Category Archives: 2008 Special Issue Oct

Palm vitamin E for aquaculture feeds

In this overview, our current research on the use of palm oil-based vitamin E in aquaculture feeds will be highlighted. While most vegetable oils contain almost exclusively tocopherols, palm oil is notable because tocotrienols represent about 80% of the vitamin E content. Almost all vitamin E research in fish nutrition has focused on α-tocopherol, usually supplied as the synthetic all-rac-α-tocopherol acetate, as it is deemed the most potent of all the isoforms. Several feeding trials were carried out to investigate the deposition of vitamin E and their antioxidant activity in various tissues of tilapia and catfish fed various palm oil products and vitamin E sources. We were the first group of researchers to show that (1) the tocotrienol-rich fraction (TRF) extracted from palm oil is more potent than all-rac-α-tocopherol acetate as an antioxidant when used in tilapia diets; (2) fish tissues varied in their ability to accumulate tocotrienols with the highest concentrations being found in perivisceral adipose tissues, followed by liver, skin and muscle; (3) tissue concentrations of α-tocopherol, α-tocotrienol and γ-tocotrienol increased linearly in response to increasing dietary concentrations originating from added TRF. As a potent in vivo antioxidant in fish tissues, palm vitamin E will have positive impacts on seafood quality such as prolonging shelf-life, maintaining colouration of pigmented seafood and enhancing the nutritional value of seafood.

Palm oil-based methyl ester sulphonate as an oil well stimulation agent

Methyl ester sulphonate (MES) is a surfactant (surface-active agent) that can reduce interfacial tension between water and oil. The compound can be diluted not only in water but also in oil. MES surfactant can be used in chemical stimulation processes to increase and enhance oil recovery (EOR) from reservoirs by reducing the interfacial tension between the oil and water formation. One of the success criteria in surfactant application as a stimulation agent is its effect on the interfacial value between oil and water droplets in a particular saline condition. Hence, the palm oil-based MES oil well stimulation agent was tested in three saline conditions before it was injected into the core. This study was aimed at determining the total oil recovery from a crude oil reservoir after injection of the palm oil-based MES stimulation agent into the core. The formulation of the palm oil-based MES as a stimulation agent consists of 70% palm oil-based MES, 20% solvent, 7% non-ionic surfactant and 3% co-solvent. Using 0.5% and 1% concentrations of the stimulation agent tested at 10 000, 20 000 and 30 000 ppm water salinity, the interfacial tension between oil and water was reduced to 10-4 dyne cm-1. The total oil recovery with a 0.5% concentration of the palm oil-based MES stimulation agent was between 88% and 94%. However, the total oil recovery increased in the range of 90%-99% with the injection of a 1% palm oil-based MES stimulation agent into the core. Based on these results, the palm oil-based MES surfactant can be used effectively as a stimulation agent in a real crude oil reservoir.

Productions of carotenoids and tocols concentrates from palm oil using supercritical carbon dioxide

A method using supercritical carbon dioxide to produce concentrated carotenoids and tocols from palm oil is described. The free fatty acids of crude palm oil were esterified by acid-catalysis followed by transesterification of the triglycerides into methyl esters. Methyl esters are considerably more soluble in supercritical carbon dioxide than the triglycerides and free fatty acids, and are preferentially dissolved leaving a solution of highly concentrated carotenoids (20.11 wt%) and tocols (10.66 wt%).

Biodiesel production from different feedstocks in pilot scale system

In this study, the preparations of biodiesel from three different feedstocks, including rapeseed oil, high acidified Chinese wood oil and trap grease, were carried out in a pilot scale of 200 t yr-1 biodiesel production system. The optimum operating conditions for transesterification of rapeseed oil in plug flow reactor were found to be as follows: the catalyst dosage is 1.2 wt%; the retention time is about 17 min; the bed temperature is 65°C; the oil/methanol ratio is 1:6; the content of methyl ester is 96.33% under these conditions. A kind of ion exchange resin, a solid acid catalyst, filled in the fixed bed reactor was used as the esterification catalyst for the pretreating of high acidified oil. The acid value of Chinese wood oil could be reduced from 7 to 0.8 mg KOH•g-1 after 88 min, the optimum operating conditions were obtained as follow: molar ratio of methanol to oil is about 6:1 , the temperature of the fixed bed, 65oC and the retention time, about 88 min. Also a kind of acidified oil, namely trap grease, with the acid value being 114 mg KOH•g-1 could be equally converted to a good biodiesel product through this system. Generally, the refined biodiesel product generated through this system could meet China #0 Biodiesel Standard, as well as Germany Biodiesel Standard for most indexes. It indicates that the designed process in this system has a good adaptability for different kinds of oil.

