CX-0883
`CX Page
`
`EP877ITC-00643401
`
`NEPN Ex. 2060
`Aker v. Neptune
`IPR2014-00003
`
`Page 1
`
`

`
`CX Page
`
`EP877ITC-00643402
`
`Library
`
`International
`
`96 83465
`of Congress Catalog Card Number
`0-91 3250-90-2
`Book Number
`
`Standard
`
`1996 by the American Association of Cereal Chemists Inc
`Second printing 1999
`
`All
`
`rights
`
`reserved
`in any form including
`No part of this book may be reproduced
`storage and retrieval
`system
`photocopy microfilm information
`electronic
`or by any means including
`or software
`database
`computer
`or mechanical without written permission from the publisher
`
`trademark proprietary product
`in this publication
`Reference
`for explicit description only and
`intended
`or company name is
`of the product to the
`or recommendation
`does not
`imply approval
`exclusion of others that may be suitable
`
`to
`
`Printed in the United
`
`States
`
`of America on acidfree
`
`paper
`
`American Association of Cereal Chemists
`3340 Pilot Knob Road
`551 21-2097
`
`St Paul Minnesota
`
`USA
`
`Page 2
`
`

`
`nected with their conversion to
`
`particular
`
`group
`
`of prostaglandins
`
`see Chapter
`The chemical
`
`the position
`
`as
`
`reactivity of unsaturated fatty acids is determined by
`the number of the double bonds in the molecule
`as well
`increases markedly with an increase in the number of double
`Reactivity
`bonds provided they are conjugcited separated only by one single bond
`-CH- unit Box 1-5 If
`separated by
`or methylene-nterrupted
`acid has two isolated double bonds separated by two or more methyl
`than that of
`fatty acid
`ene units its reactivity is only slightly greater
`are important when
`has only one double bond These
`that
`differences
`also during the hydrogena Lion
`and
`to oxidation
`the fat
`subjected
`
`fatty
`
`is
`
`process
`unsaturated fatty acids the double bonds
`In isiost naturally occurring
`on the
`are in the ds configuration This means that
`the carbon chains
`
`CX Page
`
`FUNCTIONAL PROPERTIES
`
`Carboxyl groupThe
`chemical
`functional
`
`one end of
`
`group on
`fatty acid This is
`
`carboxylic
`
`acid
`
`the same as
`COOH which can
`and become C00 or
`proton
`combinewith
`an alcohol
`group
`
`lose
`
`to form an ester
`
`AliphaticDescribing
`
`straight
`
`chain of carbons
`
`with
`
`no branching
`
`or ring structure
`
`SaturatedDescribing
`carbon chain in which the
`
`carbons
`
`are connected to each
`
`other by single bonds
`
`as CC It has no carbon-to-
`
`drawn
`
`carbon double bonds
`
`Monounsaturated
`
`Describing
`
`one double bond CC in the
`
`fatty acid that has
`
`carbon chain Olec acid is
`
`the
`
`most common of
`
`these
`
`PolyunsaturatedDescribing
`fatty acid that has more than
`
`uric double bond CC in the
`
`carbon chain Linoleic acid is
`
`an example
`
`Omega fatty acidsA method
`of nomenclature that
`
`designates
`
`the number
`
`of
`
`between
`
`the terminal
`
`carbons
`.CH3 group and the last double
`bond in the fatty acid This is
`
`useful
`
`in discussing
`
`the
`
`physiological
`
`role of certain
`
`polyunsaturated
`
`fatty acids
`
`Conjugated
`situation in which double
`
`-Describing
`
`bonds
`
`occur
`
`bond
`
`between
`
`in
`
`series with
`
`carbon atoms
`one single
`in between CCCC
`
`Methylene-interrupted
`situation in which
`
`Describing
`double bonds
`
`between
`
`carbon
`
`in
`
`atoms occur
`two single bonds
`CC-C-CC
`
`series with
`
`in between
`
`EP877ITC-00643403
`
`Page 3
`
`

`
`Hydrolysis
`
`to
`
`variety of splitting
`in food applications
`
`free
`
`The ester bonds in fat can undergo
`Ester cleavage
`Some of
`reactions Fig
`these
`are important
`while others have other
`industrial
`significance
`The addition
`of water yields
`free fatty acid and
`hydroxyl group This reaction called saponification
`is usually
`catalyzed
`with
`base such as sodium hydroxide
`and the fatty acid is neutralized
`sodium soap
`can be the hydroxyl donor
`mono-
`Glycerolysis Glycerol
`forming
`glyceride with the fatty acid and leaving
`mono- or diglyceride
`behind
`is the basis for making monoglyceride emulsifiers for food
`This reaction
`use In commercial production
`basic catalyst
`usually potassium car
`is used
`bonate
`The reaction
`Alcoholysis
`catalyzed with
`is usually
`an acid such as HC1 or
`sulfonic
`acid resin For example reaction
`with methanol
`yields the methyl
`of
`the fatty acids which
`esters
`used to analyze
`the composition of
`the fat by gas phase chromatogra
`phy
`
`of
`
`fat with alcohol
