eurotiox ®, the most cost-effective antioxidant eurotiox

Eurotiox ® , the most cost-effective antioxidant

EUROTIOXEUROTIOX


•SERIES OF DESTRUCTIVE CHEMICAL PROCESSES

•OCCURS IN ORGANIC MATERIALS

•CHANGES THE CHEMICAL NATURE OF AFFECTED MOLECULES

•INCREASINGLY FAST

•ROOM TEMPERATURE REACTION

•CAUSES RANCIDITY IN FATS, OILS

AUTOXIDATION

BIOTIN


Oxidation Oxidation influencedinfluenced by: by:

Moisture: free water in raw material and feed

Catalysts: metals promoting free radical formation,

Light: promotes oxidation

Temperature: increase oxidation also during cooling

Contact with air: improves peroxide formation

Enzymes: lipase, lipoxygenase

Time: storage time, production


Aldehydes from Fat Autoxidation

Carbonyls Flavours Threshold (ppm)

2-Decenal 5.52-Undecenal 4.22-Nonenal 0.12-Octenal 1.0Hexanal 0.152-Heptenal 0.63Heptenal 0.042Nonanal 0.32Octanal 0.0682-4=Decadienal 0.284 cis-Heptenal 0.0014-trans-Heptenal 0.324 trans, 6-trans Nonadienal 0.0012 trans, 6-cis Nonaienal 0.002

Frankel, 1984


THE INFLUENCE OF OXIDISED FAT ON THE MICRO-FLORA IN BROILERS

(11 DAYS)

0

2

4

6

8

10

Facult.Anaerobes

E.coli Lactobacilli

Fat

Fat + AO

Oxidised Fat

Oxidised Fat + AO


TOXIC METABOLITES OF FAT OXIDATION

FROM: Poul. Sci. Abstracts (1994) Vol. 73, Suppl. 1, pg 47.

Shorten small intestine villi length

Reduce nutrient adsorption


Autoxidation and Animal production Reduced Egg production in laying hens (72%)

(Voreck & Kirehgessner, 1981) Autoxidation products are cancernogenic

(Morita et al., 1983) Even low increase in Peroxide Value (>7 meq/kg) has a significant

effect on Feed Conversion Ratio (Cabel et al., 1988) Rancid Feed has an impact on the gastro-intestinal Structure, Cell

proliferation and intestinal Microflora (Shermer et al., 1995) Oxidised vegetable oil in Broiler feed reduces growth rate (5%)

(Engberg et al 1996) Rancid fish oil induced anaemia in Mink, reduced iron absorption

(Borsting et al., 1994)


Effect of peroxides on broiler Effect of peroxides on broiler performances (49 days)performances (49 days)University of ArkansasUniversity of Arkansas

1,5

1,6

1,7

1,8

1,9

2

2,1

2,2

2,3

0 2 4 7Feed Peroxide value (meq/kg feed)

FCR Body weight (kg)

Cabel, M. C., P. W. Waldroup, W. D. SHermer and D. F. Calabotta (1989), Poultry Science 67: 1725-1730

+ 4.78 %

- 6.29 %

a ab bc


Effect of raw material quality on broiler Effect of raw material quality on broiler performances (56 days)performances (56 days)

INTA (Argentina)INTA (Argentina)

1,5

1,7

1,9

2,1

2,3

2,5

2,7

2,9

2 30 68 120Meat meal Peroxide value (meq/kg) used in broiler feed

Body weight (kg) FCR

Schang et al. - 1987

- 10.69 %

+ 6.43 %

aa a

aa a

b

b


1) Initiation phaseRH -----> R° + H°RH -----> R° + H°

2) Propagation phase

3) Termination phase

ROO° + ROO° ---> stable end productsROO° + ROO° ---> stable end products

R° + O2 ----> ROO°R° + O2 ----> ROO°

ROO° + RH ----> ROOH + R°ROO° + RH ----> ROOH + R°

Fat molecule Free radical

(peroxide)

(aldehydes, ketones, short chain fatty acids)

The three stages of The three stages of OXIDATIONOXIDATION


Oxidation Process involving Oxidation Process involving Oxygen & lipidsOxygen & lipids

Lipids

temp.CatalystsLight AirTime

Damage critical nutrients

Oxygen forms

• Reaction with cell membranes• Toxic for animals• Destruction of fat soluble vitamins• Reduction of performances

AldehydesKetons

• Rancidity• Reduction of feed intake• En-products absorbed in the body• Start of in vivo oxidation

FREE RADICALS

FREE RADICALS

PEROXIDES

PEROXIDES

+


Induction Oxidation Termination period

Peroxides value (meq)

The three stages of OXIDATIONThe three stages of OXIDATION

Peroxides, radicalswater

Polimers, oxidisedfat, acids, aldehidesketones


Different antioxidantsDifferent antioxidants

Free radical scavengers:

Ethoxyquin, BHA, BHT, Propyl Gallate

Chelators:

