Green Phenolic Resins from Oil Palm Empty Fruit Bunch (EFB) Phenolated Lignin and Bio-Oil as Phenol Substitutes for Bonding Plywood.

Lignin is a natural biopolymer with a complex three-dimensional network and it is rich in phenol, making it a good candidate for the production of bio-based polyphenol material. This study attempts to characterize the properties of green phenol-formaldehyde (PF) resins produced through phenol substitution by the phenolated lignin (PL) and bio-oil (BO), extracted from oil palm empty fruit bunch black liquor. Mixtures of PF with varied substitution rates of PL and BO were prepared by heating a mixture of phenol-phenol substitute with 30 wt.% NaOH and 80% formaldehyde solution at 94 °C for 15 min. After that, the temperature was reduced to 80 °C before the remaining 20% formaldehyde solution was added. The reaction was carried out by heating the mixture to 94 °C once more, holding it for 25 min, and then rapidly lowering the temperature to 60 °C, to produce the PL-PF or BO-PF resins. The modified resins were then tested for pH, viscosity, solid content, FTIR, and TGA. Results revealed that the substitution of 5% PL into PF resins is enough to improve its physical properties. The PL-PF resin production process was also deemed environmentally beneficial, as it met 7 of the 8 Green Chemistry Principle evaluation criteria.

High-Energy Ball Milling for High Productivity of Nanobiochar from Oil Palm Biomass.

The current production method of nanobiochar (NBC), an emerging, environmentally friendly nanocarbon material, is tedious and lengthy. Therefore, in this study we aimed to improve the productivity of NBC via high-energy ball milling by manipulating the grinding media and processing time. The particle size distribution of the resulting NBC measured using dynamic light scattering showed that grinding media with steel balls of different sizes were more effective at producing NBC than small uniform steel balls, which failed to produce NBC even after 90 min of milling. Average NBC particles of around 95 nm were achieved after only 30 min of ball milling, and the size was further reduced to about 30 nm when the milling was prolonged to 150 min. Further prolonging the milling duration led to agglomeration, which increased the size of the biochar nanoparticles. The thermogravimetric analysis (TGA) data showed that the duration of milling and particle size did not cause noticeable differences in the thermal stability of the NBC. Based on the FTIR analysis, the chemical structure of the NBC was not affected by the ball milling. The results showed that 60 min of high-energy ball milling is sufficient to produce NBC particles of 75 nm, with a large surface area and high thermal stability. This could prove beneficial in a myriad of applications, ranging from agriculture to composite fabrication.

Facile Preparation of Cellulose Fiber Reinforced Polypropylene Using Hybrid Filler Method.

Dried hybrid fillers comprised of silica/CNF were successfully synthesized in ethanol/water mixed solvents at room temperature without the usage of any precursor. The as-prepared fillers were incorporated with polypropylene (PP) as a polymer matrix through a twin-screw extruder. From surface morphology analysis, the agglomeration of the silica/CNF hybrid fillers was prevented in the PP matrix and they exhibited moderate transparency, around 17.9% and 44.6% T at 660 nm. Further, the chemical structures of the polymer composites were identified by Fourier transform infrared (FT-IR) analysis. According to thermogravimetric analysis (TGA), the insertion of silica as a co-filler to the PP matrix resulted in an increase in its degradation onset temperature and also thermal stability. In addition, the mechanical properties of the PP composites also increased after the blending process with the hybrid fillers. Overall, sample PP-SS/CNF exhibited the highest tensile strength, which was 36.8 MPa, or around 73.55% compared to the pristine PP. The improvements in tensile strength were attributed to good dispersion and enhanced efficiency of the stress transfer mechanism between the silica and the cellulose within the PP matrix. However, elongation of the sample was reduced sharply due to the stiffening effect of the filler.

Performance Evaluation of Cellulose Nanofiber with Residual Hemicellulose as a Nanofiller in Polypropylene-Based Nanocomposite.

