olive, coconut, and palm oils are extracted from the fruit pulp rather than the seed of the fruit. Palm also has seeds, which provide palm kernel oil. All of the oil-bearing tree fruits require a rela- tively warm climate (i.e., tropical for coconut and palm and a warm climate for olive trees). Most of the oil-bearing tree fruits and kernels provide the highest oil yields. Oil seeds are obtained from annual plants that must be replanted each year, whereas fruit oils are harvested from trees with long life spans. Olive trees are the most hardy and can survive to be several hundred years old. Coconut trees start to bear fruit after 5 to 6 years and their life expectancy is as long as 60 years. Palm trees start to bear fruit after 4 to 5 years and continue to do so for another 20 years. Edible meat fats are supplied almost entirely by three kinds of domesticated ani- mals: lard from pigs, tallow from cattle and sheep, and milk fat or butter from cows. These animals are raised in the greatest quantities where they thrive the best — in temperate climates. Animal husbandry has evolved to the stage that these domestic animals require not only a temperate climate, but also intensive agriculture to pro- vide a plentiful supply of foodstuffs to produce the desired quality and quantity. 1.3  VEGETABLE OIL YIELDS Fats and oils are renewable resources. The achievements of agriculture and plant cultivation have made it possible to exceed the demand resulting from world popula- tion growth. The major vegetable oil seeds and fruits utilized for edible purposes are listed in Table 1.1 with their typical oil contents, yield per acre of land, and major producing areas.1-3 Palm is unparalleled in oil yield. The palm oil yield of palm trees is 3150 to 3330 pounds per acre, and an additional yield of 350 to 370 pounds per acre of palm kernel oil is obtained from the same fruit bunch. Palm trees yield almost 10 times the soybean oil yield per acre. Most oil seeds are annual crops, and the harvest is seasonal; however, palm oil is a perennial crop with two crops produced per year. Coconut, also with a high oil content and yield, requires 9 to 12 months to mature, but fruit is available each month of the year. Olives mature annually and are the most delicate fruit; extraction must be performed as soon as possible to obtain quality oil. Olives have the lowest yield per acre of all the oils evaluated, even though their
  21. 21. Raw Materials 3 oil content is about equivalent to cottonseed and much higher than corn germ. The production of one quart of olive oil requires 1300 to 2000 olives. Three of the four tree oils have the highest oil contents, but soybean, an annual oil seed crop with low oil content, still provides a large part of the vegetable oil production in the world. Corn, with the lowest oil content, is grown in large enough quantities to be the third most utilized vegetable oil in the United States. Canola, an Table 1.1  Vegetable Oils: Oil Content, Yield, and Producing Areas Oil Source Oil Content, % Oil Yield, Lbs/Acre Producing Areas Oilseeds:   Canola 40–45 647–728 Canada, China, India, France, Austria, United Kingdom, Germany, Poland, Belgium, Italy, Luxembourg, Republic of Ireland, Greece, Portugal, Spain, Denmark, Czechoslovakia, United States   Corn 3.1–5.7 215–390 United States, Mexico, Canada, Japan, China, Brazil, South Africa, Argentina, Russia, Commonwealth of Independent States (CIS), Belgium, France, Italy, Germany, Spain, United Kingdom   Cottonseed 18–20 185–210 China, Russia, United States, India, Pakistan, CIS, Brazil, Egypt, Turkey, Australia   Peanut 45–50 1384–1538 China, India, Nigeria, United States, Senegal, South Africa, Argentina  Safflower 30–35 545–635 China, India, United States, Spain, Portugal  Soybean 18–20 456–506 United States, Brazil, Argentina, China, India, Paraguay, Bolivia  Sunflower 35–45 419–539 Russia, Argentina, CIS, Austria, France, Italy, Germany, Spain, United States, United Kingdom   Tree fruits and kernels:   Coconut 65–68 350–370 Philippines, Indonesia, India, Mexico, Sri Lanka, Thailand, Malaysia, Vietnam, Mozambique, New Guinea, Ivory Coast  Olive 15–35 90–260 Spain, Italy, Greece, Tunisia, Turkey, Morocco, Portugal, Syria, Algeria, Yugoslavia, Cyprus, Egypt, Israel, Libya, Jordan, Lebanon, Argentina, Chile, Mexico, Peru, United States, Australia   Palm 45–50 3150–3330 Malaysia, Indonesia, China, Philippines, Pakistan, Mexico, Bangladesh, Columbia, Ecuador, Nigeria, Ivory Coast   Palm kernel 44–53 350–370 Malaysia, Indonesia, China, Philippines, Pakistan, Mexico, Bangladesh, Columbia, Ecuador, Nigeria, Ivory Coast
