Enhancement of batch biohydrogen production from prehydrolysate of acid treated oil palm empty fruit bunch

Carbohydrates from hydrolyzed biomass has been a potential feedstock for fermentative hydrogen production. In this study, oil palm empty fruit bunch (OPEFB) was treated by sulfuric acid in different concentrations at 120 °C for 15 min in the autoclave. The optimal condition for pretreatment was obtained when OPEFB was hydrolyzing at 6% (w/v) sulfuric acid concentration, which gave the highest total sugar of 26.89 g/L and 78.51% of sugar production yield. However, the best conversion efficiency of OPEFB pretreatment was 39.47 at sulfuric acid concentration of 4%. A series of batch fermentation were performed to determine the effect of pH in fermentation media and the potential of this prehydrolysate was used as a substrate for fermentative hydrogen production under optimum pretreatment conditions. The prehydrolysate of OPEFB was efficiently converted to hydrogen via fermentation by acclimatized mixed consortia. The maximum hydrogen production was 690 mL H₂ L⁻¹ medium, which corresponded to the yield of 1.98 molH₂/mol_xylose achieved at pH 5.5 with initial total sugar concentration of 5 g/L. Therefore, the results implied that OPEFB prehydrolysate is prospective substrate for efficient fermentative hydrogen conducted at low controlled pH. No methane gas was detected throughout the fermentation.     

Continuous production of biohydrogen from oil palm empty fruit bunch hydrolysate in tubular photobioreactors

Production of hydrogen by the photosynthetic bacterium Rhodobacter sphaeroides was compared in continuously operated tubular photobioreactors illuminated by natural outdoor sunlight (0.15–66 klux; diurnal cycle) and constant indoor artificial light (10 klux; tungsten lamps). In both cases the operating temperature was 35 °C and the organic carbon source was an acid hydrolysate of oil palm empty fruit bunch (EFB), an agroindustrial waste. In the outdoor photobioreactor, under the best production conditions, the daytime feeding rate of the mixed carbon substrate was 48 mL h^?1 and the average pseudo-steady state hydrogen production rate was 36 mL H₂ L^?1 medium h^?1. The cumulative hydrogen production was 430 mL H₂ L^?1 medium. For the indoor photobioreactor fed at the same rate as the outdoor system, the steady state average hydrogen production rate was 43 mL H₂ L^?1 h^?1 and the cumulative hydrogen production was 517 mL H₂ L^?1 medium. Reducing the feed rate to less than 48 mL h^?1, enhanced the biomass concentration, but reduced hydrogen production in both bioreactors. The sunlight-based cumulative hydrogen production was only about 17% less compared to the artificially lit system, but required only 22% of the electrical energy.     

An outlook of Malaysian energy, oil palm industry and its utilization of wastes as useful resources

Malaysia has an abundance of energy resources, both renewable and non-renewable. The largest non-renewable energy resource found in Malaysia is oil, and second, is natural gas, primarily liquefied natural gas. The production and consumption of oil, gas and coal in Malaysia are given in this paper. The energy demand and supply by source are also shown in relation to the country’s fuel diversification policy. In order to reduce the overall dependence on a single source of energy, efforts were undertaken to encourage the utilization of renewable resources. Forest residue and oil palm biomass are found to be potentially of highest energy value and considered as the main renewable energy option for Malaysia.Palm oil and related products represent the second largest export of Malaysia. The total oil palm planted area in Malaysia has increased significantly in recent years. This paper gives a detailed representation of oil palm planted and produced together with its yield from the year 1976 onwards. The large amounts of available forest and palm oil residues resulting from the harvest can be utilized for energy generation and other by-products in a manner that also addresses environmental concerns related to current waste disposal methods.     