`
`of
`
`fat
`
`are
`
`free
`
`fatty acid
`
`the
`
`soybean oil
`
`eep
`
`1ot
`he
`
`is
`
`CX Page
`
`FUNCTiONAL PROPERTIES
`
`11
`
`HydrolysisA chemical
`in which
`
`reaction
`
`molecule
`
`into two parts
`molecule
`of water
`also
`and OH which are
`to the places where the
`original bond was broken
`acid is
`removed
`from
`
`splits
`
`into
`
`added
`
`fatty
`
`splits
`
`glyceride
`by hydrolysis of the
`ester bond
`
`SaponificationA
`
`chemical
`
`reaction
`
`alkali
`
`caused
`by addition
`in which the fatty acids
`attached
`to
`
`of
`
`cleaved
`
`off
`
`glycerol are
`to produce soap
`fatty acid salts and
`molecule
`
`glycerol
`
`GlycerolysisA chemical
`in which glycerol
`with one or more
`acids to form glyceride
`
`reaction
`
`combined
`
`fatty
`
`is
`
`AlcoholyslsA chemical
`
`reaction
`
`in which fatty acids
`
`react with alcohol
`
`to form an
`
`ester
`
`InteresterificationChanging
`
`the positions of the
`
`fatty
`
`acids
`
`on triglycerides
`commercial
`
`This is
`
`processing
`
`step to
`
`change
`
`the physical
`
`properties
`
`of
`
`fat
`
`fatty acid can
`displace another
`Interesterification
`from an ester
`glyceride with somewhat
`leaving
`changed
`properties
`because its fatty acid structure
`has changed This
`is used to
`reaction
`fat properties
`Lard for example has
`change
`nonrandom fatty acid
`acid 25% of
`distribution
`in its triglycerides All
`the palmitic
`the total
`is found
`in the
`position As
`rather
`lard crystallizes
`readily in
`result
`j3 form which is not desirable for bakery purposes Heating in the
`presence of sodium methoxide or metallic sodium causes
`the fatty acids
`to shuffle their positions
`in the triglycerides randomly The resulting fat
`has
`lower SF1 profile and is stable in the
`more
`crystal state giving
`plastic shortening Another application
`blending 20 parts fully
`involves
`hydrogenated
`soybean oil which forms
`13 crystals with 80 parts refined
`then interesterifying
`The product has the SF1 profile ap
`for soft
`tub margarine
`and
`has only
`propriate
`trans double bonds
`Reduction
`
`is
`
`13 stable
`
`trace of
`
`Fat ester bonds
`
`also be
`can
`split
`reductively
`yielding
`and
`The reductant
`alcohols
`glycerol
`long-chain
`an amalgam of
`sodium and potassium metals The resulting fatty alcohols
`are used to
`make
`various
`and
`waxes
`lubricants
`and
`detergents
`economic
`
`importance
`
`is
`
`are of great
`
`fats
`
`fatty
`
`acid
`
`Oxidation Autoxidation
`of
`occurs with unsaturated
`chains The relative rates of oxidation of oleic linoleic linolenic
`and
`arachidonic acids which have one two three and
`four double bonds
`50
`The
`12 25 and
`are
`double bonds
`respectively
`in the
`polyunsaturated acids are separated
`by methylene groups and are cis in
`their configuration
`Autoxidation
`
`of
`initiated and
`reactions
`radicals
`reacting with methylene -CH2- groups that
`by free
`to double bonds Fig 1-8
`radical
`is an unpaired
`indicated
`in chemical
`heavy dot
`formulas
`the beginning
`
`is
`
`series
`
`free
`
`radical
`
`propagated
`
`are
`
`adjacent
`
`electron
`
`reactive
`
`as
`species At
`
`free
`
`of
`
`the autoxidation
`
`It
`
`is
`
`very
`
`process
`
`an acid
`
`Reduction__Changing
`group on
`fatty acid to an
`alcohol
`group This is done
`with metal
`
`reducing
`
`agents
`
`to
`
`create fatty
`
`alcohols
`
`for
`
`industrial
`
`uses
`
`Autoxidation.A reaction
`which fats undergo oxidative
`due to the double
`changes
`
`in
`
`bonds
`
`in their structure The
`
`reaction
`
`can
`
`initiate
`
`and
`
`proceed without
`
`outside
`
`influences
`
`Free radicalAn
`
`unpaired
`
`electron
`
`that
`
`is an unstable
`
`intermediate
`
`in the
`
`development
`and rancidity
`
`of
`
`lipid oxidation
`
`EP877ITC-00643404
`
`Page 4
`
`

`
`CX Page
`
`hydrogen
`
`radical
`
`and
`
`of
`
`the double bonds
`
`shifts
`
`carbon
`
`pcroxyl
`
`Dissolved
`
`this
`
`hydroperoxide
`
`radicals
`
`one
`is extracted
`the radical site to the outer
`moving
`reaction
`adds to this site generating
`oxygen
`radical reaction
`abstracts
`from
`hydrogen
`another methylene
`donorperhaps
`groupmaking
`The hydroperoxide splits to
`reaction
`two free
`hydroxyl and
`generate
`an alkoxyl
`radical reaction
`by traces of metal
`ion such as copper or
`three free
`each of which
`radicals
`can
`The rate of reaction
`
`This cleavage
`iron The
`net
`result
`
`is
`
`is catalyzed
`
`another chain of
`
`reactions
`
`is self-enhancing
`
`i.e it
`
`initiate
`
`is an autoculalytk