Advanced carbon products from oil palm biomass

A method was developed to produce advanced carbon products from oil palm biomass. Oil palm empty fruit bunch (EFB) contains polymeric lignocellulosic components such as hemicellulose, cellulose and lignin, and is therefore a potential raw material for producing advanced materials such as carbon electrode and molecular sieve carbon. Carbon precursors were prepared by slow pyrolysis of EFB under vacuum at 280°C. Powder obtained from grinding and ball milling the semi-pyrolysed EFB was then treated with 0.2, 0.4 and 0.6 M H2SO4 and dried at 100°C. The chemical changes of the treated EFB carbon precursors are discussed by their Thermogravimetric (TGA) results. Green body pellets were then prepared by molding of the carbon precursors powder at 10 t of compression force and then carbonized at 600°C, 800°C and 1000ºC using multiple heating profiles under nitrogen gas flow. The carbon pellets prepared from 0.4 M H2SO4 gave the highest density (ρ), Young’s modulus (E), Rockwell hardness (H) and electrical conductivity (σ). These indicated that the treatment had increased the crystallinity of the carbon as also evidenced by the XRD analysis results. BET surface area analysis was carried out and it was found that the carbon precursors treated with 0.6 M H2SO4 produced the activated carbon with the highest porosity. The carbon pellets produced from the treatment with 0.6 M H2SO4 and carbonized at different temperatures were further activated with CO2 to further increase their porosity, and the effects of different carbonization temperature on the pore structure and adsorptive properties for oxygen and nitrogen were investigated. This study has identified oil palm EFB as a potentially suitable raw material for the preparation of carbon electrode and molecular sieve carbon.

Gamma tocotrienol and prostate cancer: the regulation of two independent pathways to potentiate cell growth inhibition and apoptosis

Dietary vitamin E, highly expressed in palm oil, exists as either tocopherols or tocotrienols. Evidence indicates that vitamin Es may be potent cancer preventive agents. In this study, the γ- and δ- isoforms of vitamin E were found to be the most effective at cancer cell growth inhibition, with the tocotrienols being more effective than the tocopherols in androgen-independent PC-3 prostate cancer cells. To assure that these compounds were selective toward cancer cells, the growth arrest of PrEC normal prostate cells was compared to PC-3 cells. At concentrations of ≤30 μM dietary, γ-vitamin Es showed no significant growth arrest on PrEC cell growth, but selectively inhibited growth in the PC-3 cancer cells. Moreover γ-tocotrienol demonstrated a greater potential to inhibit growth in cancer cells at these lower concentrations than did γ-tocopherol. Two independent pathways important in carcinogenesis were tested: PPAR γ and NFκB. The PPAR γ was up regulated by both dietary γ-vitamin Es by the modulation of the endogenous ligand 15-S-HETE, while NFκB was only regulated by γ-tocotrienol. The modulation of NFκB was confirmed by the down regulation of the pro-apoptotic proteins cIAP, xIAP, and BcL-2 which potentiate apoptosis and are down stream effectors of NFκB.

Preparation of a low viscosity and light coloured fatty acid-based polyols

Chemical synthesis of a low viscosity and light coloured fatty acid-based polyol was conducted via a threestep reaction. The reaction variables, namely, temperature, pressure, amount of catalyst used, molar ratio of reactants and reaction time were investigated for their effects on the properties of the final polyol produced. Temperature and reduced pressure were found to have a profound impact on the rate of the first reaction step, which was an esterification reaction. In addition, it was observed that the amount of catalyst had a great influence on the colour of the product as well as the rate of the reaction. In the second reaction step, which was an epoxidation reaction, the molar ratio of reactants and reaction time play crucial roles in determining the properties of the final product. At the same time, temperature control was another important factor in this second step. The final reaction step was alcoholysis, in which the amount of catalyst used was one of the important factors that affected the properties of the final product.
Depending on the reaction parameters for this three-step reaction, fatty acid-based polyols with various properties could be prepared. However, polyols with low viscosity and light colour characteristics are preferred because they have the properties that are suitable for the production of 2K polyurethanes for the CASE industry.

Bio-based polyols for the flexible slabstock foam industry

During the last few years, interest in polyols derived from natural oils has been constantly increasing for a variety of polyurethane applications. Bio-based polyol chemistry brings new product supply options that are produced from renewable resources, have supply stability and provide the opportunity for differentiation in the foam market-place. These are some of the key drivers for the polyurethane processors to look at ways to utilize such products. Until now, the successful use of natural oil-based polyols in flexible slabstock applications has been limited due to issues with quality consistency, odour, impact on physical properties and processing limitations. Most recently, Cargill Incorporated introduced its BiOHTM polyol product line for the production of flexible foams leveraging on the company’s integrated supply chain and deep knowledge in processing oilseeds and vegetable oils on a global basis. Commercially available BiOH polyols are produced predominantly from soya-based feedstock. However, this article will show that Cargill can produce equally high quality polyols using palm feedstock. BiOH polyols are performance products produced with a chemistry that is completely detached from propylene or ethylene oxide. BiOH polyols have also resolved the odour and quality consistency issues previously encountered with other natural oil-based polyols. This article will describe the large-scale evaluation results of the first generation BiOH polyols in different foam grades and their ability to deliver the following: ease of processing with commercially available catalysts, surfactants and additives; improved flammability; improved hydrolysis resistance; performance enhancement in different foam grades such as viscoelastic; same level of microbial activity; more efficient load-bearing building capabilities than SAN copolymer polyols and smaller environmental footprint.

