D U&M Oils & Fats

D U Liquid oils

SHORTENING

MARGARINE

CH T BO TH C PH M KHC

NGU N: hng trm ngu n nguyn li u - Th c v t : h t, qu - ng v t - T o n bo Ch m t s t c hi u qu kinh t

M : ng c nhi t phng D U: l ng nhi t phng Do thnh ph n ha h c quy t nh Ph h p trong cc ng d ng

CH T BO THNH PH N CHNH Triglyceride THNH PH N KHC acid bo t do mono- v diglyceride phospholid vitamin tan trong d u sp sterol s c t : chlorophyll, carotene, gossypol protein carbohydrate kim lo i Thnh ph n khng x-phng ha (unsaponifiable fraction)

ACID BO RCOOH

ACID BO BO HA (saturated fatty acid) CH3(CH2)nCOOH

ACID BO KHNG BO HA (unsaturated fatty acid)

ACID BO KHNG BO HA N (monounsaturated fatty acid) Arachidonic acid C20:4 n-6 Eicosapentaenoic acid) C20:5 n-3 Docosahexaenoic acid C22:6 n-3
CH3(CH2)xCH=CH(CH2)yCOOH

ACID BO KHNG BO HA A (Polyunsaturated fatty acid)

CH3(CH2)xCH=CHCH3CH=CH(CH2)yCOOH

Formic acid Acetic acid 2:0 Propionic acid Butyric acid Valeric acid Caproic acid Caprylic acid Capric acid Lauric acid 12:0 Myristic acid Palmitic acid Stearic acid Oleic acid 18:1 9 Linoleic acid Linolenic acid Arachidic acid Arachidonic acid Behenic acid Erucic acid 22:1 13 Lignoceric acid Nervonic acid

1:0 3:0 4:0 5:0 6:0 8:0 10:0 14:0 16:0 18:0 18:2 18:3 20:0 20:4 22:0 24:0 24:1 9, 12 9, 12, 15 5, 8, 11, 14

15

COMPOSITION AND STRUCTURE

Fatty Acids in commodity oils and fats. Nomenclature and structure

Fatty acids: occurrence

Fatty acid content of the major commodity oils (wt%)

ACYLGLYCEROL
ACYLGLYCEROL (GLYCERIDE)

ESTER C A GLYCEROL V ACID BO

O H2C OH

O H2C glycerol O C R1 O acyl bo acid 1 1 acyl bo acid 2 2 acyl bo acid 3 3

+ + +

HO C R1 O HO C R2 O HO C R3

HC OH H2C OH

HC OHC R2 O O O H2C OH C R3

PHOSPHOLIPID

PHOSPHATIDIC ACID

O glycerol P2 R1 C O CH2 O R2 C O CH O H2C O P O O

phosphoric a.

acyl 1 acyl 2

PHOSPHATIDE

CH3 HO (CH2)2 choline N CH3 CH3 HO CH2

COOH CH NH2

acyl 1 glycerol acyl 2

serine OH H H OH OH H H OH

amino alcohol ho c sugar alcohol

HO

CH2

CH2 NH2

ethanolamine Phosphatidyl choline Phosphatidyl ethanolamine Phosphatidyl serine Phosphatidyl inositol O C O O C O CH2 CH O H2C O P O (CH2)2 O CH3

OH H OH

inositol

N CH3 CH3 choline

Phosphatidylcholine = lecithin

THN PH N KHNG X PHNG HA

CH3 H3C CH3 CH3 H3C

STEROL
H3C H3C CH3 H3C H HO Cholesterol H H HO H CH3 H3C

H H3C H3C

CH3 CH3 CH3

Ergosterol
H3C H HO

H CH3 H3C H3C CH3

Stigmasterol
H3C H HO

CH3

-Sitosterol

CH3 H2C C C H CH2

isoprene

-caroten

CH2OH

Vitamin A

CH3 HO

H3C CH3

Tocopherol

Fats and Oils Nonglyceride Components

Phosphatides (%) 2.2 1.0 2.0 1.0 1.25 0.25 0.8 0.1 0.7 0.2 0.35 0.05 <0.1 0.075 0.025 <0.07 <0.07 <0.05 <0.07 Sterols (ppm) 2965 1125 8050 3230 15,050 7100 4560 1870 3495 1055 1878 978 100 2250 250 1100 310 805 335 1150 50 1100 300 Cholesterol (ppm) 28 7 53 27 57 38 68 40 26 18 54 54 <0.5 16 3 25 15 15 9 3500 500 1100 300 Tocopherols (ppm) 1293 300 692 85 1477 183 865 35 738 82 482 345 110 40 240 60 3 63 Tocotrienols (ppm) 86 86 355 355 30 30 270 270 256 218 89 89 560 140 30 30 49 22

Fat or Oil Soybean Canola Corn Cottonseed Sunflower Peanut Olive Palm Palm kernel Coconut Lard Tallow

I M NNG CH Y chi u di chu i carbon I M NNG CH Y bo ha (s l ng n i i) T L PHA R N TR NG THI VT L C NG / M M D O / L NG c u trc tinh th , , ' c u hnh n i i (cis / trans)

TNH CH T CNG NGH

TNH CH T C M QUAN

T l pha r n (%) (solid fat content SFC) ph n trm pha r n (tinh th ) trong m t ch t bo m t nhi t . (Thng th ng trong kho ng nhi t t T<T phng n T> thn nhi t) SFC c xc nh b ng cc phng php: - dilatometry - pulsed nuclear magnetic resonance (p-NMR) - differential scanning calorimetry (DSC).

