Chemical versus Physical Refining of

Rice Bran Oil

R. Verh1,
V. Van Hoed1, J. Vila Ayala2, W. De Greyt2
1 Ghent

University
Faculty of Bioscience Engineering
Department of Organic Chemistry
2 De Smet Ballestra,, Zaventem, Belgium
Ballestra

Vera.VanHoed@
Vera.VanHoed@UGent.be

Overview

Introduction






Production of rice
Production of rice bran oil (RBO)
Composition of RBO
Bio-active compounds
Properties

Influence of chemical and physical refining on RBO

quality

Conclusions

World rice (paddy) production in 2007

(million Mt/y)

Source: FAO

Production of Rice Bran Oil

Hull

20%

Pericarp
Seed Coat
Nucellus
Aleurone layer
Endosperm
Embryo

Bran

8%

70%

2%

Rice bran: 15 20 % oil

4

Composition of crude rice bran oil

Unsaponifiable
material
~ 5,4 %

High

Saponifiable
material

Refining necessary

Main FA composition (%):

oleic (43) > linoleic (32) > palmitic acid (20)

~ 94.5 %

Other characteristics
Colour: brown
Minerals (ppm): P (488) >> Ca (27) > Mg (18) > Fe (5)
5

Bioactive compounds in rice bran oil

Qualitatively different composition of bioactive minor compounds.
- Phytosterol content: 30 g kg -1
other oils:
oils: 1 5 g kg -1

R'

R: H free sterol
R: COR fatty acid ester
R: ferulic acid  -oryzanol
RO

- Tocotrienols
6

Comparison of smoke point

and balance of fats in some
commonly used oils

OIL TYPE

SMOKE
POINT
(C)

MONOUNSATU
RATED
FAT

POLYUNSATU
RATED
FAT

SATURATED FAT

Rice Bran Oil (refined)

254

47%

33%

20%

Olive (Extra virgin)

191

77%

9%

14%

Canola (Refined)

242

61%

33%

7%

Peanut (Refined)

232

48%

34%

18%

Soybean (Refined)

232

24%

61%

15%

Grape seed (Refined)

216

14%

77%

9%
7

Comparison of natural antioxidants in edible oils

VITAMIN E
TOCOPHEROL
(ppm)

VITAMIN E
TOCOTRIENOL
(ppm)

ORYZANOL
(ppm)

TOTAL
NATURAL ANTIOXIDANTS
(ppm)

Rice Bran Oil (refined)

81

336

2000

2417

Olive (Extra virgin)

51

51

Canola (Refined)

650

650

Peanut (Refined)

487

487

Soybean (Refined)

1000

1000

Grape seed (Refined)

256

149

405

OIL TYPE

Refining of rice bran oil

Crude Rice Bran Oil
Physical refining

Chemical refining
Neutralisation

FFA

NaOH

Acid degumming

Soaps
(Na+ salt of FA)

Bleaching
2 % activated clay - 105

Dewaxing

Wax

Dewaxing

FFA

FFA stripping,
= Pre-neutralisation (packed column,
210C-2mbar-1.5%steam )

Bleaching
Deodorisation
240 C / 6-7 mbar
2 % steam 90 min

Deodorizer
volatile
volatile
compounds distillate compounds
and FFA

Chemically Refined
Rice Bran Oil

Deodorisation
(255C-3mbar-1% steam)

Physically Refined
Rice Bran Oil
9

Van Hoed et al., JAOCS, 83 (4), pp 315-321, 2006

Influence of refining on
free fatty acids (FFA) content

AD = Acid Degummed; DW = Dewaxed ; pre-N = pre-neutralized; Bl = bleached

10

Influence of refining on minerals

content and Lovibond color
Chemical refining
minerals (mg/kg)

Crude

Neutralised

Bleached

Dewaxed

Deodorised

P
Fe

488.3
5.3

3.9
0.3

0.1
0.3

0.2
0.01

0.2
ND

70Y/13R/6B

70Y/4,3R/2B

12Y/2R

70Y/10R/0,2B

35Y/3,8R

13Y/2,2R

Colour 1"
Colour 5

1/4

"

Physical refining
minerals
(mg/kg)