Variable density plantings for oil palms (Elaeis guineensis) in Peninsular Malaysia

The current planting density is a fixed option based on the duration of the economic life cycle of the oil palm, which is about 25 years in Malaysia. As space requirement increases as palm grows bigger with age, the density giving greatest yield therefore decreases gradually from high to a lower stable density at some point in the planting cycle. This behaviour is premise for one of the key options investigated in this project, the concept of variable density (VD). In this option, palms are planted at high densities and thinned when the starting density is no longer the optimum density for the given period. Because of the morphology of the oil palm, planting patterns influence greatly the yields obtained both before and after thinning. The project investigated several of the key elements in the VD concept. They are the starting and finishing densities, planting patterns, thinning periods, intensity of thinning and manuring requirements (one of the high cost items affected by density). A second option investigated is the concept of fixed high density planting (HDP) on a shorter 18-20-year cycle. This allows a quicker introduction of newer varieties which yield better or with special traits (high iodine value, disease resistant, low height increment, etc.) in successive replants with concomitant better profitability. This option is also suitable for land under acquisition threat or development potential. The strategies are evaluated over six experiments on both coastal and inland soils. Results to date suggest both strategies are viable and have potential. Results from the spacing experiments indicate that HDP, on a shorter replanting cycle is more economical. However, on conventional planting cycles of 25 years, current fixed planting densities are still valid. The results from the VD options suggest that initial starting densities at triangular spacing are better than other planting pattern despite the resultant spacing after thinning being asystematic. Starting densities at 180 – 200 palms ha-1 at triangular spacing and thinned at around the 12th – 14th year of planting by 14% – 25%, appears to be viable. Future research directions and experimental limitations are also discussed.

Palm oil tocotrienols as antioxidants and chemopreventive agents

Breast cancer leads all cancer incidence among American women, accounting for 32% of the 2005 estimated new cases in the United States. It is the second leading cause of cancer deaths, estimated at 40 000 yr-1. Estrogens, natural or synthetic, used widely in a variety of clinical conditions, from estrogen replacement therapy to cancer treatment, are themselves carcinogenic, causing uterine and breast cancers. However, the mechanism of their carcinogenic action is still not well understood. We found that both 17β-estradiol (E2) and estrone (E1) could be activated by the versatile epoxide-forming oxidant dimethyldioxirane (DMDO) to inhibit nuclear RNA synthesis and to bind DNA forming estrogen-DNA adducts both in vitro and in vivo. Since DNA adducts can cause mutation, and mutation is the molecular basis for the initiation of carcinogenesis, our findings strongly suggest the possibility that both E2 and E1 are the initiators for uterine and breast carcinogenesis. Based on this new insight, a method to screen chemopreventive agents against breast cancer, at the initiation, was developed. This screening test determines whether a chemical is able to prevent the formation of E2 or E1 epoxide as measured by both the loss of the ability of E2 or E1 to inhibit nuclear DNA-dependent RNA synthesis and the ability of [3H] E2 or E1 to bind DNA. This article summarizes the results of our recent studies on the preventive effects of Red Palm Oil, tocopherols and tocotrienols on the epoxidation of several carcinogens including E2, E1 and aflatoxin B1 (AFB1). Our data suggest that tocotrienols are more potent hemopreventive agents than tocopherols against the epoxide formation of E2 , E1 and AFB1. As a dietary supplement, tocopherols and especially tocotrienols may have the potential to prevent breast and liver cancers.