Cho n th p nin 70: - Dilatometry l phng php chu n. D a trn s khc bi t v th tch gi a pha r n v pha l ng - K t qu o c g i l Ch s pha r n (solid fat index SFI) v i n v : mm3/g ho c mm3/25g

SFI > 35: r n; SFI <10: m m d o

End of melting

b c
Beginning of melting

Temperature

Dilatometric (D) melting curve of a glyceride mixture ab/ac represents the solid fraction, and bc/ac is the liquid fraction at temperature t. The ratio of solid to liquid is known as the solid fat index

C U TRC TINH TH nhi t PHA L NG CC PHA M M D O TRUNG GIAN

ki u tinh th

PHA R N
tr ng thi v t l

di n bi n nhanh ho c ch m

cc thng s

qu trnh k t tinh

c u trc tinh th

tr ng thi v t l

i u ch nh T c h nhi t T c khu y o Nhi t KI M SOT S HNH THNH & TNG TR NG CC TINH TH Hnh d ng Kch th c S k tt

C U TRC C A S N PH M

early

Time

later

Proposed mechanism (highly schematic) for nucleation of triacylglycerols (TAGs).Straight chains indicate crystallized TAGs, whereas bent chains indicate fluid TAGs

Ch t bo tr ng thi l ng : - v n gi m t tr t t nh t nh c a cc triglyceride ( c g i l hi u ng nh tinh th crystalline memory effect) - nhi t cao hn i m nng ch y r t nhi u m i ph v h t tr t t ny Khi nhi t h th p: - tr ng thi cn hi u ng nh tinh th s hnh thnh nhi u pha khc bi t hn so v i tr ng thi khng cn hi u ng

Khi nhi t h th p nhanh: hnh thnh cc tinh th phn tn m t cch nhanh chng do hi u ng nh tinh th . Khi nhi t h th p ch m: cc phn t c th i gian s p x p thnh hnh cc phi n m ng v t o thnh tinh th 3D

Ty theo s co ch c c a m ch carbon v gc nghin c a m ch carbon m hnh thnh cc d ng tinh th khc nhau

Tng tc gi a cc chu i acid bo Hnh th glycerol

T p h p cc u t n cng methyl Tng tc gi a cc chu i acid bo

double

triple

quatro

hexa

(Orthorhombic)

carbon hydrogen

(Triclinic)

Schematic diagrams comparing the polymorphs , and as exemplified by tristearin

A schematic model of polymorphic transformation of SOS.

Ki u tinh th Bi n php c tnh i m nng ch y Hnh d ng L c gic

Lm l nh nhanh t tr ng thi l ng R t nh , d v , trong su t 54oC

Lm l nh ch m t tr ng thi l ng Nh , d v 64oC Tr g c hnh thoi

K t tinh trong dung mi L n, th 73oC Hnh nghing 3 chi u

Ch t bo
Tristearin Tripalmitin Trimyristin Trilaurin Triolein 1,2-Dipalmitoolein 1,3-Dipalmitoolein 1-Palmito-3-steari-2-olein 1-Palmito-2-stearo-3-olein 2-Palmito-1-stearo-3-olein 1,2-Diacetopalmitin 55

i m nng ch y
44,7 32,8 15,2 32 18,5 20,8 18,2 26,3 25,3 20,5

'
63,2 56,6 45,0 34 12 29,8 33 33 40,2 40,2 21,6

73,5 66,4 58,8 46,5 4,5 34,8 37,3 39

42,3

Phase behavior in binary systems: (a) monotectic, continuous solid solution; (b) eutectic

Phase behavior in binary systems: (c) monotectic, partial solution; (d) peritectic

Diagram of the polymorphic occurrence for the LLL/PPP mixtures.

Phase behavior in the SOS/SSO mixtures.

Structure models of stable polymorphs of SOS, SSO, SOS/SSO compound crystal.

Structure models of the polymorphic forms of the SOS/SLS mixtures.

TNH D O

PHA R N T L CN I PHA L NG PHA R N: Phn tn u Cc tinh th nh Kho ng cch h p PHA L NG: Khng c ch y trong cc kho ng cch gi a cc tinh th T L : Pha r n: - ch ng l i s ch y nho - khng t o thnh tinh th c ng D O

Tinh th thch h p: hnh kim nh , d v khi ch u l c, ti t o d dng Ch s pha r n (SFI): 10 20

I M B C KHI I M CHY i m b c khi (smoke point): nhi t ch t bo b t u phn h y v b c khi (t o thnh acrolein) i m chy (flash point): nhi t ng n l a xu t hi n v bng ln trn b m t ch t bo)

Lo i d u D uc i D u u ph ng D u h t bng D u u nnh D u h ng dng D ud a D uc

i m b c khi (oC) 218 207 223 213 209 194 223

Di m chy (oC) 317 315 322 317 316 288 314

GI TR DINH D NG Ch dinh d ng khng h p l Thi u ho t ng th ch t

Cung c p nng l ng 9 kcal/g

D th a nng l ng Tch ly (50 100g/ngy)

Ch ng th a cn Bo ph ACID BO KHNG BO HA - cha c ch ng c v tc h i c a cc acid bo khng bo ha - 3 lm gi m nguy c c a cc b nh tim m ch, x v a ng m ch - gia tng s h p th cc vitamin tan trong d u - l c ch t t ng h p cc hormone - t l 6/ 3 khuy n co: 4 - t l thch h p khng bo ha/bo ha

Th c ph m Cn b ng nng l ng Chuy n ha Di truy n

CHOLESTEROL Low-Density Lipoprotein (LDL) V High-Density Lipoprotein (HDL)

Th c ph m COLESTEROL T ng h p (gan) Cn b ng gi a ngu n th c ph m & t ng h p

C u trc mng t bo Ti n t cc hormone steroid Acid m t v mu i m t

Oil Oilseeds: Canola

Oil Content (%)

Oil Yield (Pounds/Acre)

Producing Areas

4045

525590

Canada, China, India, France, Austria, United Kingdom, Germany, Poland, Denmark, Czechoslovakia, United States United States, Mexico, Canada, Japan, China, Brazil, South Africa, Argentina, Russia, Commonwealth of Independent States (CIS), Belgium, France, Italy, Germany, Spain, United Kingdom China, Russia, United States, India, Pakistan, CIS, Brazil, Egypt, Turkey, Australia China, India, Nigeria, United States, Senegal, South Africa, Argentina China, United States, Spain, Portugal United States, Brazil, Argentina, China, India, Paraguay, Bolivia Russia, Argentina, CIS, Austria, France, Italy, Germany, Spain, United States, United Kingdom

Corn

3.15.7

215390

Cottonseed Peanut Safflower Soybean Sunflower

1820 4550 3035 1820 3545

185210 11201245 545635 400450 460590

Oil

Oil Content (%)