`The
`
`reaction
`
`due
`
`signs of
`rancidity musty odors bitter disagreeable
`flavors
`are
`to breakdown
`of
`the alkoxyl
`products
`radical structure
`These
`variety of aldehydes and ketones
`products are
`derived from breaking
`the fatty acid carbon chain at
`the point where it is oxidized Common
`and
`the
`ethyl hexyl ketone
`of
`
`o-aldehyde
`
`12
`
`CHAPTER ONE
`
`Peroxyl
`
`radicalAn
`
`intermediate
`
`in
`
`lipid oxidation
`
`in which the
`
`fatty
`
`acid radical
`two oxygen atoms
`free radical
`
`It
`
`is
`
`by the structure
`
`has added
`
`and is still
`
`characteri7ed
`
`Coo
`
`HydroperoxideAn
`intermediate
`
`in lipid oxidation
`
`in which the
`
`added
`
`fatty acid has
`two oxygen atoms and
`hydrogen atom at
`of
`the point
`oxidation
`is no longer
`
`It
`
`free
`
`radical
`
`but eventually
`to flavor compounds
`with rancidity
`
`degrades
`
`associated
`
`in
`
`fat
`
`RancidityAn off
`flavor
`or oil caused either by
`oxidation
`or by the release of
`
`flavorful
`
`fatty acids from the
`
`triglyceride
`
`StabilityThe
`
`resistance
`
`of
`
`fat source
`
`to the formation
`
`of
`
`rancidity
`
`AntioxidantsCompounds
`that can
`
`inhibit
`
`the
`
`development
`
`of
`
`lipid oxidation
`
`QH
`
`-OH CH CHCH-CH
`
`Fig 1-8 Reactions
`
`during autoxidation
`
`occurring
`
`of fat
`
`products
`nonanoic
`
`are heptanal
`acid
`
`initiate
`
`radicals
`
`arise
`
`inadequate refining
`excluded
`
`and
`
`as
`
`long as
`
`If
`
`are present
`to singlet
`step shown in
`
`to autocatalytic
`
`rancidity
`
`ions
`
`should be
`
`of oil
`
`also be increased
`
`with antioxidants
`
`These
`
`function
`
`to
`
`The
`reactions
`above
`described
`can
`in the dark
`occur
`molecular oxygen
`and
`an initiating free
`radical species
`the oil
`is exposed to light
`oxygen may be photoactivated
`oxygen which
`can
`the chain at
`the second
`Figure 1-8
`In summary four main factors contribute
`Chain initiation by trace free radicals
`Chain propagation by molecular oxygen
`Hydroperoxide cleavage
`catalyzed by metal
`Chain initiation by photoactivated oxygen
`These
`factors
`can
`be minimized
`by good manufacturing
`practices
`The trace free
`from peroxides
`that are left behind from
`deodorization Molecular
`oxygen
`by processing transporting
`and storing oil under
`nitrogen
`can be kept out of
`atmosphere Metal
`ions
`the oil by having properly
`designed and maintained equipment and traces of metal
`in the oil can
`be inactivated
`by chelation with citric acid Finally the exposure
`to light should be minimal With these
`oil oxidative
`precautions
`can be increased
`several fold
`stability
`Oxidative stability
`can
`react with the active free
`the antioxidant
`
`radicals
`transferring the radical
`Fig 1-9 Because
`of
`the
`ring structure
`this radical has
`low reactivity and
`antioxidant
`does not
`new
`initiate
`reaction
`chains However
`radicals continue to form due to the
`if free
`and trace metals eventually
`presence of oxygen
`all the antioxidant will
`and the autocatalytic
`sequence will devclop without hindrance
`Several
`organic compounds are in use today as antioxidants They
`in common the ring structure
`have
`shown in Figure 1-9 but
`they vary
`somewhat
`in the structure
`of the side groups The ones approved by the
`Food arid Drug Administration FDA for use in foods are
`BHA butylated
`hydroxyanisole shown in Fig 1.9
`
`of
`
`the
`
`react
`
`all
`
`BHT
`
`butylated
`
`hydroxytoluene
`
`as in Fig
`
`with CH3
`
`EP877ITC-00643405
`
`Page 5
`
`

`
`20
`
`CHAPTER
`
`TWO
`
`to measure
`
`Oxygen bombA procedure
`the speed at which
`sample consumes
`heated
`oxygen due to lipid oxidation
`
`Smoke pointThe
`at which
`heated
`temperature
`to give off smoke
`
`oil begins
`
`Flash pointThe temperature
`heated
`at which
`oil gives
`flashes of burning when
`flame
`
`exposed
`
`to
`
`Fire pointThe temperature
`heated oil burns
`at which
`flame when ignited
`
`with
`
`CX Page
`
`of
`
`fla
`
`dc
`
`ab
`
`ce
`ch
`
`sf1
`
`eh
`
`ev
`
`In
`
`ca
`
`Cc
`
`Sc
`
`ec
`
`a1
`
`in
`
`gI
`
`p1
`
`p1
`
`FL
`
`is
`
`ai
`
`al
`
`(cid:237)a
`
`lI
`
`The
`of
`the determination
`point of
`10 degree
`almost exactly doubles with each
`increase in temperature
`at 110C to shorten testing time
`and
`the apparatus
`is usually
`operated
`obtained at 110C
`correlate well with AOM values results
`Tile results
`are 4045% of the AOM numbers determined at 97.8C
`
`the
`
`autoxidation
`
`reaction
`
`rate
`
`bomb The
`is sealed
`heavy-walled container