  22. 22. 4 Fats and Oils: Formulating and Processing for Applications annual oil seed crop developed and grown for its oil composition, has moved from a virtual unknown to second in oilseed utilization to soybean oil. Canola seed has the second highest oil content and oil yield per acre of all the annual oilseed plants presented in Table 1.1; it is surpassed only by peanut or groundnut oil for oil content and yield. 1.4 AVAILABILITY OF FATS AND OILS An important contributor to the availability of fats and oils is the fact that most fats and oils production is controlled by factors other than the demand. Corn and cottonseed oils are clearly byproducts, whereas soybeans are specifically crushed to meet the demands for meal. Sunflower, canola, and peanut plantings are subsi- dized and controlled by the governments of the major countries producing the oils. Palm kernel oil production is dependent on palm oil requirements, as it is grown in the same fruit bunch. Olive, coconut, and palm oils are all produced from the fruit of trees that have long productive life spans, therefore, their production cannot be adjusted to demand changes from year to year. Animal fats are dependent on meat consumption, and butter output is subject to milk production. Thus, the availability of fats and oils is not geared to demand. Weather is another factor that affects both availability and demand for fats and oils. For example, a hurricane in Malaysia can decrease the oil available on the world market; alternatively, favorable weather in the United States, which produces a soy- bean crop with maximum yields, will increase the available oil for the world market. Other factors that affect world demand are the Russian sunflower crop, African pea- nut crop, South American soybeans and cottonseed oil yields, and so forth. This is a one-world market in which variable inputs affect availability and demand, which, in turn, affect the price structure. 1.5 United States UTILIZATION OF EDIBLE FATS AND OILS Climate and availability certainly influenced the eating habits of our ancestors. Inhabitants of central and northern Europe obtained their edible fats from animals, whereas people in southern Europe, Asia, and Africa acquired their edible oils from vegetable sources. The food products developed in these different regions used the available fats and oils products. Consequently, the cuisine of central and northern European countries developed around the use of solid fats, such as butter, lard, and tallow for breads, pastries, and other baked and fried products. Similarly, the diets of inhabitants from warmer climates were developed around the use of liquid oils for their food products, which include many sauces and dressings.4 These trends appear to continue to be the preference of their descendants. Immigrants to the United States brought their food preferences with them and introduced them to others from different regions of the world. Fats and oils tech- nology has further increased the varied and rich American diet by improvement
  23. 23. Raw Materials 5 of existing products and development of new food products. The North American eating habits that resulted have made the United States a consumer of almost every available fat and oil, but at a different rank order than for world production. Table 1.2 compares the United States and world vegetable oil consumption.3 Soybean oil does not enjoy the dominant position in the world market that it has in the U.S. market. Palm oil has becomes the major source of oil in the world, followed by soybean, rapeseed (canola), and sunflower oil. The American consumer is offered these fats and oils in the form of cooking or salad oils; butter, margarine, or spreads; and shortenings or as an ingredient in a prepared food product. The sources of the major fats and oils used in the United States are listed in Table 1.3, which reviews the annual usage of both animal fats and vegetable oils over the past five decades.3,5,6 These data indicate some distinct trends over the past 55 years: 1. Individual consumption continues to increase 2. A move away from animal fats to vegetable oils 3. Replacement of previously established fats and oils with different source oils 4. Introduction of new vegetable oils 5. The rise and fall of some individual source oils 6. Source oil changes that reflect the results of medical studies 7. Introduction of genetically modified oil seed varieties 8. And more Disappearance of fats and oils in the United States has increased to over four times the levels recorded 55 years ago. This increased usage is due to increases in popula- tion, personal consumption, food waste, and changes in the food preparation methods. The per capita use of visible fats and oils increased by 39.7 pounds during this period, Table 1.2  2004/2005 World Vegetable Oil Consumption Rank With U.S. Usage Without U.S. Usage Consumption, % Order Oil Million lbs Oil Million lbs U.S. World*   1 Palm 72,292 Palm 71,039 4.7 33.1   2 Soybean 69,828 Soybean 51,873 67.8 24.2   3 Canola 34,474 Canola 32,569 7.2 15.2   4 Sunflower 18,678 Sunflower 18,319 1.4 8.5   5 Peanut 11,088 Peanut 10,817 1.0 5.1   6 Cottonseed 10,098 Cottonseed 9,238 3.3 4.3   7 Palm kernel 8,316 Palm kernel 7,787 2.0 3.6   8 Coconut 7,260 Coconut 6,134 4.3 2.9   9 Olive 6,270 Olive 5,756 1.9 2.7 10 Corna 2,483 Corn 798 6.4 0.4  Total 240,787 214,330 100.0 100.0 Notes: a U.S. production only; * without U.S. consumption.