The effect of particle size of CaO and MgO as catalysts for gasification of oil palm empty fruit bunch to produce hydrogen

Finely ground and dried palm oil empty fruit bunch (EFB) was gasified using a temperature-programmed technique which online with mass spectrometer. Temperature-programmed gasification (TPG) was done under 5% oxygen in helium to determine the production of hydrogen, as well as CO, CO₂ and CH₄. TPG was performed from 50–700 °C at the heating rate of 10 °C min⁻¹. The temperature was held for 1 h at the final temperature. The effect of mass ratio of metal oxide:EFB was also investigated. Different particle size of calcium oxide and magnesium oxide were chosen as the catalysts. Bulk calcium oxide has shown to enhance the evolution of hydrogen. Nanosized calcium oxide enhanced the production of hydrogen compared to the bulk one and consequently reduced the production of carbon dioxide. Interestingly, when the mass ratio of metal oxide:EFB was changed to 1:2, nanosized MgO showed very significant increase of H₂ production. All the used catalysts were analyzed by XRD to show the transformation of both bulk and nanosized metal oxides to metal carbonates.     

Biohydrogen production from pentose-rich oil palm empty fruit bunch molasses: A first trial

Oil palm empty fruit bunch (OPEFB) was pretreated by local plantation industry to increase the accessibility towards its fermentable sugars. This pretreatment process led to the formation of a dark sugar-rich molasses byproduct. The total carbohydrate content of the molasses was 9.7 g/L with 4.3 g/L xylose (C₅H₁₀O₅). This pentose-rich molasses was fed as substrate for biohydrogen production using locally isolated Clostridium butyricum KBH1. The effect of initial pH and substrate concentration on the yield and productivity of hydrogen production were investigated in this study. The best result for the fermentation performed in 70 mL working volume was obtained at the initial reaction condition of pH 9, 150 rpm, 37 °C and 5.9 g/L total carbohydrate. The maximum hydrogen yield was 1.24 mol H₂/mol pentose and the highest productivity rate achieved was 0.91 mmol H₂/L/h. The optimal pH at pH 9 was slightly unusual due to the presence of inhibitors, mainly furfural. The furfural content decreased proportionally as pH was increased. The optimal experiment condition was repeated and continued in fermentation volume of 200 mL. The maximum hydrogen yield found for this run was 1.21 mol H₂/mol pentose while the maximum productivity was 1.1 mmol H₂/L/h. The major soluble metabolites in the fermentation were n-butyric acid and acetic acid.     

Potential of hydrogen from oil palm biomass as a source of renewable energy worldwide

Various catastrophes related to extreme weather events such as floods, hurricanes, droughts and heat waves occurring on the Earth in the recent times are definitely a clear warning sign from nature questioning our ability to protect the environment and ultimately the Earth itself. Progressive release of greenhouse gases (GHG) such as CO₂ and CH₄ from development of various energy-intensive industries has ultimately caused human civilization to pay its debt. Realizing the urgency of reducing emissions and yet simultaneously catering to needs of industries, researches and scientists conclude that renewable energy is the perfect candidate to fulfill both parties requirement. Renewable energy provides an effective option for the provision of energy services from the technical point of view. In this context, biomass appears as one important renewable source of energy. Biomass has been a major source of energy in the world until before industrialization when fossil fuels become dominant and researches have proven from time to time its viability for large-scale production. Although there has been some successful industrial-scale production of renewable energy from biomass, generally this industry still faces a lot of challenges including the availability of economically viable technology, sophisticated and sustainable natural resources management, and proper market strategies under competitive energy markets. Amidst these challenges, the development and implementation of suitable policies by the local policy-makers is still the single and most important factor that can determine a successful utilization of renewable energy in a particular country. Ultimately, the race to the end line must begin with the proof of biomass ability to sustain in a long run as a sustainable and reliable source of renewable energy. Thus, the aim of this paper is to present the potential availability of oil palm biomass that can be converted to hydrogen (leading candidate positioned as the energy of the millennium) through gasification reaction in supercritical water, as a source of renewable energy to policy-makers. Oil palm topped the ranking as number 1 fruit crops in terms of production for the year 2007 with 36.90 million tonnes produced or 35.90% of the total edible oil in the world. Its potentiality is further enhanced by the fact that oil constitutes only about 10% of the palm production, while the rest 90% is biomass. With a world oil palm biomass production annually of about 184.6 million tons, the maximum theoretical yield of hydrogen potentially produced by oil palm biomass via this method is 2.16×10¹⁰ kg H₂ year⁻¹ with an energy content of 2.59 EJ year⁻¹, meeting almost 50% of the current worldwide hydrogen demand.     