Oil Yield (Pounds/Acre)

Producing Areas

Tree fruits and kernels: Coconut 6568 650870 Philippines, Indonesia, India, Mexico, Sri Lanka, Thailand, Malaysia, Vietnam, Mozambique, New Guinea, Ivory Coast Spain, Italy, Greece, Tunisia, Turkey, Morocco, Portugal, Syria, Algiers, Yugoslavia, Cyprus, Egypt, Israel, Libya, Jordan, Lebanon, Argentina, Chile, Mexico, Peru, United States, Australia Malaysia, Indonesia, China, Philippines, Pakistan, Mexico, Bangladesh, Colombia, Ecuador, Nigeria, Ivory Coast Malaysia, Indonesia, China, Philippines, Pakistan, Mexico, Bangladesh, Colombia, Ecuador, Nigeria, Ivory Coast

Olive

1535

90260

Palm Palm kernel

4550

26704450

4453

267445

D U U NNH (Soybean) Glycine max H t u nnh cho 18% d u (95 97% l triglyceride) Cng v i 1,5 2,5% phospholipid v 1,6% cc ch t bo khng x phng ha. Thnh ph n ch y u: palmitic 11% stearic 4% oleic 22 25% linoleic 52 55% linolenic 7 8% Cc acid bo khc 1%: 14:0, 16:1,20:0, 22:0 IV: 132 Phospholipid: 1,5 2,5% g m PC 55,3%, PE 26,3% v PI 18,4% Sphingolipid Sterol: 235 405 mg/100 g g m -sitosterol (125-236), campesterol (62-131), v stigmasterol (47-77). Tocopherol: 1370 mg/kg trong - (10%), (1%), - (64%), v -tocopherol (25%).

Components Triacylglycerols (%) Phospholipids (%) Unsaponiable matter (%) Phytosterols Tocopherols Hydrocarbons Free fatty acids (%) Trace metals Iron (ppm) Copper (ppm)

Crude oil 9597 1.52.5 1.6 0.33 0.150.21 0.014 0.30.7 13 0.030.05

Rened oil >99 0.0030.045 0.3 0.13 0.110.18 0.01 <0.05 0.10.3 0.020.06

Fatty acid Lauric Myristic Palmitic Palmitoleic Stearic Oleic Linoleic Linolenic Arachidic Gadoleic Behenic Lignoceric 12:0 14:0 16:0 16:1 18:0 18:1 18:2 18:3 20:0 20:1 22:0 24:0

Soybean Canola Cottonseed Sunower 0.1 11.0 0.1 4.0 23.4 53.2 7.8 0.3 0.1 3.9 0.2 1.9 64.1 18.7 9.2 0.6 1.0 0.2 0.2 0.9 24.7 0.7 2.3 17.6 53.3 0.3 0.1 0.5 0.2 6.8 0.1 4.7 18.6 68.2 0.5 0.4

Peanut 0.1 11.6 0.2 3.1 46.5 31.4 1.5 1.4 0.1 3.0 1.0

Eicosadienoic 20:2

Sterol -Sitosterol Campesterol Stigmasterol 5-Avenasterol 7-Stigmasterol 7-Avenasterol

Crude 183 68 64 5 5 2

Rened 123 47 47 1 1 <0.5

Mechanically pressed Solvent extracted Solvent extracted wheat germ oil soybean oil soybean oil Total tocopherol (ppm) -Tocopherol (%) -Tocopherol (%) -Tocopherol (%) -Tocopherol (%) 1257 9.3 1.2 62.8 26.7 1370 10.5 1.2 63.5 25.0 2682 67.8 32.2

D U U PH NG (Groundnut/Peanut) Arachis hypogaea H t ch a 40 50% d u. D b n m Aspergillus sp. sinh c t aflatoxin nhng khng c trong d u tinh luy n Thnh ph n chnh oleic 43% linoleic 36% Cc acid bo khc: linolenic 0 0,3%, palmitic, stearic C20, C22, C24: 7 8 % Cc triglyceride: OLL 26.1%, OOL 21.5%, POL13.4%, PLL 8.4%, LLL 5.8%, POO 5.6%, OOO 4.5%, SOO 4.4%, OOA 4.2% Phospholipide: 500mg/100g : PA 2.2%, PG 2.5%, PE 13.3%, PI 15.7%, v PC 66.4% Tocopherol: 20 130mg/100g g m - v Sterol: 337mg/100g g m -sitosterol (217), campesterol (49), stigmasterol (36),v 5-avenasterol (26) VI: 86 - 107

16:0 Florigiant Florunner Starr KS 10.8 11.4 14.2 10

18:0 2.9 2.1 3.3 2.4

18:1 53.1 50.9 43.3 43

18:2 27.3 29.1 33.0 36

20:0 1.8 1.6 1.8 1

20:1 1.0 1.1 1.1

22:0 1.9 2.4 2.7 3

24:0 1.1 1.3 0.7 2

D U D A (Coconut oil) Cocos nuciferus Ch a nhi u acid bo bo ha v i IV: 7 10 Ch y u l lauric acid D u lauric c s d ng: trong th c ph m cng nghi p x phng v ch t ho t tnh b m t D u d a cng l ngu n C8 v C10 t o cc MCT (medium chain triglyceride) dng lm ch t bi trn trong CB th c ph m

Mean (a) 6:0 8:0 10:0 12:0 14:0 16:0 18:0 18:1 18:2 18.3 20:0 20.1 IV Melting point (C) 8.5 24.1 0.1 0.4 7.3 6.6 47.8 18.1 8.9 2.7 6.4 1.6

Range (a) 00.6 4.69.4 5.57.8 45.150.3 16.820.6 7.710.2 2.53.5 5.48.1 1.02.1 00.2 6.310.6 23.025.0

Range (b) 00.7 4.610.0 2 5.08.0 45.153.2 16.821.0 7.510.2 2.04.0 5.010.0 1.22.5 00.2 00.2 09.2 6.310.6

(a) Leatherhead Food Research Association (LFRA) survey (b) Codex Alimentarius values