`sample
`Oxygen
`pressure recorder The bomb is pressurized with
`to 100
`tached
`to
`is the time when
`boiling water bath The end point
`then placed iii
`rapidly and
`pressure drop
`to absorb
`starts
`the sample
`sharp
`oxygen
`bomb results correlate
`better with
`that oxygen
`occurs It
`reported
`than do AOM numbers
`of rancidity
`product shelf life tests appearance
`sample e.g
`the whole
`This method has
`that
`the added
`advantage
`be used in the test no prior fat extraction
`snack
`
`in
`
`psi
`
`is
`
`crackers
`
`may
`
`necessary
`
`at
`
`is
`
`cup and heated
`flash point fire point Fat is placed
`Smoke point
`in
`strong light The temperature at
`white-walled
`chamber
`under
`in
`the smoke point With further
`of smoke are observed
`which wisps
`the hot oil causes flashes
`flame that
`small open
`is passed over
`heating
`this is the flash point Upon further heating eventually
`of burning fat
`point The presence
`continuous fire can be ignited at
`the fat surface
`fried food in the oil all serve
`and bits of
`of
`free fatty acids emulsifiers
`Fig 2-4 The
`lower
`points
`250 degrees
`higher
`approximately
`100 degrees
`higher still
`is 55 degrees
`and
`the fire point
`point
`fats used in deep frying operations
`Smoke point
`is an important test
`relatively low smoke point to start with the formation
`the fat has
`
`to
`
`these
`
`temperature
`140
`
`degrees
`
`flash point
`than the smoke
`
`is
`
`is
`
`for
`
`If
`
`700
`
`600
`
`500
`
`400
`
`U-
`
`ci
`
`cci
`
`ci
`
`ci
`
`ii
`
`300
`
`Legend
`
`Smoke
`
`point
`
`ash point
`
`re point
`
`200
`
`0.05
`
`0.2
`
`ii
`0.5
`
`II
`
`10
`
`350
`
`300
`
`250
`
`200
`
`150
`
`100
`
`Free Fatty Acid Concentration
`
`Fig 2-4 Effect of
`bean oil
`
`free fatty acd content
`
`on the smoke
`
`flash arid fire points
`
`of soy
`
`EP877ITC-00643406
`
`Page 6
`
`

`
`reaction
`
`emperature
`esting time
`at 110C
`
`ntainer at
`
`to 100
`time when
`
`essure drop
`better with
`vf numbers
`mple e.g
`ctraction
`
`is
`
`and heated
`
`of free fatty acids and fat breakdown
`products during use may lower the
`be
`ignited by the heating
`that
`the fat may
`flash point sufficiently
`elements
`
`of oxidized
`
`fat
`
`and
`
`subsequent
`
`reaction
`
`measure of
`
`The
`
`ketones
`
`ability
`
`centage
`
`of
`
`of
`
`these
`
`products
`presence
`the suit
`aldehydes polymerized materials is
`The per
`the fat
`for continued use in frying see Chapter
`is determined
`sample of used fat
`fat
`
`polar materials
`weighed
`
`in
`
`on the top of
`
`chromatographically
`silica gel column
`eluted with solvent
`
`and
`
`the nonpolar
`
`sample of
`is placed
`lipids unchanged
`triglycerides
`ether The weight of
`petroleum ether/diethyl
`determined
`the solvent
`removed
`nonpolar
`evaporation The percentage
`is calculated
`of polar
`In many countries frying fat used in food preparation
`than 27%
`carded if the polar
`lipid concentration is greater
`
`lipids
`
`is
`
`after
`
`is
`
`lipids
`
`by difference
`must
`be dis
`
`are
`
`the
`
`by
`
`CX Page
`
`ANALYTICAL
`
`TESTS
`
`Polar
`
`lipidsFat
`
`components
`
`that are more like water
`
`and
`
`less
`
`like fat
`
`in their
`
`solubility
`
`properties
`
`Introduction
`
`of
`
`oxygen or nitrogen
`lipid molecules makes
`
`them
`
`atoms into
`
`more
`
`polar
`
`Nonpolar
`
`lipidsFat
`
`components
`
`that are like
`
`organic
`
`solvents
`
`and not
`
`like
`
`water
`
`in their
`
`perature
`ith further
`
`at
`
`uses flashes
`
`ventually
`
`lie presence
`
`oil all serve
`
`li point
`the smoke
`
`is
`
`igher still
`
`operations
`formation
`
`350
`
`300
`
`250
`
`200
`
`150
`
`100
`
`Oiflts of soy
`
`in their inherent depth
`from
`refined
`oil
`
`if
`
`upon the
`of color depending
`than
`is darker
`
`source
`
`it
`
`or was
`
`Color Oils differ
`source However
`specific
`the oil was either
`indicates
`improperly refined
`that
`expected
`abused Color is usually measured using the Lovibond
`Tintometer Oil
`tube of standard dimensions is compared with colored
`glass stan
`in
`combination
`red and yellow The
`the
`of
`tries
`dards usually
`analyst
`The results
`are usually ex
`match is obtained
`until
`standards
`the numbers on the glass standards i.e 1.5R 15Y
`spectro
`pressed
`photometric method for color evaluation
`is also available
`
`glass
`
`as
`
`are reversion
`
`o.xidative
`
`Flavor odor Organoleptic evaluation of oil
`test and there
`is an empirical
`for an experienced analyst The main negative
`is no substitute
`factors
`flavors and