Residual hemicellulose could enhance cellulose nanofiber (CNF) processing as it impedes the agglomeration of the nanocellulose fibrils and contributes to complete nanofibrillation within a shorter period of time. Its effect on CNF performance as a reinforcement material is unclear, and hence this study seeks to evaluate the performance of CNF in the presence of amorphous hemicellulose as a reinforcement material in a polypropylene (PP) nanocomposite. Two types of CNF were prepared: SHS-CNF, which contained about 11% hemicellulose, and KOH-CNF, with complete hemicellulose removal. Mechanical properties of the PP/SHS-CNF and PP/KOH-CNF showed an almost similar increment in tensile strength (31% and 32%) and flexural strength (28% and 29%) when 3 wt.% of CNF was incorporated in PP, indicating that hemicellulose in SHS-CNF did not affect the mechanical properties of the PP nanocomposite. The crystallinity of both PP/SHS-CNF and PP/KOH-CNF nanocomposites showed an almost similar value at 55-56%. A slight decrement in thermal stability was seen, whereby the decomposition temperature at 10% weight loss (Td10%) of PP/SHS-CNF was 6 °C lower at 381 °C compared to 387 °C for PP/KOH-CNF, which can be explained by the degradation of thermally unstable hemicellulose. The results from this study showed that the presence of some portion of hemicellulose in CNF did not affect the CNF properties, suggesting that complete hemicellulose removal may not be necessary for the preparation of CNF to be used as a reinforcement material in nanocomposites. This will lead to less harsh pretreatment for CNF preparation and, hence, a more sustainable nanocomposite can be produced.

Improving the decolorization of glycerol by adsorption using activated carbon derived from oil palm biomass.

This study provides insight into the decolorization strategy for crude glycerol obtained from biodiesel production using waste cooking oil as raw material. A sequential procedure that includes physico-chemical treatment and adsorption using activated carbon from oil palm biomass was investigated. The results evidenced decolorization and enrichment of glycerol go hand in hand during the treatment, achieving >89% color removal and > 98% increase in glycerol content, turning the glycerol into a clear (colorless) solution. This is attributed to the complete removal of methanol, free fatty acids, and triglycerides, as well as 85% removal of water, and 93% removal of potassium. Properties of the resultant glycerol met the quality standard of BS 2621:1979. The economic aspects of the proposed methods are examined to fully construct a predesign budgetary estimation according to chemical engineering principles. The starting capital is proportionate to the number of physical assets to acquire where both entail a considerable cost at USD 13,200. Having the benefit of sizeable scale production, it reasonably reduces the operating cost per unit product. As productivity sets at 33 m3 per annum, the annual operating costs amount to USD 79,902 in glycerol decolorization. This is translatable to USD 5.38 per liter glycerol, which is ~69% lower compared to using commercial activated carbon.

Optimisation of Epoxide Ring-Opening Reaction for the Synthesis of Bio-Polyol from Palm Oil Derivative Using Response Surface Methodology.

The development of bio-polyol from vegetable oil and its derivatives is gaining much interest from polyurethane industries and academia. In view of this, the availability of methyl oleate derived from palm oil, which is aimed at biodiesel production, provides an excellent feedstock to produce bio-polyol for polyurethane applications. In this recent study, response surface methodology (RSM) with a combination of central composite rotatable design (CCRD) was used to optimise the reaction parameters in order to obtain a maximised hydroxyl value (OHV). Three reaction parameters were selected, namely the mole ratio of epoxidised methyl oleate (EMO) to glycerol (1:5-1:10), the amount of catalyst loading (0.15-0.55%) and reaction temperature (90-150 °C) on a response variable as the hydroxyl value (OHV). The analysis of variance (ANOVA) indicated that the quadratic model was significant at 98% confidence level with (p-value > 0.0001) with an insignificant lack of fit and the regression coefficient (R2) was 0.9897. The optimum reaction conditions established by the predicted model were: 1:10 mole ratio of EMO to glycerol, 0.18% of catalyst and 120 °C reaction temperature, giving a hydroxyl value (OHV) of 306.190 mg KOH/g for the experimental value and 301.248 mg KOH/g for the predicted value. This result proves that the RSM model is capable of forecasting the relevant response. FTIR analysis was employed to monitor the changes of functional group for each synthesis and the confirmation of this finding was analysed by NMR analysis. The viscosity and average molecular weight (MW) were 513.48 mPa and 491 Da, respectively.

