''Oleochemicals and Sustainable Development of Palm Oil”

Minar Mahmoud M. Hassanein National Research Centre, Food Industries and Nutrition, Fats and Oils Dept. Egypt

minarmahmoud@yahoo.com

Introduction Palm oil is an important product in the Malaysian economy,

mainly through the trading of crude palm oil and its products. In most applications, foods and non-foods, refined and/or

fractionated palm oil products are utilized.

Palm oil

Phytonutrients (about 1%)

Vitamin E (600 – 1000 ppm)

Carotenoid (500 – 700 ppm)

Phytosterols (300 – 620 ppm)

Squalene (250 – 540 ppm)

Phospholipids (20 – 100 ppm)

Co-enzyme Q10 (10 – 80 ppm)

Polyphenolics (40 – 70 ppm)

Palm oil refining steps

Degumming • To remove gum

Bleaching • To reduce color

Deodorization

• To remove volatile odorous compounds. • This process produces a by-product called Palm

Fatty Acid Distillate (PFAD).

By-product from palm oil refining. During the process of

palm oil refining, palm fatty acid distillate (PFAD) is co-produced as a by-product at the step of deacidification-deodorization, entraining some of the phytochemicals.

Oleochemical The quantity of PFAD from Crude Palm Oil (CPO) is about

4% and about 3.66 ton PFAD is produced from every 100 tons of CPO.

Commonly PFAD is used as fatty acids source for non food industries mainly oleochemical industries and this by-product is usually used for soap, feed and oleochemicals.

Bioactive compounds from PFAD

PFAD contains fatty acids and glycerides of 96.1% and other minor bioactive compounds such as:

tocopherols and tocotrienols (0.48%) phytosterols (0.37%) squalene (0.76%) and other hydrocarbons (0.71%).

Tocopherol and tocotrienols During deodorization, about 5-57% of tocopherols and

tocotrienols are removed from CPO and some of them are accumulated in PFAD that results PFAD with 0.7-1.0% of vitamin E.

There are two antioxidants in the vitamin E family, tocopherols and tocotrienols. Tocotrienols are a “super” antioxidant of the vitamin E family.

Recently, tocotrienols have been found to have several medical uses: combating heart disease lowering “bad” cholesterol levels neutralizing “free radicals” and even fighting cancer.

Tocotrienols are important for pharmaceutical, food, supplement products due to their activity as:

hypocholesterolaemic antioxidant antithrombotic anti-atherogenic anti-inflammatory immunomodulator hepatoprotector.

All forms of vitamin E are able to induce antioxidant effects and to protect food and biologic membranes against the lipid peroxidation .

TOCOTRIENOLS PALM OIL

1995,1998,2004, Yu et al. 2005) CORN OIL

neuroprotection (Sen et al. 2000) SOY BEAN

OIL

neurodegeneration (Khanna et al . 2002) FLAX SEED OIL

SESAME OIL

Anti-cancer effects • Human prostate cancer cells • Breast cancer cells • Anti-angiogenesis Neuroprotection

α- tocotrienols at nanomolar concentration provide

Independent of anti-oxidant property Tocotrienols inhibit c-Src activity in glutamate-induced

Cardiovascular Protection • Inhibition of cholesterol synthesis

• Reversing Artherosclerosis

Phytosterols Phytosterols in PFADs from several palm oil refineries had variety in

quantity and composition. The major components of palm phytosterols are:

β sitosterol, followed by stigmasterol and campesterol.

Phytosterols compounds having anticancer and cholesterol-lowering properties and thus they find wide applications in nutraceuticals and functional foods.

The use of phytosterols and its hydrogenated forms, phytostanols, as such or as esters in functional food formulations as a cholesterol lowering agent has now been well-accepted by the consumers.

PFAD is the by-product of physical refining of crude palm oil products. Thus, utilization of PFAD as a source of phytosterols would represent a value addition strategy for palm oil industry.