Crude

Acid Degummed

Dewaxed

Pre- Neutralized

Bleached

Deodorised

391

16

8.6

0.9

0.9

Fe

17.5

0.33

0.4

0.3

0.35

0.3

70Y/6R

70Y/6.3R/0.5B

44Y/4.4R/0.5B

27Y/2.7R/0.4B

50Y/6.8R

35Y/2.8R

Colour 1"
Colour 5 1/4 "

11

Influence of chemical and physical

refining on fatty acid composition
Chemical refining

Physical refining

Fatty Acid composition

(%)

Crude

ChemRef

Crude

PhysRef

C14:0

0,4

0,4

0,5

0,4

C16:0

20,7

21,0

20,5

20,2

C16:1

0,1

0,1

0,2

0,2

C18:0

1,4

1,5

2,1

2,2

C18:1

43,5

44,3

42,8

43,4

C18:2

32,6

31,8

32,8

32,0

C18:2 trans

0,5

0,3

C18:3

1,3

0,3

1,3

1,1

C18:3 trans

0,1

0,1

Sum trans

0,6

Physical refining: slightly lower total t-FA : 0,4 %

0,4
12

Changes in unsaponifiable matter during refining

1.Oryzanols
Chemical refining

Physical refining

AD = Acid Degummed; DW = Dewaxed ; pre-N = pre-neutralized; Bl = bleached

13

Changes in unsaponifiable matter during refining

2. Phytosterols
Chemical refining
Changes in phytosterol composition during chemical refining
3,50

24-Methylene cycloartanol

Main decrease: 24-methylene cycloartanol

(24-M) (oryzanol component)

3,00
2,50
g/100g

Isomer 24-Methylene cycloartanol =

cyclobranol
Citrostadienol

Bleaching step:
step: Formation of
isomers of 2424-M

2,00

Isomer 24-Methylene cycloartanol

D7-Avenasterol
D7-sitosterol+cycloartanol
Gramisterol
D5(24)-stigmastadienol

1,50

Sitostanol+D5-avenasterol
B-sitosterol

1,00
Clerosterol
D7-campesterol

0,50

Stigmasterol

0,00

Campesterol+campestanol

Crude

Neutralised

Bleached

Dewaxed

Deodorised

Changes in unsaponifiable matter during refining

2.Phytosterols
Physical refining
cyclobranol
citrostadienol

Changes in phytosterol content and composition

during physical refining

24-methylenecycloartanol

4,00

24-methylene cycloartanol

3,50

Bleaching :
isomers of 2424-M

isomer 24-methylenecycloartanol
isomer 24-methylenecycloartanol

3,00

7-avenasterol
cycloartenol
7-sitosterol
gramisterol

2,50

5-avenastanol

2,00

sitostanol+5-avenasterol
-sitosterol

1,50

clerosterol
7-campesterol

1,00

episterol

0,50

stigmastanol
stigmasterol

0,00
Crude

Acid
degumming

1st Bleaching

Dewaxing

Pack column

BL2

DEO2

campestanol
campesterol

Changes in unsaponifiable matter during refining

3.Tocopherols
Chemical refining

Total tocopherol content

from 780 to 620 mg/kg
Only significant change: during deodorizing: decrease in gamma-tocopherol

16

Changes in unsaponifiable matter during refining

3.Tocopherols
Physical refining
-T
-T

CRUDE

-T3
ADG

-T3

1ST BL

d-T3

DEWAX
PC
BL2
DEO2
0

200

400

600

800

mg/kg

Overall: similar tocopherol losses as in chemical refining

17

Comparison unsaponifiable matter in chemical

deodoriser distillate refined rice bran oil
Parameters
(g/100g)
Unsaponifiable
matter

FFA

Crude RBO

5,4

Refined
RBO
2,7

Deodoriser
distillate
37,9

Squalene
Total tocos

0,028
0,078

0,008
0,062

1,9
3,2

Total sterols

2,94

1,83

14,83

7,5

0,04

32,9

Valorisation of rice bran oil deodorizer distillate (RBODD):

Crystallisation of sterols: yield 60-70 %
18

Conclusions
RBO: rich in minor components, especially sterols
(oryzanol)  functional food!
Refining
1. Chemical
 Neutralisation: major influence on general composition
 Sterol and oryzanol content:
 Decrease of content
 Isomerisation
 Deodorisation  valuable waste product (RBO deodorizer distillate)

2. Physical
 Target:

similar quality parameters as chemical refining

(especially: color)
 Main advantage: better oryzanol retention

19

Thank you

for your
attention!
20