`rancidity Various oils upon storage
`flavors reversion flavors Soy oil
`characteristic
`develop
`refining
`beany note while palm oil
`for example develops
`develops
`caused
`metallic flavor Odors due
`to oxidative
`are primarily
`rancidity
`compounds from the breakdown
`by volatile aldehydic and
`has been
`that
`is best done
`Evaluation
`acid peroxides
`using oil
`warmed to about 4050C 104113F in water bath
`
`after
`
`fatty
`
`ketonic
`
`of
`
`Relationship
`
`As
`
`is
`
`break
`
`to SF1/C and crystal structure Plasticity creaminess
`shortening or margarine is an important property
`of
`spreadability
`but one that
`instruments
`to specify exactly
`is difficult
`using analytical
`plasticity when the SF1
`rough rule of thumb
`fat shows
`of 1025 units It
`in the range
`that
`the crystal
`is also important
`be stabilized in the
`form in this form the small needles
`structure
`stress but also reform quickly when
`readily under
`the stress
`removed Such
`for example functions
`shortening
`fat
`in making layered
`or
`in the creaming
`doughs
`cookie manufacture
`sec Chapter
`
`acceptable
`
`is
`
`properly
`
`as
`
`roll-in
`
`operation
`
`during
`
`By contrast
`
`crystals
`
`give the
`
`solubility
`
`properties
`
`Unaltered
`
`triglycerides are usually very
`
`nonpolar
`
`Organoleptic evaluation
`
`Evaluating
`sense such
`
`quality using
`as taste or smell
`
`Oxidative
`
`flavors
`
`in
`
`rancidityOff-
`fat or oil due to the
`
`reaction
`
`of oxygen with fat
`molecules
`
`PeroxidesOxidized
`
`fat
`
`molecules
`
`that eventually
`degrade to off-flavors
`
`EP877ITC-00643407
`
`Page 7
`
`

`
`CX Page
`
`ANALYTICAL
`
`TESTS
`
`23
`
`rans double oonds
`is and
`tultt
`
`iii
`
`ypical
`
`iodine
`
`values
`
`IVs are given for
`
`Cnniiertien In nhvsir1
`ub
`
`rnt
`ci
`
`rfje Th
`
`po
`
`rf
`
`tn
`
`hrnic
`
`gy
`
`ved
`
`for cxample two diffcrcnt
`qu
`physical
`
`and
`
`other
`
`ranges
`eed
`
`fcc
`
`aL
`
`catalysts
`
`fe
`
`get
`and conditions and
`et
`ies
`
`at
`
`the resulting
`
`ast
`
`properties
`av
`
`Ic
`
`Likewise
`
`soy oil and
`
`cot
`
`ara
`rc
`only when
`compaies
`hydrogcnation conditions
`
`one
`
`thc
`
`correlatcs with physical
`functionality
`same starting oils and thc samc procescuig
`
`Peroxide value PV Hydroperoxides
`formed by fat oxidation
`with iodide ions to form iodine which in turn is measured
`by titration
`The resulting PV is expressed
`with thiosulfate
`of
`as milliequivalents
`the classical method for
`formed per kilogram of
`fat This
`of oxidation
`determining the extent
`fat As part of
`has been
`
`react
`
`raw material
`
`properly
`
`refined
`
`iodine
`
`specification
`and handled
`
`it ensures
`
`that
`
`the ingredient
`
`is
`
`of
`
`the
`
`products
`
`is
`
`ASTM
`
`pene
`work
`onal
`
`to
`
`with
`
`fication
`
`or puff
`
`ming
`food
`
`rides
`
`to
`The
`is and
`can be
`
`ions of
`
`taming
`the
`
`as
`
`Tith the
`
`do not
`
`nfrared
`
`used
`
`to
`
`solvent
`
`ns pos
`is and
`
`getable
`
`nple of
`lroxide
`
`cc
`
`fatty
`
`in the
`
`ned oil
`
`ontent
`
`ears to
`
`in Un
`up the
`ssed as
`
`LIi both
`
`Anisidine value AV PV does not measure all the breakdown
`formed from peroxides
`in particular
`3-unsaturated
`aldehydes
`form
`adduct with anisidiæe the color
`However
`these
`colored
`at 350 nm and converted to AV The test
`is seldom used in
`quantitated
`the United States but
`is widely used in Europe particularly
`the Totox number
`
`part of
`
`as
`
`Anisidlne
`
`value-A test
`determine the amount
`
`to
`
`of
`
`measure of
`
`the total oxidation
`
`of
`
`the fat or oil
`
`is the
`
`reaction
`
`products
`
`produced by
`
`Totox number
`Totox number
`
`Totox
`
`AV
`
`PV
`
`During storage stability testing of high-fat products it is often observed
`that PV first rises then falls as hydroperoxides decay Totox however
`and their breakdown
`measures both hydroperoxides
`tends
`products It
`to rise continuously
`and
`of
`the progressive
`gives
`oxidative
`degradation of the fat
`acid TBA value TBA forms colored adducts with the
`2-Thjobarbjturic
`products formed from fatty acid peroxides The aldehyde
`at 450 nm while
`form
`yellow pigment with an absorption
`products
`the 24-dienals for example from the breakdown
`at 530 nm The test
`red adduct with absorption
`hydroperoxide
`breakdown
`of fatty acid oxidative
`
`better measure
`
`breakdown
`
`give
`
`of
`
`linoleic acid
`
`is
`
`lipid
`
`oxidation
`
`Totox numberA measure of
`the total amount
`of
`
`intermediate
`compounds