PHYTOSTEROL RICE BRAN OIL

CORN OIL

WHEAT GERM OIL

FLAX SEED OIL

COTTON SEED OIL

Β-sitosterol campesterol stigmasterol

Cardiovascular benefits • Cholesterol lowering effect • Inhibition of cholesterol absorption

Anticancer properties

Immune functions • Stimulates lymphocytes proliferation

Squalene PFAD hydrocarbon was squalene (C30H50) as main

components; PFAD had higher quantity of squalene (up to 1.03%) than other vegetable oils.

Squalene like other isoprenoids (carotens, vitamin A,K,D,E) is a lipophilic antioxidant having unique characteristics which enable it to anchor itself to cell membrane. This explains the presence of squalene as one of the major components of skin surface lipids.

Squalene can easily produce oxygen by combining with water. Thus, it is an oxygen carrier with superior ability to transmit oxygen.

Squalene has the ability to maintain healthy skin due to its antioxidant activity and protect skin from detrimental environmental effects as well as to reduce blood cholesterol level and anticancer.

Research has show that supplementing the human diet with 900mg of squalene daily for seven to 30 days could be beneficial to cardiovascular health.

SQUALENE DEEP SEA SHARK LIVER OIL

OLIVE OIL

PALM OIL

WHEAT GERM OIL

AMARANTH OIL

Cardiovascular Benefits • Inhibition of cholesterol synthesis Anti-cancer effects • Protection against colon, breast and skin cancer • Suppress skin carcinogenesis • Anti-tumor activity • Suppress colon carcinogenesis • Inhibition of lung tumorigenesis

Co-enzyme Q10 Co-enzyme Q10 is structurally related to the vitamin E and

K. Co-enzyme Q10 is claimed to exhibit 10 times greater

antioxidant property than vitamin E; however, the greater concentration of carotenes and vitamin E in palm oil tends to overshadow its viability.

Low concentration of co-enzyme Q10 may be detrimental to health.

Some government officially approved for use co-enzyme Q10 as drug for treatment of congestive heart failure way back and for use in food and dietary supplements.

Co-enzyme Q10 has anticancer properties of its own.

COENZYME Q10 BEEF

MACKEREL

SOY

SPINACH

PEANUTS

Cardiovascular benefits • Protects Ischemic heart muscle) • Antihypertensive)

Anti-cancer effects • Breast cancer cells

Enhance Production of cellular Energy • Exercise Performance)

Antioxidative defense mechanism • In plasma and blood cells

As a result, PFAD is relatively a rich

source of beneficial phytochemicals, with potential for use as bioactive ingredients

in nutraceuticals industry.

Bioactive compounds of oil from palm leaves The phytochemical screening demonstrated the

presence of different types of phytochemical constituents in oil palm leaves including: Phenolic compounds, Flavonoids, Tannins, Coumarins, Alkaloids, Saponins, Terpenoids Steroids which could be responsible for the

biological activities.

Polyphenolics Polyphenols are large family of natural compounds that can

be classified into phenolic acids and flavonoids. Phenolics act as free radical terminators, resistance against

oxidation of human LDL in vitro and in vivo. Flavonoids are most potent free radical scavengers and ion

chelators as well as reduce blood pressure and risk of many diseases.

POLYPHENOLS ONIONS

APPLES

TEA

RED WINE

GRAPES

Ferulic acid

Coumaric acid Cinnamic acid

Antioxidants

Free radical scavengers

Iron chelating activity

Anticarcinogenic • Breast cancer • Prostate cancer

Bioactive compounds from palm-pressed fiber oils

The various types of carotenes found in palm fiber oil are summarized in Table. Carotenoids have been used as medicines for the treatment of cancer, cardiovascular disease and as immune system regulators.

Furthermore, carotenoids have been shown to be beneficial to human health, especially in the role of pro-vitamin A which is known to prevent a hardening of eye tissue related to night blindness.

Among all other carotenoids, β-carotene is commonly and commercially used in food processing industry for its excellent coloring properties.