  24. 24. 6 Fats and Oils: Formulating and Processing for Applications confirming an increase in personal usage either from consumption or waste. The changes in the food fats utilized reflect the changing eating habits of Americans in relation to time, place, and frequency of eating. During the periods of high increases, the popularity of convenience and snack foods rose sharply, accompanied by rapid growth in the fast food industry, which relies heavily on deep-fat frying. Fats and oils consumption has been categorized into visible and invisible sources. Visible fats and oils are those isolated from animal tissues, oilseeds, or oil fruits and used for food preparation as shortening, margarine, or liquid oil or for specialty uses. Invisible fats and oils are consumed as part of meats, poultry, eggs, dairy products, fish, fruits, or vegetables and account for approximately 60% of an individual’s fat consumption. The values for pounds per person reported in Table 1.3 are those from visible sources only. A shift from animal fats to vegetable oils began long before 1950. Animal fats dominated the U.S. market until animal fat supply shortages and new process developments helped cottonseed oil gain popularity. In 1950, animal fats were only slightly behind in market share, but 20 years later, in 1970, edible vegetable oils accounted for three fourths of the total and animal fats for only one fourth. This trend has continued, with vegetable oil commanding almost 90% of the U.S. edible oil market in 2005. On a per capita basis, edible vegetable oil consumption increased Table 1.3 U.S. Food Fats and Oils Disappearance and Per Capita Consumption Fats and Oils Millions of pounds Year 1950 1960 1970 1980 1990 2000 2005 Canola 577 1743 1905 Coconut 129 172 788 1032 897 983 1126 Corn 223 310 445 673 1149 1630 1685 Cottonseed 1445 1225 891 523 851 672 860 Olive 79 51 67 58 211 459 514 Palm 1 182 299 256 385 1253 Palm kernel 26 53 94 NR 362 256 529 Peanut 103 62 193 112 197 244 271 Safflower 100 58 122 87 Soybean 1446 3011 6253 9112 12164 16318 17955 Sunflower 64 200 357 359 Lard 2050 1889 1645 1023 825 630 722 Tallow 156 328 518 995 955 1449 1464 Butter 1062 890 860 814 790 1013 1081  Total 6719.0 7992 12036 14705 19492 26261 29810 Consumption Pounds per person Vegetable oils 24.0 26.7 39.0 44.7 52.5 63.0 75.2 Animal fats 21.9 18.5 14.1 12.3 8.5 10.2 10.4  Total 45.9 45.3 53.1 57.0 61.0 73.2 85.6
  25. 25. Raw Materials 7 during the second half of the twentieth century from 24 to 75.2 pounds; meanwhile, animal fats usage fell from 21.9 to 10.4 pounds. During this period, cottonseed oil lost its dominant vegetable oil position to soybean oil, due to cottonseed supply shortages and economics surrounding the shortage. Vegetable oils became dominant mainly because of competitive pricing (first for cottonseed oil and then for soybean oil), increased hydrogenation capacity, consumer preference shifts from butter to margarine, and nutritional concerns. Nutritional issues regarding cholesterol and saturated fats led to the demise of animal fats for food use and helped vegetable oils other than soybean and cottonseed obtain a share of the U.S. market. Canola, corn, olive, sunflower, and safflower oils have all been marketed as oils with more attractive nutritional values, such as lower levels of saturated fat and higher levels of polyunsaturated fat. Now, the 2005 data is beginning to indicate efforts to eliminate trans fatty acids in the diet. Increased usage of palm oil and butter probably indicate efforts by consumers and processors to avoid trans fatty acids. 1.6  CHARACTERIZATION OF FATS AND OILS The chemical and physical properties of fats and oils are largely determined by the fatty acids that they contain and their position within the triacylglycerol molecule. Chemically, all fats and oils are esters of glycerin and fatty acids; never- theless, the physical properties of natural fats and oils vary widely because (1) the proportions of fatty acids vary over wide ranges, and (2) the triacylglycerol struc- tures vary for each individual oil and fat. Fats and oils are commonly referred to as triglycerides because the glycerin molecule has three hydroxyl groups where a fatty acid can be attached. All triglycerides have the same glycerin unit, so it is the fatty acids that contribute the different properties. The fatty acid components