Distributed production of hydrogen by auto-thermal reforming of fast pyrolysis bio-oil

We demonstrated an auto-thermal reforming process for producing hydrogen from biomass pyrolysis liquids. Using a noble metal catalyst (0.5% Pt/Al₂O₃ from BASF) at a methane-equivalent space velocity of around 2000 h⁻¹, a reformer temperature of 800 °C–850 °C, a steam-to-carbon ratio of 2.8–4.0, and an oxygen-to-carbon ratio of 0.9–1.1, we produced 9–11 g of hydrogen per 100 g of fast pyrolysis bio-oil, which corresponds to 70%–83% of the stoichiometric potential. The elemental composition of bio-oil and the bio-oil carbon-to-gas conversion, which ranged from 70% to 89%, had the most significant impact on the yield of hydrogen. Because of incomplete volatility the remaining 11%–30% of bio-oil carbon formed deposits in the evaporator. Assuming the same process efficiency as that in the laboratory unit, the cost of hydrogen production in a 1500 kg/day plant was estimated at $4.26/kg with the feedstock, fast pyrolysis bio-oil, contributing 56.3% of the production cost.     

Characterization of bio-oil obtained from fruit pulp pyrolysis

Apricot pulps was pyrolyzed in a fixed-bed reactor under different pyrolysis conditions to determine the role of final temperature, sweeping gas flow rate and steam velocity on the product yields and liquid product composition with a heating rate of 5 °C/min. Final temperature range studied was between 300 and 700 °C and the highest liquid product yield was obtained at 550 °C. Liquid product yield increased significantly under nitrogen and steam atmospheres. For the optimum conditions, pyrolysis of peach pulp was furthermore studied. Liquid products obtained under the most suitable conditions were characterized by FTIR and ¹H-NMR. In addition, gas chromatography/mass spectrophotometer was achieved on all pyrolysis oils. Characterization showed that bio-oil could be a potential source for synthetic fuels and chemical feedstock.     

Production of a hydrogen-rich gas from fast pyrolysis bio-oils: Comparison between homogeneous and catalytic steam reforming routes

The aim of the present work is to produce hydrogen from biomass through bio-oil. Two possible upgrading routes are compared: catalytic and non-catalytic steam reforming of bio-oils. The main originality of the paper is to cover all the steps involved in both routes: the fast pyrolysis step to produce the bio-oils, the water extraction for obtaining the bio-oil aqueous fractions and the final steam reforming of the liquids. Two reactors were used in the first pyrolysis step to produce bio-oils from the same wood feedstock: a fluidized bed and a spouted bed. The mass balances and the compositions of both batches of bio-oils and aqueous fractions were in good agreement between both processes. Carboxylic acids, alcohols, aldehydes, ketones, furans, sugars and aromatics were the main compounds detected and quantified. In the steam reforming experiments, catalytic and non-catalytic processes were tested and compared to produce a hydrogen-rich gas from the bio-oils and the aqueous fractions. Moreover, two different catalytic reactors were tested in the catalytic process (a fixed and a fluidized bed). Under the experimental conditions tested, the H₂ yields were as follows: catalytic steam reforming of the aqueous fractions in fixed bed (0.17 g H₂/g organics) > non-catalytic steam reforming of the bio-oils (0.14 g H₂/g organics) > non-catalytic steam reforming of the aqueous fractions (0.13 g H₂/g organics) > catalytic steam reforming of the aqueous fractions in fluidized bed (0.07 g H₂/g organics). These different H₂ yields are a consequence of the different temperatures used in the reforming processes (650 °C and 1400 °C for the catalytic and the non-catalytic, respectively) as well as the high spatial velocity employed in the catalytic tests, which was not sufficiently low to reach equilibrium in the fluidized bed reactor.     