Mechanical Strength, Thermal Conductivity and Electrical Breakdown of Kenaf Core Fiber/Lignin/Polypropylene Biocomposite.

Mechanical strength, thermal conductivity and electrical breakdown of polypropylene/lignin/kenaf core fiber (PP/L/KCF) composite were studied. PP/L, PP/KCF and PP/L/KCF composites with different fiber and lignin loading was prepared using a compounding process. Pure PP was served as control. The results revealed that tensile and flexural properties of the PP/L/KCF was retained after addition of lignin and kenaf core fibers. Thermal stability of the PP composites improved compared to pure PP polymer. As for thermal conductivity, no significant difference was observed between PP composites and pure PP. However, PP/L/KCF composite has higher thermal diffusivity. All the PP composites produced are good insulating materials that are suitable for building. All PP composites passed withstand voltage test in air and oil state as stipulated in IEC 60641-3 except PP/L in oil state. SEM micrograph showed that better interaction and adhesion between polymer matrix, lignin and kenaf core fibers was observed and reflected on the better tensile strength recorded in PP/L/KCF composite. This study has successfully filled the gap of knowledge on using lignin and kenaf fibers as PP insulator composite materials. Therefore, it can be concluded that PP/Lignin/KCF has high potential as an insulating material.

Characterization and Cellular Internalization of Spherical Cellulose Nanocrystals (CNC) into Normal and Cancerous Fibroblasts.

The aim was to isolate cellulose nanocrystals (CNC) from commercialized oil palm empty fruit bunch cellulose nanofibre (CNF) through sulphuric acid hydrolysis and explore its safeness as a potential nanocarrier. Successful extraction of CNC was confirmed through a field emission scanning electron microscope (FESEM) and attenuated total reflection Fourier transmission infrared (ATR-FTIR) spectrometry analysis. For subsequent cellular uptake study, the spherical CNC was covalently tagged with fluorescein isothiocyanate (FITC), resulting in negative charged FITC-CNC nanospheres with a dispersity (Ð) of 0.371. MTT assay revealed low degree cytotoxicity for both CNC and FITC-CNC against C6 rat glioma and NIH3T3 normal fibroblasts up to 50 µg/mL. FITC conjugation had no contribution to the particle's toxicity. Through confocal laser scanning microscope (CLSM), synthesized FITC-CNC manifested negligible cellular accumulation, indicating a poor non-selective adsorptive endocytosis into studied cells. Overall, an untargeted CNC-based nanosphere with less cytotoxicity that posed poor selectivity against normal and cancerous cells was successfully synthesized. It can be considered safe and suitable to be developed into targeted nanocarrier.

Dynamics of Microbial Populations Responsible for Biodegradation during the Full-Scale Treatment of Palm Oil Mill Effluent.

Despite efforts to address the composition of the microbial community during the anaerobic treatment of palm oil mill effluent (POME), its composition in relation to biodegradation in the full-scale treatment system has not yet been extensively examined. Therefore, a thorough analysis of bacterial and archaeal communities was performed in the present study using MiSeq sequencing at the different stages of the POME treatment, which comprised anaerobic as well as facultative anaerobic and aerobic processes, including the mixed raw effluent (MRE), mixing pond, holding tank, and final discharge phases. Based on the results obtained, the following biodegradation processes were suggested to occur at the different treatment stages: (1) Lactobacillaceae (35.9%) dominated the first stage, which contributed to high lactic acid production; (2) the higher population of Clostridiaceae in the mixing pond (47.7%) and Prevotellaceae in the holding tank (49.7%) promoted acetic acid production; (3) the aceticlastic methanogen Methanosaetaceae (0.6-0.8%) played a role in acetic acid degradation in the open digester and closed reactor for methane generation; (4) Syntrophomonas (21.5-29.2%) appeared to be involved in the degradation of fatty acids and acetic acid by syntrophic cooperation with the hydrogenotrophic methanogen, Methanobacteriaceae (0.6-1.3%); and (5) the phenols and alcohols detected in the early phases, but not in the final discharge phase, indicated the successful degradation of lignocellulosic materials. The present results contribute to a better understanding of the biodegradation mechanisms involved in the different stages of the full-scale treatment of POME.