are distin- guished in three ways: (1) chain length, (2) number and position of the double bonds, and (3) position of the fatty acids within the glyceride molecule. Variations in these characteristics are responsible for the chemical and physical differences experienced with edible fats and oils. The structure of a fatty acid may be denoted by a systematic name after the nomenclature of its parent hydrocarbon, by the biochemist system, by its common name, or by a convenient shorthand designation showing the number of carbon atoms and the number of double bonds. The fatty-acid carbon-chain lengths vary between 4 and 24 carbon atoms with up to six double bonds. The most prevalent saturated fatty acids are lauric (C-12:0), myristic (C-14:0), palmitic (C-16:0), stearic (C-18:0), arachidic (C-20:0), behenic (C-22:0), and lignoceric (C-24:0). The most important monounsaturated fatty acids are oleic (C-18:1) and erucic (C-22:1). The essential polyunsaturated fatty acids are linoleic (C-18:2), linolenic (C-18:3), EPA (eicosapen- taenoic acid) (C-20:5), and DHA (docosahexaenoic acid) (C-22:6). The triglyceride structure of an edible fat or oil is affected by the fatty acids that are present and the point of attachment of each fatty acid to the glycerin. Triglycerides with three identical fatty acids are called monoacid triglycerides. Triglycerides con- taining more than one type of fatty acid are called mixed triglycerides. A mixed
  26. 26. 8 Fats and Oils: Formulating and Processing for Applications triglyceride containing three different fatty acids has three regioisomeric forms and six stereoisomeric forms, depending on which fatty acid is in the beta or middle posi- tion (sn-2) of the glycerol portion of the molecule and which fatty acids are in the alpha or outer positions (sn-1 and sn-3). The distribution of the fatty acids is consid- ered to be nonrandom when the saturated fatty acids are positioned predominantly in the sn-1 or sn-3 positions and the unsaturated fatty acids are positioned predomi- nantly in the sn-2 position.7 The fatty acid compositions of natural fats and oils vary significantly depending, not only on the plant or animal species, but also within the same species. Among the factors that affect the vegetable oil fatty acid compositions are climate conditions, soil type, growing season, plant maturity, plant health, microbiological conditions, seed location within the flower, and genetic variation of the plant. Animal fat and oil composition varies according to the animal species, diet, health, fat location on the carcass, and maturity.8 1.7 NONGLYCERIDE COMPONENTS OF FATS AND OILS The primary constituents in crude fats and oils are the triglycerides, but they also contain varying amounts of minor components, many of which significantly affect their chemical and physical properties. Exclusive of free fatty acids, crude vegetable oils commonly contain 2% or more nonglyceride substances, and animal fats contain much smaller quantities. These minor components, referred to as the unsaponifiable fraction, consist of phospholipids, tocopherols, sterols, resins, carbohydrates, pesti- cides, proteins, trace metals, and pigments, such as gossypol, carotene, and chloro- phyll. Some, but not all, of the nonglyceride materials are undesirable, therefore, the objective in all edible oil processing is to remove the objectionable impurities with the least possible damage to the desirable constituents. 1.7.1  Phospholipids These compounds are better known to oil processors as phosphatides and are frequently referred to, together with small quantities of carbohydrates and res- ins, as gums, which have adverse effects on product quality and refined oil yield. Phosphatides are emulsifiers and hinder the separation of oil and water phases in the chemical refining process, interfere with effective bleaching, are catalyst poisons, shorten shelf life, and foul equipment surfaces. Phosphatides consist of polyhydric alcohols esterified with fatty acids and phosphoric acid, which is combined with a nitrogen-containing compound. The phosphatides are divided into two catego- ries: hydratable and nonhydratable, depending on the effect that water has on them. The hydratable phosphatides (phosphatidylcholine and phosphatidylinositol) can be separated from the oil phase with water. The nonhydratable phosphatides (phospha- tidic acid and lysophosphatidic acid) and the calcium and magnesium salts of these acids remain in the oil after water degumming. A typical water degumming process will remove the hydratable phosphatides to a level of 200 ppm (parts per million)