Cellulolytic enzymes produced by a newly isolated soil fungus Penicillium sp. TG2 with potential for use in cellulosic ethanol production

A newly isolated soil fungus, Penicillium sp. TG2, had cellulase activities that were comparable to those of Trichoderma reesei RUT-C30, a common commercial strain used for cellulase production. The maximal and specific activities were 1.27 U/mL and 2.28 U/mg for endoglucanase, 0.31 U/mL and 0.56 U/mg for exoglucanase, 0.54 U/mL and 1.03 U/mg for β-glucosidase, and 0.45 U/mL and 0.81 U/mg for filter paper cellulase (FPase), respectively. Optimal FPase activity was at pH 5.0 and 50 °C. We used a simultaneous saccharification and fermentation (SSF) process, which employed the yeast Kluyveromyces marxianus and Penicillium sp. TG2 cellulolytic enzymes, to produce ethanol from empty palm fruit bunches (EFBs), a waste product from the palm oil industry. The present findings indicate that Penicillium sp. TG2 has great potential as an alternative source of enzymes for saccharification of lignocellulosic biomass.     

Effect of kaolin addition on ash characteristics of palm empty fruit bunch (EFB) upon combustion

Palm empty fruit bunch (EFB), a by-product of the palm oil industry, is being recognized as one of the most potential kinds of biomass for energy production in Thailand. However, it has been reported that, in combusting EFB in boilers, some compounds evolving from abundant alkali metals in EFB into gas-phase condense and deposit on low-temperature surfaces of heat exchange equipment, causing fouling and corrosion problems. To come up with a solution to impede the deposition, kaolin, which is abundant in kaolinite (Al₂Si₂O₅(OH)₄), is employed to capture the alkali metal vapours eluding from the combustion region. The experiments were designed to simulate the combustion situations that may take place when kaolin is utilized in two different approaches: premixing of kaolin with EFB prior to combustion and gas-phase reaction of volatiles from EFB with kaolin. The amounts of kaolin used were 8% and 16% by weight based on dry weight of EFB, which were equivalent to one and two times of the theoretical kaolin requirement to capture all potassium originally present in the EFB. The furnace temperatures used for EFB combustion were 700–900 °C and ashes were analyzed by XRF and XRD. The results revealed that, under the kaolin premixing condition, 8% kaolin addition was sufficient to capture the potassium compounds at low temperature, i.e. 700 and 800 °C. However, when the temperature was increased to 900 °C, 16% kaolin addition was needed to completely capture the potassium compounds. The results from gas-phase experiments showed that kaolin can capture volatile potassium at maximum 25% at 900 °C. The XRD results showed, for both experimental cases, the evidence of formation of the high melting temperature potassium-alumino-silicates, which confirmed the reaction of potassium compounds with kaolin. The study also suggests that the premixing method is better than the other because of its higher overall capture efficiency.     

Influence of mineral matter on pyrolysis of palm oil wastes

The influence of mineral matter on pyrolysis of biomass (including pure biomass components, synthesized biomass, and natural biomass) was investigated using a thermogravimetric analyzer (TGA). First, the mineral matter, KCl, K₂CO₃, Na₂CO₃, CaMg(CO₃)₂, Fe₂O₃, and Al₂O₃, was mixed respectively with the three main biomass components (hemicellulose, cellulose, and lignin) at a weight ratio (C/W) of 0.1 and its pyrolysis characteristics were investigated. Most of these mineral additives, except for K₂CO₃, demonstrated negligible influence. Adding K₂CO₃ inhibited the pyrolysis of hemicellulose by lowering its mass loss rate by 0.3 wt%/°C, while it enhanced the pyrolysis of cellulose by shifting the pyrolysis to a lower temperature. With increased K₂CO₃ added, the weight loss of cellulose in the lower temperature zone (200-315 °C) increased greatly and the activation energies of hemicellulose and cellulose pyrolysis decreased notably from 204 to 42 kJ/mol. Second, studies on the synthetic biomass of hemicellulose, cellulose, lignin, and K₂CO₃ (as a representative of minerals) indicated that peaks of cellulose and hemicellulose pyrolysis became overlapped with addition of K₂CO₃ (at C/W = 0.05-0.1), due to the catalytic effect of K₂CO₃ lowering cellulose pyrolysis to a lower temperature. Finally, a local representative biomass—palm oil waste (in the forms of original material and material pretreated through water washing or K₂CO₃ addition)—was studied. Water washing shifted pyrolysis of palm oil waste to a higher temperature by 20 °C, while K₂CO₃ addition lowered the peak temperature of pyrolysis by . It was therefore concluded that the obvious catalytic effect of adding K₂CO₃ might be attributed to certain fundamental changes in terms of chemical structure of hemicellulose or decomposition steps of cellulose in the course of pyrolysis.     