D U C (Palm) Elaeis guinensis Qu c : 20 24% d u v + 4% d u nhn D uv palmitic 44% stearic 4% oleic 39% linoleic 11% Cc triglyceride: POP (30%), POO (20%), PLO (10%), PLP (10%), tripalmitin (5%) Cc diglyceride: 5% Mu s m c a d u th do 500 700ppm carotenoid, ch y u -carotene (~56%) v -carotene (~35%) IV: 51 55 Phospholipid: 5 to 130 ppm tinh luy n b ng pp v t l

 Thnh ph n isoprenoid C15, C20 v squalene (C30) (980 ppm) Tocopherol: tocopherol v tocotrienol 710 1140 ppm Cc sterol: 200 600 ppm g m -sitosterol, campesterol, and stigmasterol S n ph m ch y u: palm olein, palm stearin v palm mid-fraction S d ng: d u chin: palm olein ch bi n: margarine, vanaspati, v shortening thay th b cacao (cocoa butter equivalent) (palm mid-fraction)
Palm oil 12:0 14:0 16:0 16:1 18:0 18:1 18:2 18:3 20:0 0.2 1.1 44.1 0.2 4.4 39.0 10.6 0.3 0.2 4.2 41.5 11.6 0.4 0.4 3.8 45.1 13.4 0.3 0.3 2.5 52.0 14.6 0.4 0.2 Palm olein 0.3 1.1 40.9 Super olein 0.3 1.0 35.4 Top olein 1.0 28.8 Stearin 0.10.6 1.11.9 47.273.8 0.050.2 4.45.6 15.637.0 3.29.8 0.10.6 0.10.6 Soft stearin 0.1 1.1 49.3 0.1 4.9 34.8 9.0 0.2 0.4 4.76.7 32.041.2 2.611.5 00.2 00.6 Palm mid-fraction 00.3 0.81.4 41.455.5

D UC

NHN (Palm kernel) Elaeis guinensis

Nhn c cho 45% d u, ch a nhi u lauric (tng t d u d a) Tocopherol: 10 ppm ch y u -tocopherol IV: 14 21 D u nhn c th phn o n thnh olein (IV21-26, MP 22-26C v stearin (IV 6-8, MP 31-33C) Mean 6:0 8:0 10:0 12:0 14:0 16:0 18:0 18:1 18:2 IV MP (C) 0.2 3.3 3.5 47.8 16.3 8.5 2.4 15.4 2.4 17.5 26.4 Range 00.8 2.14.7 2.64.5 43.653.2 15.317.2 7.110.0 1.33.0 11.919.3 1.43.3 14.121.0 24.028.3 Range 00.8 2.46.2 2.65.0 45.055.0 14.018.0 6.510.0 1.03.0 12.019.0 1.03.5 14.121.0

D U C I (Rapeseed/Canola) Brassica napus, B. rapa, v Brassica sp. D u c i erucic th p: oleic (>60%), linoleic (22%), linolenic (10%) (t l 6/3 cn i) Cc acid bo khc: chu i phn nhnh, chu i s l , khng bo ha n n-7, acid bo trans Triglyceride: LOO (22%), OOO (22%), LnOO (10%), LLO (9%), LnLO (8%), LOP (6%), v POO (5%) Phospholipid: dung mi 529 mg/kg p 242 mg/kg ch y u: PC, PA, PI, PE Sterol: 0,7 1,0% g m -sitosterol (52%), campesterol (28%), brassicasterol (14%)

Tocopherol: 770 mg/kg ch y u l - (270) v - (420) tocopherol. Chlorophyll v d n xu t: pheophytins a & b v pyropheophytins a & b Carotenoids: 130 ppm, trong 90% xanthophylls, xu ng 10 ppm D u erulic th p s d ng trong th c ph m: d u n s ng, d u chin t acid bo bo ha, nhi u acid bo khng bo ha, t l 6/3 thch h p Ch bi n ch t bo d o: spreads v shortening d u tinh luy n

LEAR Saturated acidsa 16:0 18:0 Monunsaturated acidsb 18:1 20:1 22:1 Polyunsaturated acids 18:2 18:3 6.3 3.6 1.5 62.4 61.6 1.4 0.2 31.3 21.7 9.6

HEAR 7.1 4.0 1.0 69.7 14.8 10.0 45.1 23.2 14.1 9.1

LLCAN 6.6 3.9 1.3 63.1 61.4 1.5 0.1 30.2 28.1 2.1

HOCAN 7.7 3.4 2.5 79.9 77.8 1.6 0.1 12.4 9.8 2.6

LTCAN 48.1 2.7 1.6 34.3 32.8 0.8 0.5 17.6 11.3 1.3

GLCAN 9.9 4.2 3.7 25.5 24.4 0.8 0.1 64.6 26.1 1.8

a Also 14:0, 20:0, 22:0, and 24:0 all at low levels. b Also 16:1. LEAR: Low-erucic rapeseed oil (canola). HEAR: High-erucic rapeseed oil. LLCAN: Low-linolenic rapeseed oil. HOCAN: High-oleic rapeseed oil. LTCAN: Rapeseed oil enriched in lauric acid (also contains 12:0 38.8%, 14:0 4.1%). GLCAN: Rapeseed oil enriched in -linolenic acid (also contains -linolenic acid 37.2%).

D U H NG DNG (Sunflower) Helianthus annuus H t h ng dng: 40 50% d u ch y u l linoleic oleic 20% palmitic 6% stearic 5% Triglyceride: LLL, LLO, v LLP Tocopherol: 530 700 ppm ch y u l tocopherol Sterol: 0,26 to 0,30% (sterol t do 72%, sterol ester 28%) Phospholipid: 0,72 to 0,86% Carotenoid: 1,1 1,6 ppm Sp: 300 600 ppm (t v h t)

Traditional Saturate dacids Oleic acid Linoleic acid Iodine value (approx) 1113 2030 6070 128