`peroxides and end-product
`from
`that
`
`result
`
`compounds
`
`lipid oxidation
`
`acid value
`
`Thiobarbturi
`oflpd df
`Ar
`ad
`iine
`cet
`odu
`
`rof
`
`pd
`
`tar
`
`ata
`
`quite sensitive
`
`registering the presence
`very early stage in the development
`
`products
`
`at
`
`of rancidity
`
`During the refining of corn and soybean oil
`lecithins phospholipids
`gums must be removed
`Residual
`lecithin in
`as completely as possible
`the oil contributes
`and
`instability and leads to fishy taste
`to oxidative
`odor in foods
`fried in the oil The
`standard method for measuring
`
`EP877ITC-00643408
`
`Page 8
`
`

`
`24
`
`CHAPTER
`
`iWO
`
`to ash the sample and determine phosphorus
`ash colorimetrically
`or by atomic absorption
`spectro
`quicker method useful
`photometry
`for monitoring the completeness
`of degumming during refining
`uses the fact
`that
`lecithin is insoluble
`The oil sample
`acetone
`and made
`is dissolved
`in acetone
`50 ml The
`turbidity due to
`gums of
`read
`in
`and
`nephelometer
`to phosphorus
`standard curve
`
`phospholipid
`in the residual
`
`content
`
`is
`
`volume
`
`of
`
`suspension is
`content using
`
`in
`
`to
`
`the
`
`insoluble
`
`is
`
`related
`
`sterols and hydrocarbons
`Waxes
`in fats and oils are generally
`termined as unsaponifiable material The weighed
`sample is saponified
`refluxed with aqueous
`sodium hydroxide The cooled mixture is
`re
`extracted with petroleum ether and/or diethyl ether The sol
`peatedly
`vent
`removed
`from the combined dried
`which
`are then
`extracts
`material
`
`is
`
`weighed
`
`and
`
`reported
`
`as
`
`unsaponifiable
`
`The
`
`content
`
`of
`
`de
`
`material
`unsaponificable
`than 0.5% and is not
`
`in
`
`refined
`properly
`problem with respect
`
`fat or oil
`
`is generally
`
`less
`
`to quality
`
`TABLE 2-2 Raw Material
`
`Specification
`
`for All-Purpose
`
`Shortening
`
`Chemical
`
`CX Page
`
`Pr
`
`cus
`
`SUP
`
`the
`
`issu
`
`det
`bu
`Iwi
`
`Tab
`
`spe
`spe
`sto
`
`stat
`
`top
`
`itel
`
`Peroxide value
`
`Free fatty acid as oleic acid
`
`Phosphorus
`AOM stability
`
`content
`
`Oil
`
`stability
`
`index
`
`Wiley mp
`
`Physical
`
`Color Lovibond
`
`Flavor
`
`Odor
`
`Solid fat profiles
`
`meqlkg maximum
`0.05% maximum
`
`ppm maximum
`75 hr minimum
`
`30 hr minimum
`1C
`
`46
`
`Cd 8b-90
`
`Ca Sa-40
`
`Ca
`
`2-55
`
`Cd 12-57
`
`Cd 12b-92
`
`Cc 2-38
`
`1.5
`
`15
`
`maximum
`
`Cc
`
`3c-92
`
`Bland
`
`Neutral when warmed
`
`See chart
`
`below
`
`SFC Cd
`
`6b-93
`
`SF1 Cd 10-57
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`383
`293
`223
`172
`122
`81
`41
`
`50
`
`70
`
`80
`
`92
`
`104
`
`283
`202
`171
`131
`71
`
`EP877ITC-00643409
`
`Page 9
`
`

`
`losphorus
`
`spectro
`
`ipleteness
`
`soluble in
`
`ade
`
`to
`
`of
`
`the
`
`osphorus
`
`rally de
`ponified
`
`tre is
`re
`The sol
`are then
`
`ntent of
`
`rally
`
`less
`
`6b-93
`
`-57
`
`CX Page
`
`10
`
`ANALYTICAL
`
`TESTS
`
`25
`
`chemical
`
`requirements
`
`set of
`Specifications
`and physical quality
`that
`product or
`ingredient must meet before
`
`it
`
`is acceptable
`
`cussed
`
`It
`
`is
`
`written list of
`
`tests
`
`It
`
`is
`
`and
`
`to
`
`are
`
`The main reason for expending
`to perform the tests dis
`resources
`fat or oil communicate to the
`above
`is to help the buyer of
`precisely what
`is needed This communication
`is in the form of
`supplier
`product or raw material specification
`for each analysis
`the buyers responsibility
`the desired result
`Of course frequently
`the actual numbers
`issue this specification
`with the suppliers
`In essence the
`determined through collaboration
`buyer is saying If you supply material
`that meets these specifications
`will consider purchasing it from you
`for an all-purpose
`typical specification
`2-2 This is only
`of
`the sources
`
`Table
`
`specify
`
`in
`
`to
`
`shortening is presented
`The buyer may want
`partial specification
`the oils used to make the shortening
`and
`the
`such matters
`as packaging kind size
`should also address
`for Good Manufacturing
`Practices
`at all
`storage conditions necessity
`and other matters
`stages of production
`that are outside
`covered in this chapter
`brief comment on the reason for and
`items listed in Table 2-2 might be helpful
`
`specification
`
`topics
`
`the specific
`
`importance of each of
`
`the
`
`Peroxide value Since
`peroxides
`PV greater
`than
`meq/kg indicates
`Chapter
`have
`reduced stability in the finished product
`
`are initiators
`
`of autoxidation
`
`see
`
`that
`