Oil Palm Biomass Biorefinery for Sustainable Production of Renewable Materials.

Oil palm biomass is widely known for its potential as a renewable resource for various value-added products due to its lignocellulosic content and availability. Oil palm biomass biorefinery is an industry that comes with sociopolitical benefits through job opportunities, as well as potential environmental benefits. Many studies have been conducted on the technological advancements of oil-palm biomass-derived renewable materials, which are discussed comprehensively in this review. Recent technological developments have made it possible to bring new and innovative technologies to commercialization, such as compost, biocharcoal, biocomposites, and bioplastics.

Subcritical Water-Carbon Dioxide Pretreatment of Oil Palm Mesocarp Fiber for Xylooligosaccharide and Glucose Production.

The present work aimed to investigate the pretreatment of oil palm mesocarp fiber (OPMF) in subcritical H2O-CO2 at a temperature range from 150⁻200 °C and 20⁻180 min with CO2 pressure from 3⁻5 MPa. The pretreated solids and liquids from this process were separated by filtration and characterized. Xylooligosaccharides (XOs), sugar monomers, acids, furans and phenols in the pretreated liquids were analyzed by using HPLC. XOs with a degree of polymerization X2⁻X4 comprising xylobiose, xylotriose, xylotetraose were analyzed by using HPAEC-PAD. Enzymatic hydrolysis was performed on cellulose-rich pretreated solids to observe xylose and glucose production. An optimal condition for XOs production was achieved at 180 °C, 60 min, 3 MPa and the highest XOs obtained was 81.60 mg/g which corresponded to 36.59% of XOs yield from total xylan of OPMF. The highest xylose and glucose yields obtained from pretreated solids were 29.96% and 84.65%, respectively at cellulase loading of 10 FPU/g-substrate.

Isolation and characterization of microcrystalline cellulose from roselle fibers.

In this study, microcrystalline cellulose (MCC) was extracted from roselle fiber through acid hydrolysis treatment and its properties were compared with those of commercially available MCC. The physicochemical and morphological characteristics, elemental composition, size distribution, crystallinity and thermal properties of the obtained MCC were analyzed in this work. Fourier transform infrared spectroscopy (FTIR) analysis provided clear evidence that the characteristic peak of lignin was absent in the spectrum of the MCC prepared from roselle fiber. Rough surface and slight aggregation of MCC were observed by scanning electron microscopy (SEM). Energy dispersive X-ray (EDX) analysis showed that pure MCC with small quantities of residues and impurities was obtained, with a similar elemental composition to that of commercial MCC. A mean diameter of approximately 44.28µm was measured for MCC by using a particle size analyzer (PSA). X-ray diffraction (XRD) showed the crystallinity increased from 63% in roselle pulp to 78% in roselle MCC, the latter having a slightly higher crystallinity than that of commercial MCC (74%). TGA and DSC results indicated that the roselle MCC had better thermal stability than the roselle pulp, whereas it had poorer thermal stability in comparison with commercial MCC. Thus, the isolated MCC from roselle fibers will be going to use as reinforcing element in green composites and may be a precursor for future roselle derived nanocellulose, and thus a promising subject in nanocomposite research.

Impact strength and flexural properties enhancement of methacrylate silane treated oil palm mesocarp fiber reinforced biodegradable hybrid composites.