Citric acid, phosphoric acid


Differences between antioxidantsDifferences between antioxidants

Ethoxyquin:

very stable, only feed grade, raw materials

Gallates:

very stable, regenerates ethoxyquin or BHA activity

BHA:

heat stable, mainly food and petfood

BHT:

heat stability problem, repartition problem,

readily broken down in premixes


Triple Mode of Action Triple Mode of Action

EUROTIOX

1.Citric acid forms reversible bonds with metal pro-oxidantsin the premix and feed to inhibit them from initiatingoxidation2. Ethoxyquin blocks oxidation by donating hydrogen ionsto free and peroxy radicals formed during the onsetand propagation stages3. Propyl gallate restores and potentiates ethoxyquin activity up to 3 times by donating hydrogen ions from its 3 activesites to oxidised (spent) ethoxyquin molecules


Efficacy of synthetic antioxidantsEfficacy of synthetic antioxidants

20

25

40

60

0 10 20 30 40 50 60 70

BHA 200 g/ton

BHT 200 g/ton

Propyl gallate100g/ton

Ethoxyqin 150g/ton

Days to reach 20meq/kg peroxides

Days

Stability test in mixed fat - Dr. M. Coelho (1995)


Formation of Ellagic Acid from Propyl Gallate


Antioxidant Activity of BHA, Propyl Gallate and Heterodimers

Antioxidant Activity (t – t0)/(tBHA – t0)

Compound (0.01%)

Lard Soybean Oil

BHA 1.0 1.0

Propyl Gallate 1.50 12.25

Heterodimer A 0.88 4.0

HeterodimerB 0.91 1.50

T. Kurechi and A.Kunugi, J. American Oil Chem. Soc. 60:33 (1983)


Ethoxyquin/Propyl GallateEthoxyquin/Propyl Gallate SYNERGY mechanism SYNERGY mechanism

oxid a tio n p o int

C H3

C H3

C H2H5O

C H3

C H3NH

C H2H5O

C H3NO

ETHOXYQUIN

OXIDIZED ETHOXYQUIN


Ethoxyquin/Propyl GallateEthoxyquin/Propyl Gallate SYNERGY mechanism SYNERGY mechanism

CH3

CH3N

ETHOXYQUIN

CH2H5OCH3

CH3N

CH2H5OCH3

CH3N

PROPYL GALLATE COOCH2CH2CH3

H OO H

O H

CH3 CH3 CH3


Mustakas et Al. (1984)

0

50

100

150

200

250

300

Pe

roxi

de

s (m

eq

/kg

)

No citric acid 46,6 293 85,4 288

with citric acid 10,7 125 13,1 44,4

CTR Fe Mn Cu

Metal chelatingMetal chelatingEffect of citric acid on soya oil stability Effect of citric acid on soya oil stability


Inhibition of Initiation by Chelation of Copper

+ Cu++HOCCOOH

CH2COOH

CH2COOH

Citric Acid

OOC CH2 C

CH2

COO

OH CO

C C

O

O HO

CH2

CH2

COO

COO

O

Cu++

CuCitrate complex with divalent cation,

forming two five-membered rings


Eurotiox 32-PremixEurotiox 32-PremixComparative granulometryComparative granulometry

0

20

40

60

Eurotiox

O ther

Eurotiox

Other

Eurotiox 50 42,4 6,2 0,6 0,4 0,2 0

Other 0,1 3,9 11 6,6 12,9 45,9 11,2

0,05-0,13 0,13-0,22 0,34-0,46 0,46-0,67 0,67-1,10 1,10-1,67 >1,67

Particle size class ( Mesh, mm) - Sieve analysis by industrial lab, Belgium, July 1996


EUROTIOX unique antioxidant EUROTIOX unique antioxidant complexcomplex

ETHOXYQUIN- high purity (% mono)- high stability

PROPYL GALLATE-highly effective- EtQ regenarator

CITRIC ACID-metal scavenger

Only provensynergism

Very effectiveeconomicalcomplex

UNIQUE CARRIER- high absorption- free-flowing- impr. stability

+

+

stablemicro-pearled

ALUMINIUM bag-protected

+

Maximum protection at low dosage

Two very potent free

radical scaven-

gers


EUROTIOX ANTIOXIDANT EUROTIOX ANTIOXIDANT PROGRAMPROGRAM

Vitamins, Pigments protection

in premixes & feed

Preventing rancidity in

fat, oils, bone meals

EUROTIOX 32-Premix

EUROTIOX L-32


EUROTIOXEUROTIOX

Dosage in feed and raw materialsDosage in feed and raw materials


EUROTIOX 32 Premix in feed

Eurotiox 32 Premix at 20 - 25 g/t in Feed with < 4% fat and < 1 month storage time

+ 5 g/t for each 2% fat increase

+ 5 g/t for each month storage increase


EUROTIOX 32 Premix in feed

FAT LEVEL IN FEED EUROTIOX 32 Premix

< 4 % 20 - 25 g/t

4 to 6 % 25 – 30 g/t

6 to 8 % 30 – 35 g/t

> 8 % 35 – 45 g/T


EUROTIOX 32 Premix in premixes and concentrates

Vitamin premix: 50g/ton

Vitamin and traces premix: 100 g/ton

Vitamin and traces and choline chloride: 200 g/ton

Higher dosages are required in case proteins are present.