High-Oleic 910 8090 59 79

Mid-Oleic<10 5575 1535 108

D U -LIU (Olive) Olea europaea Thnh ph n chnh palmitic 10,5% stearic 2,6% oleic 76,9% linoleic 7,5% Cc acid khc: myristic, palmitoleic, heptadecanoic, heptadecenoic, linolenic, v C20, C22, C24 bo ha Cc triglyceride: OOO (4059%), LOO (12 20%), POO (1220%), POL (67), v StOO (37%). Phospholipid 40 135mg/kg S t 0,5 3,0 ppm. ng 0,002 0,2 ppm Thnh ph n khng x phng ha 0,5 1,5% g m: -tocopherol 100 300mg/kg squalene

Minor components by type Carotenes Chloropylls Desmethylsterols 4-Methylsterols 4,4-Dimethylsterols (triterpene alcohols) Triterpene dialcohols Fatty alcohols Waxes Polyphenols Volatile compounds

Concentration in virgin olive oil 120 mg/kg, usually <10 1030 mg/kg 100200 mg/100g oil 2070 mg/100g oil 100150 mg/100g oil 120 mg/100g oil <35 mg/100g oil <35 mg/100g oil

Major components within the category -carotene, lutein (3,3-dihydroxy- ,carotene) pheophytin-a -sitosterol, 5-avenasterol, campesterol obtusifolol, cycloeucalenol gramisterol, citrostadienol -amyrin, butyrospermol, cycloartenol, 24methylene-cycloartenol erythrodiol, uvaol 22:0 to 26:0 C36 to C46 saturated and unsaturated esters and esters of nonfatty alcohols A range of aromatic compounds, mainly carboxylic acids or alcohols, with one or more phenolic groups Mainly short-chain saturated and unsaturated aldehydes and alcohols

D U B P (Maize) Zea mays c trch ly t m m h t: l ph ph m c a cng ngh tinh b t L lo i d u c l i cho c c kh e v ch a t acid bo bo ha, nhi u linoleic nhng r t t linolenic 16:0 10,9% 18:0 2,0% 18:1 25,4% 18:2 59,6% 18:3 1,2% a s cc triglyceride ch a t 2 n 3 linoleic LLO 20 23% LLL 18 25% LLP 14 15% OOL 11 12% PLO 10 11% Thnh ph n khng x phng ha: 1,3 2,3% g m - sterol: -sitosterol (55-67%), campesterol (19-24%) 5avenasterol (4-8%), stigmasterol (4-8%) - tocopherols ( 23-573, 0-356, 268-2468 v 23-75) m c ppm

D U M (Sesame) Sesamum indicum H t m ch a 50 60% d u v i cc ch ng oxy ha nh sesamolin, sesamin, sesamol v tocopherol D u m tinh luy n ch a palmitic 9,2% stearic 5,8% oleic 40,6% linoleic 42,6% Cc acid bo khc 2% Sterol: 0,51 0,76%, trong 35% d i d ng ester ch y u l desmethylsterol (85 to 89%), monomethylsterol (10%) v triterpene alcohol (2 to 4%) Tocopherol: 400 700ppm trong -tocopherol (98%), Lignan: sesamin (0,02 1,13%), sesamolin (0,02 0,59%), (trong qu trnh tinh luy n, sesamolin c chuy n thnh cc h p ch t phenol ch ng oxy ha)

D U CM G O (Rice bran) Oryza sativa Cm g o ch a 24% d u + 6% acid bo t do D u cm g o th: triglyceride 83 86% di-, monoglyceride, FA t do, sp: 3 4% glycolipid 6 7% phospholipid 4 5% khng x phng ha 4% Thnh ph n acid bo palmitic 20% oleic 42% linoleic 32% stearic 2 4% linolenic 0,5 1,8% 14:0,16:1, 20:0, 20:1, 22:1 Triglyceride OOO, PLO, v PLL Sp: 1 4%. Ester c a acid bo bo ha C16 C26 v i alcohol bo ha C24 C30

Sterol 4,8g/100g: desmethylsterols (3225 mg/100 g), monomethylsterols (420 mg/100 g), dimethylsterols ho c triterpene alcohols (1176 mg/100 g). a s cc sterol d i d ng ester v i ferulic acid v c g i chung l oryzanol (115 787mg/100g) c tc d ng ch ng oxy ha Tocopherol: 915mg/kg g m -, , -tocopherols (347, 89, 42,) v -, -, -tocotrienols (126, 301, 10,). D u cm g o c nh gi lm gi m cholesterol trong mu b ng cch gi m LDL v VLDL nhng khng thay i HDL. Tc d ng ny c cho l do thnh ph n khng x phng ha c a d u nh t l oryzanol.

D U H T BNG V I (Cottonseed) Gossypium hirsutum v G. barbadense H t bng v i cho 16% d u c mu vng s m v ch a gossypol (tetracyclic phenolic compound). S d ng ch y u trong th c ph m Thnh ph n acid bo ch y u: palmitic 23% oleic 17% linoleic 56% Cn l i 4%: myristic, stearic, arachidic, behenic, palmitoleic v linolenic Ch a 10% acid c vng cyclopropene: malvalic (C18) v sterculic (C19) gy tc ng x u n cc protein (gi m nng xu t tr ng g v bi n mu trng tr ng thnh h ng Cc phospholipid ch y u l PC, PE, PI D u th ch a - (~350 ppm) v tocopherols (~500 ppm) IV: 99 - 113

D U LANH (Linseed/Flaxseed) Linum usitatissimum Thnh ph n palmitic 6,0% stearic 2,5% oleic 19,0% linoleic 24,1% linolenic 47,4% Tocopherol: 588mg/kg ch y u -tocopherol Sterol: 4200mg/kg g m -sitosterol (46%), campesterol (29%), 5-avenasterol (13%), v stigmasterol (9%). S d ng ch y u cho d u sn, vc-ni do khng bo ha cao Ngy nay do vai tr c a acid -3 nn d u lanh c dng trong th c ph m V ph i tr n v i cc lo i d u khc

TH U D U (Castor) Ricinus communis D u th u d u c nh t cao, t ha tan trong hexane, ha tan t t trong ethanol Ricinoleic acid (12-hydroxyoleic) chi m 90%, m t l ng nh palmitic, oleic, linoleic, 9,10-dihydroxystearic. a s cc triglyceride l triricinolein ho c ester c a 2 ricinoleic v 1 acid bo khc. Dng trong cng nghi p v m ph m