  27. 27. Raw Materials 9 phosphorus for soybean and canola oils. Pretreatment of good-quality crude oils with phosphoric or citric acid before refining is successful in removing both nonhy- dratable and hydratable phosphatides to a phosphorus level of approximately 20 to 30 ppm. Two common phosphatides occurring in vegetable oils are the lecithins and cephalins, which may be considered triglycerides that have one fatty acid replaced with phosphoric acid. The gums separated with a water degumming process can be dried for lecithin processing; however, the gums isolated with acid degumming pro- cesses are not suitable for standard lecithin because their phosphatide composition differs and they contain the degumming acid. As indicated in Table 1.4, all the seed oils contain significant quantities of the phosphatides.9-11 1.7.2  Tocopherols and Tocotrienols Tocols, natural antioxidants found in plant-based oils, include four tocopherol and four tocotrienol isomers, each designated as alpha (α), beta (β), gamma (γ), and delta (δ) depending on the number and position of methyl groups on a chromane ring; they also possess vitamin E activity. The tocopherols have a saturated side chain, whereas the tocotrienols have an unsaturated side chain. These antioxidants inhibit lipid oxidation in foods by stabilizing hydroperoxy and other free radicals and their presence has a major effect on oil flavor quality. The antioxidant activity of tocopherols in foods is least for α-tocopherols, while the β- and γ-isomers have inter- mediate activities and the δ-isomer is the most active. Tocotrienols are less effective than their corresponding tocopherols.12 The stability of many vegetable oils has been credited to the presence of these natural antioxidants; however, too high a tocopherol level will enhance oxidation of the unsaturated fatty acids.13 Seed oils are the major sources of tocopherols and there seems to be a direct relationship between the degree Table 1.4 Fats and Oils Nonglyceride Components Fat or Oil Phosphatides % Sterols ppm Cholesterol ppm Tocopherols ppm Tocotrienols ppm Soybean 2.2 ± 1.0 2965 ± 1125 28 ± 7 1293 ± 300 86 ± 86 Canola 2.0 ± 1.0 8050 ± 3230 53 ± 27 692 ± 85 — Corn 1.25 ± 0.25 15050 ± 7100 57 ± 38 1477 ± 183 355 ± 355 Cottonseed 0.8 ± 0.1 4560 ± 1870 68 ± 40 865 ± 35 30 ± 30 Sunflower 0.7 ± 0.2 3495 ± 1055 26 ± 18 738 ± 82 270 ± 270 Safflower 0.5 ± 0.1 2373 ± 278 7 ± 7 460 ± 230 15 ± 15 Peanut 0.35 ± 0.05 1878 ± 978 54 ± 54 482 ± 345 256 ± 218 Olive < 0.1 100 < 0.5 110 ± 40 89 ± 89 Palm 0.075 ± 0.025 2250 ± 250 16 ± 3 240 ± 60 560 ± 140 Tallow < 0.07 1100 ± 300 1100 ± 300 — — Lard < 0.05 1150 ± 50 3500 ± 500 — — Coconut < 0.07 805 ± 335 15 ± 9 6 ± 3 49 ± 22 Palm kernel < 0.07 1100 ± 310 25 ± 15 3 ± 3 30 ± 30
  28. 28. 10 Fats and Oils: Formulating and Processing for Applications of unsaturation and the total tocopherol content, that is, higher tocopherol concentra- tions are present when the unsaturation level indicates a need to prevent oxidation. The tocotrienols are found predominantly in palm oil and cereal oils, such as barley and rice bran oil. Vitamin E functions in humans as a nonspecific chain-breaking antioxidant that prevents the propagation of lipid oxidation. With respect to their vitamin E activity, α-tocopherol is the most active compound present, while the activity of the other compounds is: β-tocopherol, 15–40; γ-tocopherol, 1–20; δ-tocopherol, 1; α-tocotrienol, 15–30; β-tocotrienol, 1–5; and γ- and δ-tocotrienol, 1% of that of the α-tocopherol. The natural occurring α-tocopherol has been found 35% more active than that of the synthetic all racemic α-tocopherol.12 Table 1.4 lists the tocopherol and tocotrienol contents of most of the major fats and oils before processing.11,13-15 The natural antioxidant content decreases during each stage of processing, with the highest reduction occurring during chemical refin- ing and deodorization. Refining with caustic can remove as much as 10 to 20% of the tocopherols and tocotrienols, but 30 to 60% can be lost with deodorization or steam distillation. Distillates from deodorized or chemically refined oils have economic