Natural fiber as reinforcement filler in polymer composites is an attractive approach due to being fully biodegradable and cheap. However, incompatibility between hydrophilic natural fiber and hydrophobic polymer matrix restricts the application. The current studies focus on the effects of incorporation of silane treated OPMF into polylactic acid (PLA)/polycaprolactone (PCL)/nanoclay/OPMF hybrid composites. The composites were prepared by melt blending technique and characterize the composites with Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). FTIR spectra indicated that peak shifting occurs when silane treated OPMF was incorporated into hybrid composites. Based on mechanical properties results, incorporation of silane treated OPMF enhances the mechanical properties of unmodified OPMF hybrid composites with the enhancement of flexural and impact strength being 17.60% and 48.43%, respectively, at 10% fiber loading. TGA thermogram shows that incorporation of silane treated OPMF did not show increment in thermal properties of hybrid composites. SEM micrographs revealed that silane treated OPMF hybrid composites show good fiber/matrix adhesion as fiber is still embedded in the matrix and no cavity is present on the surface. Water absorption test shows that addition of less hydrophilic silane treated OPMF successfully reduces the water uptake of hybrid composites.

The influence of green surface modification of oil palm mesocarp fiber by superheated steam on the mechanical properties and dimensional stability of oil palm mesocarp fiber/poly(butylene succinate) biocomposite.

In this paper, superheated steam (SHS) was used as cost effective and green processing technique to modify oil palm mesocarp fiber (OPMF) for biocomposite applications. The purpose of this modification was to promote the adhesion between fiber and thermoplastic. The modification was carried out in a SHS oven at various temperature (200-230 °C) and time (30-120 min) under normal atmospheric pressure. The biocomposites from SHS-treated OPMFs and poly(butylene succinate) (PBS) at a weight ratio of 70:30 were prepared by melt blending technique. The mechanical properties and dimensional stability of the biocomposites were evaluated. This study showed that the SHS treatment increased the roughness of the fiber surface due to the removal of surface impurities and hemicellulose. The tensile, flexural and impact properties, as well as dimensional stability of the biocomposites were markedly enhanced by the presence of SHS-treated OPMF. Scanning electron microscopy analysis showed improvement of interfacial adhesion between PBS and SHS-treated OPMF. This work demonstrated that SHS could be used as an eco-friendly and sustainable processing method for modification of OPMF in biocomposite fabrication.

Oil palm frond juice as future fermentation substrate: a feasibility study.

Oil palm frond (OPF) juice is a potential industrial fermentation substrate as it has high sugars content and the OPF are readily available daily. However, maximum sugars yield and storage stability of the OPF juice are yet to be determined. This study was conducted to determine the effect of physical pretreatment and storage duration of OPF petiole on sugars yield. Storage stability of OPF juice at different storing conditions was also investigated. It was found that OPF petiole squeezed by hydraulic pressing machine gave the highest sugars recovery at almost 40 g/kg, accounting for a recovery yield of 88%. Storage of OPF petiole up to 72 hrs prior to squeezing reduced the free sugars by 11 g/kg. Concentrated OPF juice with 95% water removal had the best storage stability at both 4 and 30°C, when it was stored for 10 days. Moreover, concentrated OPF syrup prepared by thermal processing did not give any Maillard effect on microbial growth. Based on our results, OPF juice meets all the criteria as a good fermentation substrate as it is renewable, consistently available, and easy to be obtained, it does not inhibit microbial growth and product formation, and it contains no impurities.

Modification of oil palm mesocarp fiber characteristics using superheated steam treatment.

In this study, oil palm mesocarp fiber (OPMF) was treated with superheated steam (SHS) in order to modify its characteristics for biocomposite applications. Treatment was conducted at temperatures 190-230 °C for 1, 2 and 3 h. SHS-treated OPMF was evaluated for its chemical composition, thermal stability, morphology and crystallinity. OPMF treated at 230 °C exhibited lower hemicellulose content (9%) compared to the untreated OPMF (33%). Improved thermal stability of OPMF was found after the SHS treatment. Moreover, SEM and ICP analyses of SHS-treated OPMF showed that silica bodies were removed from OPMF after the SHS treatment. XRD results exhibited that OPMF crystallinity increased after SHS treatment, indicating tougher fiber properties. Hemicellulose removal makes the fiber surface more hydrophobic, whereby silica removal increases the surface roughness of the fiber. Overall, the results obtained herewith suggested that SHS is an effective treatment method for surface modification and subsequently improving the characteristics of the natural fiber. Most importantly, the use of novel, eco-friendly SHS may contribute to the green and sustainable treatment for surface modification of natural fiber.