Sau khi trch ly, bnh d u ch a ricinie (alkaloid c c tnh nh ) v ricin (protein c c tnh m nh v gy d ng)

B CACAO (Cacoa butter) Theobroma cacao Cc s n ph m chnh: liquor, b cacao v b t cacao 100g h t: 40g b cacao + 40g bt cacao i m nng ch y c a b cacao: 32 35oC Thnh ph n ch y u: palmitic 24 30% stearic 30 36% oleic 32 39% Cc triglyceride th ng l SOS c ng ph thu c vo FSC, th ng gi m t 45% xu ng 1% khi T bi n i t 30 ln 35oC

Ghana odine value Melting point C Diacylglycerols (%) Free acid (%) Component acids (%) Palmitic Stearic Oleic Linoleic Arachidic Trisaturated Monounsaturated POP POSt tOSt Diunsaturated Polyunsaturated 24.8 37.1 33.1 2.6 1.1 0.7 84.0 15.3 40.1 27.5 14.0 1.3 35.8 32.2 1.9 1.53

Ivory Coast 36.3 32.0 2.1 2.28 25.4 35.0 34.1 3.3 1.0 0.6 82.6 15.2 39.0 27.1 15.5 1.3

Brazil 40.7 32.0 2.0 1.24 23.7 32.9 37.4 4.0 1.0 trace 71.9 13. 6 33.7 23.8 24.1 4.0

Malaysia 34.2 34.3 1.8 1.21 24.8 37.1 33.2 2.6 1.1 1.3 87.5 15.1 40.4 31.0 10.9 0.3

Component triacylglycerols (%)

Specific gravity Canola Castor Cocoa butter Coconut Corn Cottonseed Groundnut Linseed Olive Palm Palm kernel Palm olein Palm stearin Rice branoil Sesame Soybean Sun flower 0.9140.920 0.9560.970 0.9730.980 0.9080.921 0.9170.925 0.9180.926 0.9140.917 0.9240.930 0.9100.916 0.8910.899 0.8990.914 0.8990.920 0.8810.891 0.9160.921 0.9150.923 0.9190.925 0.9180.923

Temp C 20/20 15.5/15.5 25/25 15.5/15.5 15.5/15.5 20/20 20/20 25/25 20/20 50/20 40/20 40/20 60/20 25/25 20/20 20/20 20/20

Refractive index 40C 1.4651.467 1.4661.473 1.4561.458 1.4481.450 1.4651.468 1.4581.466 1.4601.465 1.4721.475 1.4681.470 (20) 1.4491.455 (50) 1.4521.488 1.4581.459 1.4471.451 1.4651.468 1.4651.469 1.4661.470 1.4671.469

Iodine value 110126 8191 3240 611 107128 100115 86107 170203 7594 5055 1421 >55 <49 99108 104120 124139 118145

Sapon. value 182193 176187 192200 248265 187195 189198 187196 188196 184196 190209 230254 194202 193205 181189 187195 189195 188194

Nonsap (%) <2.1 0.21.0 <1.5 13 <2 <1.1 0.12.0 1.5 <1.4 <1.1 <1.4 <1.0 35 <2.1 <1.6 <1.6

CH T BO S A Milk fat S a b ch a: ch t bo: 3,8% protein: 3,3% carbohydrate: 4,7% triacylglycerols (95 98%) diacylglycerols (1,3 1,6%) monoacylglycerols (v t) acid th do (0,1 0,4%) phospholipids (0,8 1,0%) sterols (0,2 0,4%) Cc acid bo ch y u: C4C12 (13,8%), myristic acid (10,6%) palmitic acid (28,2%) stearic acid (12,6%) oleic acid (21,4%) acid bo ha m ch th ng 65,8% acid bo ha phn nhnh 2,6% acid khng bo ha n 27,4% acid khng bo ha a 4,1% Linoleic (2,4%) linolenic acid (1,1%) ARA (0,14%) EPA (0,09%) DHA (0,01%) PC PE SM

Thnh ph n khng x phng ha: 0,40% 2/3 l cc sterol, ch y u l cholesterol (95%) cn l i l lathosterol, 7-dehydrosterol,24-methylenecholesterol, v fucosterol 1/3 l cc vitamin A, D, E v hydrocarbon

Acid 4:0 6:0 8:0 10:0 12:0 14:0 15:0i 15:0 16:0 17:0i 17:0 18:0

Milk 4.5 2.3 1.3 2.7 3.0 10.6 0.7 1.0 28.2 0.7 0.6 12.6

Butter 5.3 2.8 1.6 3.1 3.4 10.8 0.3 1.0 28.1 0.5 0.6 10.6

Acid 14:1 16:1 n-7 18:1 c 18:1 t 20:1 18:2 n-6 Saturated Monounsaturated Polyunsaturated Not included

Milk 0.9 1.8 21.4 1.7 0.6 2.9 69.1 25.5 2.9 2.5

Butter 0.9 1.4 20.8 0.3 2.0 69.0 22.5 2.0 6.5

The major phospholipids (PL) in milk and the major fatty acids present in each PL class PL %mol 14:0 16:0 18:0 18:1 18:2 Other PC 34 PE 32 SM 25 8 1 2 36 11 22 11 12 4 26 54 5 5 12 1 14% 10% 22:0 15%, 23:0 27%, 24:0 15% other 9%

Other PL present include phosphatidylserine (3%), phosphatidylinositol (5%), and plasmalogens (3%) Other acids present include 12:0, 15:0, 16:1, 17:0, 18:3, 20:3, and 20:4.