`the fat will
`
`fat are removed during re
`Free fatty acid The free
`fatty acids in
`An FFA level of more than
`fining and deodorizing see Chapter
`0.05% indicates
`steps were not properly
`done or that
`that
`these
`high level of citric acid in the oil
`
`there is
`
`content More than
`ppm phosphorus
`indicates
`Phosphorus
`the oil used to make the shortening The
`incomplete degumming of
`residual
`lecithin promotes
`autoxidation
`rancidity
`AOM and OSI One or the other of these
`the shortening has sufficient
`tended purposes
`
`that
`is included to ensure
`for its in
`
`oxidation
`
`against
`
`stability
`
`for an all-purpose
`Wiley melting point This is unimportant
`ening but is significant
`for fats present
`in high concentration in the
`food product e.g sandwich
`cookie
`filler
`coatings
`
`fats
`
`confectionery
`
`short
`
`Color Lovibond This primarily
`the shortening
`were properly
`numbers
`in part upon the parent oils
`
`ensures
`
`refined
`
`that
`
`and
`
`the oils used to make
`bleached
`The
`
`exact
`
`depend
`
`If
`
`Flavor
`
`it should be
`the shortening has any noticeable
`off-flavors
`for bad flavors none
`There are many sources
`immediately
`rejected
`of which are acceptable
`
`Odor The same comments apply here
`for flavor Any noticeable
`as
`for immediate rejection of
`off-odor
`shipment
`is grounds
`
`NEP877ITC-0064341
`
`Page 10
`
`

`
`CX Page
`
`11
`
`fi rjadlrdctx
`
`Processing and Refining
`they exist in nature must be processed
`Fats and oils as
`before they are
`suitable for use as edible fats and oils In some cases this is minimal for
`example churning cream to obtain butter In other
`the route
`is much lengthier
`in making salad
`to edible oil
`from natural product
`as
`oil from soybeans or cottonseed Processing
`isolates the fat or oil from its
`natural matrix while refining
`removes
`and
`edible product
`
`impurities
`
`gives
`
`fully
`
`instances
`
`cells
`
`of
`
`oil
`
`depending
`
`and
`Crushing extracting All plant
`contain
`certain
`seeds
`to carbohydrates and protein which
`is nec
`amount of fat
`in addition
`essary to sustain
`the methods
`their growth Generally
`speaking
`The oil
`follow very simple principles
`is either squeezed
`recovering
`from the seed using
`combination or it is
`press hydraulic screw or
`the two methods are combined
`solvent Frequently
`extracted using
`on the nature of
`and the cost of
`the operation The
`the seed
`these methods is to obtain
`the maxi
`
`that
`
`is as
`
`in using any of
`prime objective
`mum amount of an unaltered
`oil
`Most oil seeds except
`This makes
`extraction
`it easier
`
`free of impurities as possible
`canola are dehulled before
`from the meats
`and
`to extract oil
`in
`by the hulls The meats are
`oil absorption
`for ease of ex
`causing sufficient cell breakage to release the oil
`and 4-2 Mechanical
`is simpler and safer
`extraction
`traction Figs
`but
`than solvent extraction
`less efficient
`product press meal
`that contains 36% oil whereas
`meal
`contains 0.5
`1.5% oil
`In solvent extraction
`the flakes or press meal are soaked in
`the solvent normally hexane
`light petroleum fraction The recov
`ered solvent-oil mixture is called miscella and the extracted
`flakes are
`have more economic
`flakes These
`referred
`often
`to as spent
`than the oil being used as
`animal
`feed or as
`high protein
`for human food
`isolated
`
`for
`
`rapeseed
`
`creases yield by decreasing
`
`flaked
`
`It
`
`leaves
`
`solvent-extracted
`
`value
`
`source
`
`of
`
`protein
`
`Refining Oilseeds are natural biologically active materials
`many color and flavor precursors
`as well
`as degradation and breakdown
`products Some of
`the extraneous materials
`in crude oil are phosphat
`ides gums free fatty acids
`color compounds carotenoids
`and chloro
`phyll
`fines and dirt
`waxes moisture meal
`vitamin
`tocopherois
`The oil must be refined
`to remove these
`impurities
`
`that contain
`
`47
`
`ProcessingRemoving
`
`or
`
`otherwise
`
`extracting
`from its natural matrix
`
`fat or oil
`
`RefiningRemoving
`from an extracted
`
`impurities
`
`fat or oil
`
`Press mealThe material
`when oil is extracted
`
`remaining
`
`by mechanical
`seeds
`
`means
`
`from oil
`
`MiscellaThe
`
`mixture
`
`of
`
`solvent
`
`and oil
`
`that
`
`results
`
`from
`
`the solvent
`
`extraction
`
`of oil
`
`from oil seeds
`
`Spent
`
`remaining
`removed
`
`flakesThe material
`when the oil
`from oil seeds
`
`is
`
`NEP877ITC-0064341
`
`Page 11
`
`

`
`CX Page
`
`12
`
`a.