Planting material as key input for sustainable palm oil

The trends generally agreed for the future of palm oil as an important commodity are the combination of a demand for food that will double over the next 20 years, the emergence of new uses as a renewable energy source, and (until the recent price exuberance over biodiesel) the falling price trend of palm oil in real terms on the world market.
For more than 30 years, the average crop yield of the land under exploitation in the world does not exceed 3 t ha-1 yr-1. The boom in availability of the commodity is thus, almost entirely due to the large increase in cultivated surface area, resulting in competition with the other food crops for arable land, and participating in the disappearance of tropical rain forest and needless environmental degradation. In turn, this fuels the regular disparaging media campaigns against the oil palm industry.
The principles and criteria for sustainable palm oil were adopted by the general assembly of the Roundtable for Sustainable Palm Oil in November 2005. They embody a commitment to long-term economic and financial viability, the use of appropriate best management practices, and an improvement of environmental and socially positive impacts whilst reducing the negative ones. The planting of improved and adapted oil palm planting material is a key input to achieve these commitments.
This article presents evidence of the effects of continuous improvement of planting material on the profitability of the crop. Highlighted is the widespread use of poor quality material, and the alternative value, for example, of PT Socfindo planting materials enhanced by the cooperation of Cirad – France and its network. The challenges to be faced for the future by breeders and seed producers, as well as plantation management are discussed

Effect of new palm oil mill processes on the EFB and POME utilization

New palm oil mill processes are characterized by advanced oil separation technologies with zero dilution water (‘ECO-D’ for example as a new system for oil recovery without dilution water) and continuous sterilization of the fresh fruit bunch (FFB). These processes have a deep impact on the amount and composition of waste water (POME). Compared to conventional palm oil mills the total amount of palm oil mill effluent (POME) can be reduced from 0.65 m3 t-1 FFB to 0.45 m3 t-1 (conventional sterilization and zero dilution water) and 0.25 m3 t-1 (continuous sterilization and zero dilution water). These changes influence the treatment processes and its cost significantly. One process for the EFB and POME utilization which can fulfil the demand of a sustainable palm oil production is the co-composting of both of the materials. The composting process is used also for biological drying of the POME. The final product of the process is compost or mulch which unifies the nutrients of both in one product. The POME can be used also for biogas production (in fixed bed reactors for POME with low dry matter content and in totally mixed reactors for ECO-D biomass) before composting. The investment cost and profitability of the composting and fermentation process is calculated in detail based on data from practise in Indonesia. The new developments of processes in palm oil mills can reduce the cost for the waste and waste water treatment up to 35%. The benefits from biogas production and composting are the energy production, saved POME treatment cost in pond systems, total utilization of the POME nutrients, reduced cost for the EFB transport and utilization, higher empty fruit bunch (FFB) yields and from clean development mechanism (CDM).

Eco-friendly approaches to sustainable palm oil production

There have been many innovations in mill technologies, oil palm agronomy and pest management over past decades that are increasingly meeting the certification criteria of the Roundtable on Sustainable Palm Oil (RSPO). In addition, because oil palm plantations may be functionally analogous to forests, and remain undisturbed for several decades, they can provide some essential ecosystem services to local/national stakeholders in terms of direct use-values (products, economics) and indirect use-values (carbon sequestration, biodegradation, hydrology); though the economic value of indirect services, such as maintenance of water quality, have not been recognized as national assets. On the other hand, option values (gene pools) and existence values (biodiversity) for oil palm plantations are low and loss of these values is contentious when natural systems are converted. Negative perceptions of oil palm being ‘eco-friendly’ also reflect the extent to which forest and peatland conversion to oil palm have resulted in off-site effects such as carbon mobilization, damage to river systems from sedimentation and loss of biodiversity. It is concluded that the industry could improve its image by adopting mitigation measures, including better landscape design and documentation of the areas under development, and by improving the visibility that some sectors of the industry are making to address these environmental issues.

Process development with bifunctional chiral epoxides to access single enantiomers of pharmaceutical intermediates

Two selected case studies on process development will be discussed: one is on the enantiocontrolled synthesis of (S)-3-hydroxytetradecanoic acid (2), an intermediate of ONO-4007 (3) possessing anti-tumour activity, which employs double homologation of (S)-epichlorohydrin (ECH) (1b) with its termini being differentiated. The other is on the enantioselective access to N-4-cyano-3-trifluoromethylphenyl-(S)-2,3-dihydroxy-2- methylpropanamide (5a), an intermediate of (R)-bicultamide (5b) exhibiting potent anti-androgen activity, which starts with enantioconvergent preparation of (R)-3-benzyloxy-2-methylpropane-1,2-diol (4) from Obenzyl (±)-2-methylglycidol (1c) by the enantiocomplementary hydrolysis using Bacillus subtilis epoxide hydrolase (BSEH) and H2SO4 in sequence. In each case study, emphasis will be placed on how to select viable synthetic routes on the basis of availability of single enantiomers of chiral starting materials and preparative methods thereof. In the chemoenzymatic synthesis of (S)-5a, BSEH indispensable for building its quaternary stereogenic centre is developed from scratch, which culminates in successful overexpression of its gene from B. subtilis JCM 10629 under the influence of an amylase promoter and terminator of B. amyloliquefaciens NBRC 15535 in an engineered strain of B. subtilis MT-2 deficient in neutral protease. The discussion should help to develop process chemistry in producing value-added fine chemicals from glycerol, one of its natural sources being palm oil.