Production of hydrogen by lignins fast pyrolysis

This paper reports the results of experiments performed on the flash pyrolysis of lignin samples submitted to controlled heat flux densities (short flashes of a concentrated radiation). Two types of lignins are used: Kraft and Organocell lignins. Microscopic observations of the reacted samples reveal the formation of an intermediate liquid compound that precedes the further formation of char, vapours and gases. The rates of mass loss and the production rates of the products are determined for both lignins. The results are compared to each other and to those obtained in former similar studies made with cellulose.

The analyses of the produced gases reveal high syngas and H₂ contents (respectively 87 and 50 mol%). This composition is compared to results obtained in other different thermal conditions with lignins and other types of biomasses. The possible mechanism of hydrogen formation is further discussed.     

Analysis of syngas production rate in empty fruit bunch steam gasification with varying control factors

Biomass gasification is a prevailing approach for mitigating irreversible fossil fuel depletion. In this study, palm empty fruit bunch (EFB) was steam-gasified in a fixed-bed, batch-fed gasifier, and the effect of four control factors—namely torrefaction temperature for EFB pretreatment, gasification temperature, carrier-gas flow rate, and steam flow rate—on syngas production were investigated. The results showed that steam flow rate is the least influential control factor, with no effect on syngas composition or yield. The gasification temperature of biomass significantly affects the composition of syngas generated during steam gasification, and the H₂/CO ratio increases by approximately 50% with an increase in temperature ranging from 680 °C to 780 °C. The higher H₂/CO ratio at a lower gasification temperature increased the energy density of the combustible constituents of the syngas by 3.43%.     

Evaluation and optimization of organosolv pretreatment using combined severity factors and response surface methodology

In this study, ethanol organosolv pretreatment was investigated and optimized for the pretreatment of empty palm fruit bunch using (1) response surface methodology based on three-variable central composite design and (2) the combined severity parameters. The reaction parameters studied were sulfuric acid concentration (0.5–2.0%), reaction temperature (160–200 °C) and residence time (45–90 min). Both models provide valuable and complementary informations: using combined severity parameters, very good predictions were obtained concerning xylan and lignin extraction whereas central composite design is the best model for glucose production. The optimal values of the variables were as the followings: sulfuric acid 2.0% w/w, 160 °C, 78 min and the experimental values (96.0%) concerning glucose and lignin recovery were in excellent agreement with the central composite design prediction (100%).     

Empty fruit bunches from oil palm as a potential raw material for fuel ethanol production

In this paper the fuel ethanol production from empty fruit bunches was experimentally evaluated using alkaline pretreatment and enzymatic hydrolysis for sugars release. Fermentation was accomplished using a native Saccharomyces cerevisiae strain. Ethanol concentration was carried on using a glass bench-scale distillation column. Experimental results were used for planning and designing the process scheme using Aspen Plus. Process simulation allowed calculating the mass and energy balances. It was found that coupling alkaline pretreatment with a later autoclaving improved the sugars yield in enzymatic hydrolysis. However, the use of the remaining soaking solution from pretreatment as hydrolysis medium had negative effects on sugars yield suggesting that there exist inhibit substance for the enzyme. Better results for enzymatic hydrolysis were obtained when sodium acetate buffer was used. Ethanol yield obtained from both experiments and simulation were very similar (66.50 and 65.84 dm³ of ethanol per each t of empty fruit bunches, respectively). These low ethanol yields were obtained because the native S. cerevisiae does not assimilate all reducing sugars, suggesting that those sugars were pentoses. Simulated alkaline and autoclaving pretreatment contributed only with 2% of the total energy consumption (198.4 GJ m⁻³ ethanol) while product recovery represented 57% of the total energy.     