`
`Wi
`
`in
`
`Fi
`
`ti
`
`st
`
`fs
`
`et
`
`ag
`
`Pt
`
`bC
`
`PC
`
`cc
`
`st
`
`ac
`
`as
`
`cient
`
`control
`
`are
`
`to achieve
`
`the
`
`of
`
`48
`
`CHAPTER
`
`FOUR
`
`BleachingRemoving
`from an oil by
`substances
`borbing them onto
`
`solid
`
`colored
`
`material
`
`such
`
`as clay
`
`Degumming Dry gums are soluble in crude oil but become oil-insolu
`ble upon hydration The degumming process
`and
`is enhanced
`the
`of phosphoric acid and
`by the addition
`rate is accelerated
`rehydration
`citric acid to the water After mixing and contact
`time suffi
`sometimes
`Good
`to hydrate the gums these
`by centrifugation
`separated
`and
`the amount
`of water and acid the temperature
`of
`the maximum extent
`time is
`length of contact
`required
`degumming while minimizing oil
`
`losses and maximizing product qual
`
`ity
`
`Neutralization
`
`Crude
`
`fatty acids from natural hy
`oils contain free
`These are removed by the addition
`of aque
`the triglycerides
`drolysis of
`ous sodium hydroxide solution which
`converts
`the fatty acids to water-
`is removed either by simply draining
`soluble soaps The soap solution
`rerr oved the oil
`After the solution
`it off or by centrifugation
`the removal of all
`traces of
`washed
`once or twice with water to ensure
`soap and is dried
`
`is
`
`is
`
`Sunflower and corn oils contain relatively large amounts of
`Dewaxing
`the oil does not cloud when refrig
`that must he removed
`so that
`waxes
`is cooled to 5C mixed with water containing
`surfac
`erated The oil
`tant and allowed to stand for several hours If neutralization is done
`at
`them into
`and bring
`the soaps wet
`the wax crystals
`this temperature
`sodium lauryl sulfate is
`suspension in the aqueous phase Alternatively
`The aqueous wax suspen
`to the water to serve the same purpose
`added
`sion is removed by centrifugation
`
`Bleaching Colored substances
`bleaching Bleaching earths are natural
`
`and oxidation
`
`products
`
`are removed
`by
`treated with
`
`clays bentonites
`
`Fig 4-1 Soybeans
`
`at several
`
`stages of processing
`
`Courtesy
`
`Buhler
`
`Inc Minneapolis MN
`
`NEP877ITC-0064341
`
`Page 12
`
`

`
`oil-insolu
`
`and
`the
`acid and
`ime suffi
`on Good
`and
`the
`
`extent
`
`of
`
`duct qual
`
`tural hy
`of aque
`to water-
`
`draining
`
`the oil
`
`is
`
`traces of
`
`nounts of
`en refrig
`surfac
`
`at
`
`is done
`hem into
`sulfate is
`
`suspen
`
`tnoved by
`ated with
`
`acid to improve theii adsorptivity
`earth is one of
`
`with acid-activated
`ing When
`done
`correctly
`nearly colorless with
`peroxide value
`
`Proper bleaching
`in oil process
`steps
`from the bleaching press is
`the oil emerging
`of zero
`
`and
`
`filterability
`
`the most critical
`
`CX Page
`
`13
`
`REFINING AND PRODUCTION
`
`49
`
`DeodorizatonRemoval
`of
`odors from an oil by injecting
`steam The undesirable
`odors
`
`are carried away because of
`
`their
`
`volatility
`
`RBD olRefined bleached
`and deodorized
`oil These
`
`three treatments
`
`are frequently
`
`applied
`
`in series
`
`to convert
`
`extracted
`
`oils into more
`
`desirable
`
`products
`
`Filtration Complete
`
`tive
`
`filtration
`
`fineries
`
`removal of bleaching earth from the oil by effec
`important because residual
`as
`clay acts
`very
`is very
`downstream Some re
`and
`foul
`the equipment
`can
`strong prooxidant
`which
`still use the old plate and
`frame filter presses
`are very
`of equipment However more modern filtering
`equip
`pieces
`effective
`oil should be protected
`is on the market The
`recovered
`bleached
`ment
`thermal and oxidative abuses as the oil at this point
`in the refining
`against
`should
`stable state The headspace in storage tanks
`process is in its least
`gas to exclude oxygen and prevent autoxidation
`be filled with nitrogen
`com
`salad oil numerous
`to be used as
`odors and flavors must be removed These
`causing undesirable
`pounds
`compounds are relatively volatile and can be removed
`by bubbling live
`steam through the hot oil 200275C under high vacuum 310 mm
`Hg Deodorization does not have
`effect upon the fatty
`any significant
`acid composition of most fats and oils The oil at this step is referred to
`deodorized RBD oil Deodorization
`removes
`bleached
`
`DeodoriZatiOfl
`
`If the oil
`
`is
`
`as
`
`refined
`
`free
`
`FIg 4-2 Flaking mills Courtesy
`
`Buhler
`
`Inc Minneapolis MN
`
`NEP877ITC-0064341
`
`Page 13
`
`

`
`50
`
`Rendering
`
`dehydrating
`
`dryHeating and
`animal
`tissue to
`
`extract and separate
`
`the fat
`
`This process
`
`with
`
`increased
`
`results
`
`in products
`color and flavor
`
`so it
`
`is not commonly used
`
`for
`
`edible
`
`animal
`
`fats
`
`Rendering wetHeating
`tissue by steam under
`animal
`released
`pressure so the fat
`allow separation
`
`is
`
`to
`
`GheeThe
`remaining when
`the water and other
`
`fat
`
`are removed
`from
`components
`butter Also termed anhydrous
`is nearly 100% fat
`milk fat
`
`it
`
`CX Page
`
`14
`
`bac
`
`tb
`
`di
`sol
`bu
`
`toc
`ch
`
`ani
`
`in