L N (Lard)

M l n: palmitic (26%), oleic acid (44%), v palmitoleic (5%) Cc triglyceride ch y u: MSS (33%), MSM (28%), MSD (12%), SSD (7%), SSS (7%), MMM (5%), MDM (3%), (S = saturated, M = monoene, D = diene) Ch a nhi u cholesterol: 3000 to 4000 mg/kg Thi u cc ch t ch ng oxy ha t nhin
Fatty Acid 10:0 12:0 14:0 16:0 16:1 18:0 18:1 18:2 18:3 Saturated Monounsaturated Polyunsaturated Beef Tallow 0.9 3.9 26.0 4.4 19.8 27.7 3.2 0.1 50.6 43.7 4.2 Mutton Tallow 4.0 22.5 2.4 20.4 39.3 5.8 2.4 46.8 42.4 8.1 Lard 0.1 0.2 1.4 24.9 2.8 14.1 43.1 10.7 1.0 40.7 47.2 11.7

D U C (Fish oil) D u c: acid bo bo ha: myristic, palmitic acid bo khng bo ha n: t hexadecenoic n docosenoic acid bo khng bo ha a: C20, C22 thu c h -3

Fatty acids identified in fish oils Acid type Saturated straight chain Monounsaturated Polyunsaturated Number of carbon atoms 12, 1424 odd and even members 14, 16, 17, 18, 19, 20, 22, 24 16:24, 18:24, 20:25, 21:5, and 22:36

Saturated branched chain 15, 17, 18, 19

Three classes of lipids found in fish bodies

Lipids that may be found in marine oils. Free fatty acids: up to 5% or even 10% of oils. Cholesterol and its esters: 0.51.0%, wax esters may be major oil components in oils from certain fish.

Phytol, pristane and phytane, are associated and may be found in some fish oils. Phytanic, pristanic, and 4,8,12-trimethyltridecanoic acids are common fish oil components derived from phytol. Squalene is usually of animal origin and a feature of some shark liver oils.

Typical fatty acid composition of some commercial fish oils Anchovy Capelin Cod Liver Men-haden Saturated 14:0 16:0 16:1 18:1 20:1 22:1 20:5 22:5 22:6 Other 16 13 15 24 17 17 17 9 17 13 10 1 1 22 2 9 7 10 10 14 17 15 8 6 4 10 8 25 10 7 10 1 10 9 19 12 11 1 14 2 8 8 18 10 13 4 3 16 2 9 5 12 6 20 10 9 7 3 11 3 22 3 21 1 3 6 2 22 Sardine Salmon Tuna (Farmed)

Monounsaturated

Polyunsaturated (n-3)

Squalene (C30H50): g m 6 m v isoprene. H u nh ch c trong d u gan c m p. L h p ch t quan tr ng c chuy n ha thnh mavalonic acid (C6), triterpene (C30) v cc sterol Vitamin: d u gan c l ngu n vitamin A v D Glycerol ether: d u gan c m p ch a nhi u glycerol ether, nhng khng hon ton d i d ng diacyl. Cc ether mang ch y u cc chu i bo ha c khng bo ha n th ng l 16:0 (chimyl), 18:1 (selachyl), v 18:0 (batyl). Acid bo chu i di khng bo ha a (Long-chain polyunsaturated fatty acids) Khng bo ha n : (16:1, 18:1, 20:1, 22:1) c trch (herring) 62%, gan c tuy t (cod) 57% Khng bo ha a -3: EPA (20:5), DHA ( 22:6) h c thu 6% EPA v 22% DHA c sardine 16% EPA v 9% DHA c mi d u 14% EPA v *% DHA c h i 7% EPA v 11% DHA

Original acids (%) Hours Herring Tuna Sardine Chileanfishoil 24 24 28 12 EPA 5.5 5.2 16.8 20.0 DHA 8.0 24.5 12.3 7.2

Recovered free acids Weight % EPA 1.9 6.0 13.2 15.8 DHA 50.6 71.1 50.0 25.7 Recovery % EPA 3.1 28.6 14.1 13.1 DHA 67.6 89.8 78.4 51.5

Council for Responsible Nutrition Quality Standards for Nutraceutical Grade Fish Oils in the United States.

Peroxide Value (PV) by iodine titration The first compounds formed by oxidation of an oil are hydroperoxides. The usual method of hydroperoxide assessment is by determination of the Peroxide Value, which is reported in units of millimole of hydroperoxide per kilogram of oil (or expressed as milliequivalents of iodine per kilo of oil).

Anisidine Value (AV) which detects aldehydes by a color reaction the PV of an oil may therefore be reduced or eliminated by heating the oil in the absence of oxygen. A large portion of non-volatile carbonyl compounds are formed by decomposed peroxides during the processing of a fish oil. The Anisidine assay measures the high-molecular weight saturated and unsaturated carbonyl compounds. The AV represents the level of aldehydes, principally 2-alkenals, present in the oils Totox Value The Totox Value is used as a measure of the precursor non-volatile carbonyls present in a processed oil, plus any further oxidation compounds developed during storage. This value is determined by the following formula: Anisidine Value + 2PV.

C B NGHI N N U CHN N C N U C CHN P D CH P L C TH D CH P L NG D CH P TCH PHA PHA D U N C TCH PHA BAY HI S Y LM L NH XAY PHA N C C N XC

D U C

N C R A

B T C

NGHI N Nguyn li u c nghi n nh

Ph v mng t bo, phng thch d u c

GIA NHI T Gia nhi t trong n i h p hnh tr di c trang b m t bng t i tr c vt Nhi t 100oC Th i gian 20 pht

P Th ng s d ng my p c tr c xo n i Tch pha l ng (ph n n c bao g m d u) v pha r n (ph n xc c)

Ph n xc c c th ch a n 50% n c, c nh ti ra v s y kh n m 8 10%. Cu i cng xay thnh b t c.

Trong qui trnh Alfa-Laval Centrifish, thi t b Decanter centrifuge c s d ng tch pha thay cho thi t b p

Self-cleaning disc centrifuge

Pha l ng sau c tch thnh pha d u v pha n c (stickwater) b ng my ly tm Pha d u: r a n c, s y kh d u th Pha n c: c c c v tr n chung v i xc c b t c

Quadruple effect stickwater evaporator

NGUYN LI U C

Pha d u Pha r n Pha n c

1000kg

N U 1000kg

680kg P 650kg

320kg

30kg TCH PHA 542kg 350kg 92kg C C 320kg S Y

D U
108kg LY TM 450kg

442kg XC C 212kg

Mass balance

Production of pharmaceutical-grade fish oil or nutritional supplements.