Photofermentive production of biohydrogen from oil palm waste hydrolysate

Oil palm empty fruit bunch (OPEFB) was hydrolyzed with dilute sulfuric acid (6% v/v; 8 mL acid per g dry OPEFB) at 120 °C for 15-min to release the fermentable sugars. The hydrolysate contained xylose (23.51 g/L), acetic acid (2.44 g/L) and glucose (1.80 g/L) as the major carbon components. This hydrolysate was used as the sole carbon source for photofermentive production of hydrogen using a newly identified photosynthetic bacterium Rhodobacter sphaeroides S10. A Plackett–Burman experimental design was used to examine the influence of the following on hydrogen production: yeast extract concentration, molybdenum concentration, magnesium concentration, EDTA concentration and iron concentration. These factors influenced hydrogen production in the following decreasing order: yeast extract concentration > molybdenum concentration > magnesium concentration > EDTA concentration > iron concentration. Under the conditions used (35 °C, 14.6 W/m² illumination, initial pH of 7.0), the optimal composition of the culture medium was (per L): mixed carbon in OPEFB hydrolysate 3.87 g, K₂HPO₄ 0.9 g, KH₂PO₄ 0.6 g, CaCl₂⋅2H₂O 75 mg, l-glutamic acid 795.6 mg, FeSO₄⋅7H₂O 11 mg, Na₂MoO₂⋅2H₂O 1.45 mg, MgSO₄⋅7H₂O 2.46 g, EDTA 0.02 g, yeast extract 0.3 g). With this medium, the lag period of hydrogen production was 7.65 h, the volumetric production rate was 22.4 mL H₂/L medium per hour and the specific hydrogen production rate was 7.0 mL H₂/g (xylose + glucose + acetic acid) per hour during a 90 h batch culture of the bacterium. Under optimal conditions the conversion efficiency of the mixed carbon substrate to hydrogen was nearly 29%.     

Utilization possibilities of palm shell as a source of biomass energy in Malaysia by producing bio-oil in pyrolysis process

Agriculture residues such as palm shell are one of the biomass categories that can be utilized for conversion to bio-oil by using pyrolysis process. Palm shells were pyrolyzed in a fluidized-bed reactor at 400, 500, 600, 700 and 800 °C with N₂ as carrier gas at flow rate 1, 2, 3, 4 and 5 L/min. The objective of the present work is to determine the effects of temperature, flow rate of N₂, particle size and reaction time on the optimization of production of renewable bio-oil from palm shell. According to this study the maximum yield of bio-oil (47.3 wt%) can be obtained, working at the medium level for the operation temperature (500 °C) and 2 L/min of N₂ flow rate at 60 min reaction time. Temperature is the most important factor, having a significant positive effect on yield product of bio-oil. The oil was characterized by Fourier Transform infra-red (FT-IR) spectroscopy and gas chromatography/mass spectrometry (GC-MS) techniques.     

Effect of reactor configuration on the yields and structures of pine-wood derived pyrolysis liquids: A comparison between ablative and wire-mesh pyrolysis

Product distributions from the pyrolysis of a common sample of pine-wood have been determined for two reactors with different configurations. The ablative pyrolysis reactor operates on the principle of “scraping” a continuous stream of biomass particles onto a heated surface under conditions of high relative motion and high applied pressure. In the wire-mesh reactor configuration, fine dispersion of a small quantity [4–6 mg] of sample and the rapid removal of volatiles from the reaction zone ensures that volatiles released during pyrolysis are captured under conditions minimising extra particle secondary reactions.

Comparison of liquid yields determined for the two reactors has been undertaken in order to assess the effect of secondary reactions on yields during ablative pyrolysis. Structural characterisations and comparison of liquids produced in the two reactors have been carried out by size exclusion chromatography, UV-fluorescence spectroscopy and FTIR spectroscopy. Slight differences in structures were apparent either due to cracking of lignin-derived macromolecules on the heated reactor surface or low molecular weight components formed during slow pyrolysis reactions of a small proportion of the feed material. Comparison of the ablative liquids with those from other ablative pyrolysis reactors show similar trends in molecular mass distributions and structures suggesting that the ablative pyrolysis process inherently cracks some liquids during volatilisation. Dry organic liquid yields from the ablative pyrolysis reactor were between 2.5 and 5.3% lower than the wire-mesh reactor between 55° and 600°C. This is believed to be a result of non-optimised reactor operation of the ablative pyrolysis reactor.