value due to the sterol and tocopherol contents that are sources for natural vitamin E, natural antioxidants, and other pharmaceuticals. The fat-soluble natural antioxidants are light yellow to colorless, but acquire a deep red hue with oxidation, which causes a noticeable intensification of the red–yellow color.8 1.7.3  Sequalene Squalene is an unsaturated hydrocarbon, C30H50, with important biological prop- erties. Sequalene is a low-density compound that is lighter than water with a specific gravity of 0.855. It can easily produce oxygen by combining with water. It is a meta- bolic precursor of the entire steroid family. Oxidation of one of the terminal double bonds forms an oxide, which is enzyme catalyzed to lanosterol, and then elaborated into cholesterol and other steroids. A chemopreventive effect of squalene on some forms of cancer has been reported. Sequalene has also been shown to possess moder- ate antioxidant properties; however, it sustains a significant loss of these properties during storage. Shark liver oil is a rich source of squalene and small amounts are found in some vegetable oils. Olive oil and amaranth seed oil are two rich plant sources of squalene. It also is a natural byproduct of natural vitamin A commercial production.16-19 1.7.4  Sterols Sterols are minor components of all natural fats and oils and comprise most of the unsaponifiable matter, the remainder consists essentially of hydrocarbons. The sterols are high melting, colorless, and somewhat inert. It was thought that ste- rols did not contribute any property to a fat or oil; however, an antipolymerization activity has been identified for some sterols in heated oils, they can undergo oxida- tion to form a variety of oxidation products, and they can lower LDL (low-density
  29. 29. Raw Materials 11 lipoproteins) cholesterol levels in hypercholesterolemic individuals. Caustic refining removes a portion of the sterols, but more effective removal requires fractional crys- tallization, molecular distillation, or high-temperature steam distillation. Table 1.4 lists the total sterol levels and identifies the cholesterol portion for each of the major fats and oils.11 Cholesterol is the main sterol component of animal fat and fish oil and is found in vegetable oils in only trace amounts. In humans, the liver synthesizes cholesterol, but it is also consumed through the diet. Its presence in the body is essential for life. Being water soluble, cholesterol can only be transported in the body by combining with water-soluble proteins to form lipoproteins. It is the form of these lipoproteins that has been the subject of many investigations involving heart disease. There are several types of lipoproteins that have different densities. These are classified as high-density lipoproteins (HDL), low-density lipoproteins (LDL), and very low- density lipoproteins (VLDL). Elevated levels of LDL and VLDL cholesterol can be oxidized to ultimately form plaque that can build up on artery walls to restrict blood flow and cause elevated blood pressure. HDL cholesterol apparently carries choles- terol out of the bloodstream and back to the liver for breakdown and excretion. The levels of serum cholesterol and the LDL and HDL fractions in the blood are influ- enced by several factors including age, sex, genetics, diet, and physical activity. Diet and exercise are controllable factors for reducing coronary heart disease risk factors. The general diet guidelines that relate to fats and oils are:21 Saturated fatty acids increase total, LDL, and HDL cholesterol. Palmitic, myristic• and lauric fatty acids increase both LDL and HDL cholesterol, but stearic and the medium-chain fatty acids (6 to 10 carbon atoms) have neutral effects on blood lipids and lipoproteins. Trans• fatty acids have been shown to increase serum LDL cholesterol and some stud- ies have indicated that trans fatty acids tend to lower serum HDL cholesterol. Monounsaturated and polyunsaturated fatty acids lower serum cholesterol when• they replace saturated and trans fatty acids. Vegetable oil sterols are collectively called phytosterols. Campesterol, stigmas- terol, and sitosterol are the best-known vegetable sterols. Vegetable sterols, primarily sitosterol as a fatty acyl ester, have been shown to reduce both serum cholesterol and LDL cholesterol and are promising additions to foods to lower