β-carotene is a precursor of vitamin A and plays an important role in human health as well as the cellular regulatory system.

β-carotene is known to have several other physiological functions, including antioxidant activity and inhibition of colon cancer cell growth.

It also has pharmaceutical, cosmetic and therapeutic uses.

Human beings cannot synthesis carotenoids in the body, so they need intake from food sources.

Lycopene is another important carotenoid.

Lycopene is a natural red pigment and has extensive applications in the nutraceutical, pharmaceutical and in cosmetics market due to its natural deep-red pigments.

Furthermore, it has potent antioxidant and anticarcinogen activity.

HEALTH-PROMOTING FUNCTIONS OR ACTIONS ATTRIBUTED TO CAROTENOIDS

Provitamin Actvity

A Inhibition of Cancer

Prevention of Cardiovascular Disease

Immuno- enhancement

CAROTENOIDS

Prevention of Macular Degeneration Decreased risk

of Cataract Formation

CAROTENOIDS CARROTS

TOMATOES

EGG YOLK

GARAPE FRUIT

APRICOT

Provitamin A activity • Improves vitamin A status of lactating women and their infants • Improve serum retinol concentrations • Combat vitamin A deficiency Anti-cancer effects • Breast cancer cells Cardiovascular Benefits • Protection against Ischemia/ Reperfusion heart injury

α-carotene Β-carotene

Lycopene

Palm-pressed fiber oil contains high level squalene, phytosterols, carotenes and vitamin E, ranging from 1,102 to 4,638 mg/kg each, depending on whether fresh or dried fiber is used .

The average vitamin E concentration in fiber oil is 2,882 mg/kg.

In palm-pressed fiber oil, the major compound is α-tocopherol, which is about 60–70%.

Natural tocopherols and tocotrienols are well absorbed by body tissue; therefore extraction of these components from natural sources is of interest.

Phytosterols are used as intermediates for the synthesis of hormones and drugs and widely used as cholesterol-lowering agents in food and pharmaceuticals industries.

β-sitosterol is the major constituent at 70% and is potentially hypocholesterolemic .

Squalene acts as chemopreventive agent against some type of cancers .

Health Promoting Phytonutrients

Table 3: Phytonutrient components and Health benefits Health benefits Phytonutrients

Anti-cancer effects Antioxidants Anti-ageing

Cardio-protective effects Inhibition of cholesterol synthesis

Vitamin E

Cholesterol lowering properties Phytosterols

Cardio-protective effects Inhibition of cholesterol synthesis

Anti-cancer

Squalene

Enhance production of cellular energy Antioxidative defence mechanism

Cardio-protective effects Anti-cancer

Co-enzyme Q10

Cholesterol inihibition Aids various circulation problems

Anti-cancer

Polyphenols

Pro-vitamin A activity Cardio-protection effects

Anti-cancer

Carotenoids

Brain development Energy endurance

Eases digestion and nutrition absorption

Phospholipids

Modern techniques for extraction of antioxidants:

1- Super Fluid Extraction (SFE)

2- Pressurized Liquid Extraction (PLE)

2- Microwave Assisted Extraction (MAE)

3- Ultrasound Assisted Extraction (UAE)

Conclusion Natural compounds with biological activity have recently

attracted special interest as a source of ingredients for nutraceutical food and pharmaceutical industries.

From the above mentioned facts, there is an abundance of waste being generated from the industry which can be turned to value-added products.

Bioactive components have been receiving great attention because they bring benefits to the health and food fields.

The natural antioxidants, belonging to the GRAS (Generally Recognized As Safe) group of FDA (Food and Drug Administration), are extracted from herbs or plants and are commonly phenolic compounds that present health benefits, as the prevention of diabetes, cancer, hypertension.

Obtaining bioactive components from by-products using novel extraction techniques is increasing, and scientific investigations are progressively focusing on the natural antioxidants which are present in these by-products.

Also, the suitability of using each novel technique for obtaining different antioxidant phytochemicals, based on target compound characteristics, was emphasized.