EUROTIOX L 32 for raw material protection

Raw material Eurotiox L 32 doseg/t

Protection periodmonths

Vegetable oil(crude)

200 3

Palm oil (crude) 200 3

Rice Bran oil(crude)

400 3

Rice Bran oil(Refined)

200 3

Sunflower oil(crude)

300 3

Copra oil (crude) 200 3

Soya oil (crude) 200 3


EUROTIOX L 32 for raw material protection

Raw material Eurotiox L 32 doseg/t

Protection periodmonths

Fish oil (crude) 400 3

Poultry fat 300 3

Lard 200 3

Tallow 100 3

Mixed fat 200 3

Squid oil 300 3

Used fat 500 2


0

50

100

150

200

250

300

350

400

450

500

0 1 2 3 4 5 6

Months

Vit

am

ine A

(g

r)

Control

45 g/t EUROTIOX 32200, g/t ETQ-66%

EUROTIOX 32-Premix - 45 g/ton

Vitamin recovery test against oxidationVitamin recovery test against oxidation (Vitamin A in a vitamin mineral premix) (Vitamin A in a vitamin mineral premix)

HPLC assay - 6 months testing period March ‘95-Sep ‘95HPLC assay - 6 months testing period March ‘95-Sep ‘95


Vitamin A Stability comparative testVitamin A Stability comparative test Broiler feed - March 1997Broiler feed - March 1997

7540

7255 7295

7135

7000

6500

7000

7500

8000

Eurotiox Pdt A Pdt B Pdt C Pdt D

Vit

A (

U.I

./g)

EUROTIOX 32-Premix

Project with large industrial company(Broiler integration) in Philippines. Vitamin detection analysis performed by an independent laboratory (SERLABO) in the Netherlands.

At 25 g/ton, EUROTIOX provides the best VITAMIN A protection of all products tested


Trial results


EUROTIOX 32 PREMIX vs ENDOX

Feed, 7% fat

0

1

2

3

4

5

6

7

8

0

0,61

1,21

1,81

2,41

3,01

3,61

4,21

4,81

5,41

6,01

6,61

7,21

7,81

8,41

9,01

9,61

10,2

10,8

11,4 12

12,6

13,2

13,8

14,4 15

15,6

16,2

16,8

17,4 18

18,6

19,2

19,8

20,4 21

Time (h)

Pre

ssu

re (

bar

)

400 ppm ENDOX

80 ppm EUROTIOX 32 PREMIX


Eurotiox 32 Premix in meat and bone meal (poultry origin)

Trial set-up:– A control sample (no anti-oxydant added) and a treated

sample (150 ppm Eurotiox 32) was incubated in the OXIPRESS.

– The OXIPRESS was running until the control sample was completely oxidised.

– Both samples were analysed on their nutritional value and compared to a control sample which was not put in the OXIPRESS at all.



CONTROL WITHOUT OXIPRESS

CONTROL WITH OXIPRESS

CONTROL WITH OXIPRESS + 150 PPM EUROTIOX 32 PREMIX

Crude fat (g/kg)

121.2 105.4 115.6

Metaboliseble Energy (MJ/kg)

11.13 10.22 10.95



9,6

9,8

10

10,2

10,4

10,6

10,8

11

11,2

ME (poultry, MJ/kg)

Control

Control +OxipressControl + oxipress+ Eurotiox-

8.1%

-1.6%


OXIPRESS RESULTSMBM oxypress 100°C

0

1

2

3

4

5

6

7

8

0 5 10 15 20 25 30time (h)

pres

sure

(bar

)

control 150 ppm EUROTIOX 32 Premix


Eurotiox 32 Premix in meat and bone meal (Poultry origin)

Conclusions:– Oxidation is responsible for loss of nutrients, mainly

energy

– EUROTIOX 32 PREMIX is able to prevent nutrient losses due to oxidation.


Effect of EUROTIOX 32 PREMIX on energy values (kcal/kg) of MBM (ruminant origin)

2400

2600

2800

3000

3200

3400

3600

DAY 20 DAY 36 DAY 48

Control

27.5 ppmEUROTIOX 32PREMIX

Source: Trial AO 002: INDIA


Eurotiox 32 Premix versus competitor in feed (8% fat)AR139 oxypress 100°C

0

1

2

3

4

5

6

7

8

0 5 10 15 20 25

time (h)

pre

ssu

re (

bar

)

Controle

25 ppm Eurotiox 32 premix

Competitor

eurotiox ®, the most cost-effective antioxidant eurotiox

Documents

days slide

stages of oxidation

production slide

propyl gallate slide

phosphoric acid slide

oils energy slide

nutrient adsorption

abb c slide