Step 1 : Extraction of fish oil Step 2 : Winterizationremove limited amounts of saturated fats Step 3 : Absorptionremove heavy metals Step 4 : Preliminary Molecular Distillationrefining touch up" to reduce PCBs and cholesterol Step 5 : Oil conversion into ethyl esters Step 6 : Ethyl Ester Thermal Fractionationremove additional saturated fats Step 7 : True Molecular Distillationfinal refining to assure removal of all manmade pollutants such as PCBs and long-chain monoenes Step 8 : Pharmaceutical-grade fish oil concentrates Step 9 : Quality Controlprior to packaging

PCB : dioxin-like polychlorinated biphenyls

100 kgs of health food-grade fish = oil 1 kg of pharmaceutical-grade fish oil concentrate Producing pharmaceutical-grade fish oil concentrates = to assure maximum EPA/DHA purity and concentration of long chain omega-3 fatty acids essential for eicosanoid modulation.

EPA > 40% DHA > 20% EPA/DHA > 65% Total W-3 > 75% Total Polyunsaturated Fatty Acids > 85% PCB < 10ppb/g

Crude Fish Oil Quality Guidelines and Physical Characteristics.

Council for Responsible Nutrition Quality Standards for Nutraceutical Grade Fish Oils in the United States.

scheme for production of ethyl ester concentrates of marine oil fatty acids,

QU OLIVE

NGHI N G m 3 cng o n chnh: NHO TR N Nghi n nt (crushing) Nho tr n (malaxation) P Tch pha (separation)

LY TM D U P L NH EXTRA VIRGIN OLIVE OIL Acidity < 1% VIRGIN OLIVE OIL 1% < Acidity < 3% D U TH TINH LUY N D U OLIVE (virgin oil + refined oil) Acidity < 1,5%

Flow diagram of steps to prepare olives for extraction of oil.

Flow diagram of olive oil extraction and processing to yield olive oil products and byproducts.

Flow diagram of solvent extraction of pomace.

Pressure extraction of oil. 1, movement of the rack; 2, movement of the oil; A, mobile head; B, fixed head.

Centrifuge for oil extraction from olive-pomace

QU OLIVE

NGHI N

FINE PASTE

Lm v cc t bo gi i phng d u

c i

Millstone

Hammer mill

NHO TR N: fine paste c khu y tr n nh c th gia nhi t nh

H i t cc h t d u

Malaxer

R n P: Tch pha L ng (vegetation water + olive oil)

Oil Press

Oil Expeller Italy : a three-phase decanter yielding a Spain : two-phase decanter providing a wet (65 to 72% moisture) pomace pomace of 55 to 60% moisture and separate vegetation water and oil streams stream

N c (vegetation water) LY TM: Tch pha D u R A N C S Y KH L C B O QU N R a n c: khng ph bi n v c th lm gi m hm l ng polyphenol Tng hi u su t : - thm b t tan (talc/talcum) (Mg3(Si4O10)(OH)2), vo trong paste (4% tr ng l ng) - enzyme pectolitic + (hemi)cellulolytic

100

Qu olive

100

Fine paste

100

100 + 30

Nho tr n v i n c nng

Pha r n

40

90

Pha l ng

press cake (pomace) D u L ng d u cn l i trong b 6% 1,8% l ng d u trong qu 20 70 N c

Virgin olive oil: the oil obtained from the fruit of the olive tree solely by mechanical or other physical means under conditions, particularly thermal conditions, that do not lead to alterations in the oil, and which has not undergone any treatment other than washing, decantation, centrifugation, and filtration.

Extra virgin olive oil: virgin olive oil that has an organoleptic rating of 6.5 or more as determined by the IOOC method and a free acidity, expressed as oleic acid, of not more than 1 g per 100 g. Fine virgin olive oil: virgin olive oil that has an organoleptic rating of 5.5 or more and a free acidity, expressed as oleic acid, of not more than 1.5 g per 100 g.

Semifine virgin olive oil (or ordinary virgin olive oil): virgin olive oil that has an organoleptic rating of 3.5 or more and a free acidity, expressed as oleic acid, of not more than 3.3 g per 100 g. Refined olive oil: olive oil obtained from virgin olive oils by refining methods that do not lead to alterations in the original triglyceride structure. Olive oil: the oil consisting of a blend of refined olive oil and virgin olive oil in various proportions.

Fatty acid composition of oilve oil

CAN: carbon atom number

BU NG QU TI TI T TRNG TU T QU NINH TRCH LY PH N R N D U L C TRONG S Y KH D UC TH L C TH L NG C N LY TM C N C N TH I D U X + NHN TCH V NGOI X

H T S Y KH/LM NGU I XAY V TCH V NHN S Y KH NHN C 11% 15h

TI T TRNG

B t ho t enzyme th y phn lipid Tch qu ra kh i bu ng Lm m m qu ng t protein

S d ng hi n c nng: 3 bar (3kg/cm2) (143oC) - bi kh - th i gian x l hi n c 60 pht Th i gian x l 1 m : 80 90 pht bao g m c qu trnh n p v tho nguyn li u

TU T QU

Th ng l thi t b l ng quay: 1. L c m nh, 2. p giai o n ny qu tng i m m nhng v n cn nguyn v n

NINH

Hm nng qu c T o i u ki n cho ph n v tch kh i nhn Thi t b : N i hi Ngu n nhi t: hi n c nng + n c nng Nhi t : 90 100oC Th i gian: 20 pht Digester:cylindrical, steam-jacketed vessel.

Pha r n: x + nhn P TR C XO N screw press Pha l ng: 53% d u + 7% c n b + 40% n c (66%) (10%) (24%)

L ng L C TH R n S d ng sng rung (vibrating screen)

D u L NG C n S d ng b n l ng (settling tnak)

S Y KH

S y chn khng D u: 0,1 0,12% n c < 0,02% t p ch t

Fatty acid composition of malaysian palm oil

Carotenoid composition of palm oil

Tocopherols and Tocotrienols in crude palm oil

Cholesterol levels in crude oils and fats

Sterol composition of crude and refined palm oil and their products

Major physical properties of palm oil

Palm oil (100%)

First fractionation

First olein (85 95%)

First stearin (10 15%)

Second fractionation

Second olein (55 65%)

Palm midfraction (25 30 %) Fractionation and palm midfraction

Palm midfractions solids content