Factors affecting poly(3-hydroxybutyrate) production from oil palm frond juice by Cupriavidus necator (CCUG52238(T)).

Factors influencing poly(3-hydroxybutyrate) P(3HB) production by Cupriavidus necator CCUG52238(T) utilizing oil palm frond (OPF) juice were clarified in this study. Effects of initial medium pH, agitation speed, and ammonium sulfate (NH(4))(2)SO(4) concentration on the production of P(3HB) were investigated in shake flasks experiments using OPF juice as the sole carbon source. The highest P(3HB) content was recorded at pH 7.0, agitation speed of 220 rpm, and (NH(4))(2)SO(4) concentration at 0.5 g/L. By culturing the wild-type strain of C. necator under the aforementioned conditions, the cell dry weight (CDW) and P(3HB) content obtained were 9.31 ± 0.13 g/L and 45 ± 1.5 wt.%, respectively. This accounted for 40% increment of P(3HB) content compared to the nonoptimized condition. In the meanwhile, the effect of dissolved oxygen tension (DOT) on P(3HB) production was investigated in a 2-L bioreactor. Highest CDW (11.37 g/L) and P(3HB) content (44 wt.%) were achieved when DOT level was set at 30%. P(3HB) produced from OPF juice had a tensile strength of 40 MPa and elongation at break of 8% demonstrated that P(3HB) produced from renewable and cheap carbon source is comparable to those produced from commercial substrate.

Renewable sugars from oil palm frond juice as an alternative novel fermentation feedstock for value-added products.

In this paper, we report that pressed juice from oil palm frond (OPF) contained renewable sugars such as glucose, sucrose and fructose. By using a simple sugarcane press, 50% (wt/wt) of OPF juice was obtained from fresh OPF. The glucose content in the juice was 53.95±2.86g/l, which accounts for 70% of the total free sugars. We have examined the effect of various OPF juice concentrations on the production of poly(3-hydroxybutyrate), P(3HB) by Cupriavidus necator CCUG 52238(T). The cell dry mass in shake flask experiment reached 8.42g/l, with 32wt.% of P(3HB) at 30% (v/v) of OPF juice, comparable with using technical grade sugars. The biopolymer had a molecular mass, M(w) of 812kDa, with a low polydispersity index of 1.61. This result indicates that OPF juice can be used as an alternative renewable carbon source for P(3HB) production and has potential as a renewable carbon source.

Production of bacterial endoglucanase from pretreated oil palm empty fruit bunch by bacillus pumilus EB3.

In this study, endoglucanase was produced from oil palm empty fruit bunch (OPEFB) by a locally isolated aerobic bacterium, Bacillus pumilus EB3. The effects of the fermentation parameters such as initial pH, temperature, and nitrogen source on the endoglucanase production were studied using carboxymethyl cellulose (CMC) as the carbon source. Endoglucanase from B. pumilus EB3 was maximally secreted at 37 degrees C, initial pH 7.0 with 10 g/l of CMC as carbon source, and 2 g/l of yeast extract as organic nitrogen source. The activity recorded during the fermentation was 0.076 U/ml. The productivity of the enzyme increased twofold when 2 g/l of yeast extract was used as the organic nitrogen supplement as compared to the non-supplemented medium. An interesting finding from this study is that pretreated OPEFB medium showed comparable results to CMC medium in terms of enzyme production with an activity of 0.063 U/ml. As OPEFB is an abundant solid waste at palm oil mills, it has the potential of acting as a substrate in cellulase production.