heart disease risk.13 Phytosterols, and to a greater extent phytostanols, inhibit absorption of cholesterol in the intestine, while not being absorbed themselves in significant amounts.22 The U.S. Food and Drug Administration (FDA) has approved a health claim for plant sterol/stanols esters: Diets low in saturated fat and cholesterol that include at least 1.3 grams plant sterol esters or 3.4 grams of plant stanol esters, consumed in two meals a day with other foods may reduce the risk of heart disease. Additionally, the claim states that they can reduce cholesterol levels.23 Phytosterols were used as a supplement and as a drug to lower serum cholesterol levels in hypercholesterolemic individuals before the “statin” drugs were introduced. The crystalline nature and poor solubility of free phytosterols limited their use as a
  30. 30. 12 Fats and Oils: Formulating and Processing for Applications supplement, drug, or in food applications. A major breakthrough occurred when sci- entist at Raisio Group in Finland discovered that phytostanols fatty acid ester deriva- tives could be readily incorporated into fatty foods, such as margarine and salad dressings. The phytosterols derived from vegetable oils or “tall oil’ are refined and purified, hydrogenated to phytostanols, and then esterified with fatty acids. Stanols derived from tall oil contain primarily sitostanol and campestanol in a ratio of ~92/8; stanols derived from soybean oil contain a sitostanol/campestanol ratio of ~68/32. Both blends appear to have equal efficacy. Clinical studies have shown that stanol esters lower LDL cholesterol levels up to ~14% in adults and children. Phytosterol esters have also been shown to lower serum LDL cholesterol levels in more than 14 efficacy studies. Sterol esters are made by esterifying vegetable oil derived phytoster- ols with fatty acids; no hydrogenation is required with the sterol esters.22 Commercial sterols are derived from vegetable oils indirectly — soapstock from alkali refining and deodorizer distillate are sources of sterols. Processors distill them from the vegetable oil processing byproducts and market the phytosterol ingredients as free sterols and sterol esters. A pine tree byproduct of the pulp-making process is another source of sterols. Natural sitostanol is rare in plants and the sitostanol used in commercial food applications is produced by catalytic hydrogenation of the two most common plant phytosterols: β-sitosterol and stigmasterol.22 The sterols and stanols are esterified with fatty acids from vegetable oils, converting them to fat- soluble stanol esters that do not alter the physical properties of food products. Stanol and sterol esters, esterified with long-chain fatty acids are hydrolyzed into free ste- rols during digestion in the body. The phytosterols ingredients have been approved for addition to fat-based products, such as spreads, dressings, and low-fat foods like yogurt, cheese, and breakfast cereals. Free sterols incorporate into low-fat foods easier than sterol esters.24 1.7.5  Pigments The color bodies in fats and oils include the carotenes that impart yellow and red colors to the oil, chlorophylls that give it a greenish cast, degraded proteins and carbohydrates that have a brownish cast, gossypol that provides the yellowish color to cottonseed oil, and some other components still not completely identified, such as the one giving a blue color that is observed occasionally in lard. Beta-carotene, one of several provitaminA compounds, is the main precursor of vitamin A. Its conversion to vitamin A occurs via cleavage of the molecule at the central double bond by the action of the enzyme carotene deoxygenase, which is present in human intestinal mucosa and the liver. The protective action of beta- carotene and its oxygenated derivates, known as xanthaphylls, against deleterious effects of radiation on light sensitized cells has been well recognized. This effort has been attributed to the conjugated double bonds capable of quenching singlet oxygen; unfortunately, they also have the capability of forming radicals, which initiate oxi- dation degradation of oils.12 Carotene concentrations are low in most fats and oils except for palm oil, which contains 0.05 to 0.2%.8 The carotenes are heat sensitive and readily adsorbed by bleaching earths.

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