Adsorption and desorption characteristics of zinc on ash particles derived from oil palm waste

Solid waste such as palm fibre and shell produced by the palm oil industry is used by palm oil mills as boiler fuel to produce steam for electricity generation. The ash produced after combustion creates a disposal problem for the palm oil industry. This study explored the potential of oil palm ash as an adsorbent material for removal and recovery of zinc ions from aqueous solutions. The equilibrium uptake of zinc was found to increase with solution pH in the range 3–6, yielding a maximum adsorption capacity of 0.163 mmol g^?1 of ash at a pH of 6. The affinity constant of oil palm ash was found to greatly exceed that of a commercial ion exchange resin, suggesting that oil palm ash may find potential application in treating dilute zinc‐containing waste streams. Four isotherm models were used to fit the constant pH equilibrium isotherms obtained at four different pH values. The entire data set was successfully simulated using two of the isotherm models: a Langmuir model with pH‐dependent parameters and an extended Langmuir–Freundlich model with pH‐independent parameters. The rates of adsorption and desorption for zinc were measured using a stirred‐batch contactor. The contact time required to reach apparent adsorption equilibrium was found to decrease with increasing adsorbent dosage. Both the rate and the extent of zinc desorption were affected by the pH of the desorbing solution. The adsorption and desorption rates were consistent with simple first‐order rate models. © 2002 Society of Chemical Industry     

Adsorption of carotene from palm oil by acid-treated rice hull ash

Rice hull ash obtained by heat treatment and acid activated followed by washing was not effective as an adsorbent for carotene in palm oil in contrast to that reported for adsorption of soy oil lutein. However, unwashed acid-activated ash had activity much higher than carbon and silica but slightly less than a commercial bleaching clay. Heat treatment of raw rice hulls at temperatures below 300°C resulted in the most active adsorbent after acid activation. Drying the unwashed acid-activated ash at temperatures higher than 200°C reduced the activity. The activity of the acid ash was attributed to adsorbed acid. The results also suggested that the removal of carotene in palm oil was caused by chemical interactions involving the adsorbed acid and the carotene. The small amount of Fe³⁺ in the ash was not responsible for the activity.     

Bio-oil production from oil palm biomass via subcritical and supercritical hydrothermal liquefaction

This paper presents the studies on the liquefaction of three types of oil palm biomass; empty fruit bunch (EFB), palm mesocarp fiber (PMF) and palm kernel shell (PKS) using water at subcritical and supercritical conditions. The effect of temperature (330, 360, 390 °C) and pressure (25, 30, 35 MPa) on bio-oil yields were investigated in the liquefaction process using a Inconel batch reactor. The optimum liquefaction condition of the three types of biomass was found to be at supercritical condition of water i.e. at 390 °C and 25 MPa, with PKS yielding the maximum bio-oil yield of 38.53 wt%, followed by EFB and PMF, with optimum yields of 37.39 wt% and 34.32 wt%, respectively. The chemical compositions of the bio-oils produced at optimum condition were analyzed using GC–MS and phenolic compounds constituted the major portion of the bio-oils, with other minor compounds present such as alcohols, ketones, aromatic hydrocarbons and esters.     

Isothermal crystallization kinetics of refined palm oil

The induction times for the crystallization, under isothermal conditions, of refined, bleached, and deodorized palm oil from the melt were studied by viscometry. At temperatures below 295 K, the crystallization of palm oil was observed to occur in a two-stage process. This two-stage process was caused by the fractionation of palm oil, most probably into the stearin and olein fractions. At temperatures higher than 295 K, only a single-stage crystallization process was observed. As seen under polarized light microscopy, spherical crystals were initially formed from the first fraction at temperatures from 287 to 293 K. The diameters of these spherical crystals decreased as the temperature increased. After that, needle-shaped crystals were formed from the second fraction and continued to grow from the surface of these spherical crystals until the spherical crystals were fully enclosed, i.e., the cocrystallization of two polymorphs was observed. At temperatures higher than 293 K, the needle-shaped crystals formed from a mixture of the two fractions were found to be the only polymorphs developed with the onset of crystallization. X-ray diffraction results showed that for temperatures below 295 K, the spherical crystals formed from the first fraction were in α form, whereas the needle-like crystals that nucleated later from the second fraction were in β′ form. β′ crystals were the only polymorphs formed for temperatures above 295 K. The results obtained were in good agreement with the discontinuity observed in the induction time vs. temperature curve. Activation free energies for nucleation were calculated according to the Fisher-Turnbull equation for the various polymorphic forms. Viscometry was observed to be a sensitive method for characterizing the overall crystallization process. This technique is suitable for induction time studies of palm oil crystallization, especially at lower temperatures and with viscous oil.     

Chemical and physical characteristics of soap made from distilled fatty acids of palm oil and palm kernel oil

Manufacture of soaps from distilled fatty acids of palm oil (PO) and palm kernel oil (PK) is a well-established technology in Malaysia. Data on quality and characteristics of various blends of PO/PK fatty acid-based (palm-based) soaps made in Malaysia are not available, however. In view of this, the study described in this paper was undertaken. Eleven blends of palm-based bar soaps were made, and their properties were evaluated. There was an increase in the acid value of blended raw materials with increasing amounts of PK fatty acids. The iodine value and titer (°C) of blended raw materials, however, bear an inverse relationship with the amount of PK fatty acids. As expected, the hardness of the soap bars from the various blends increased with increasing PK fatty acid. Total fatty matter ranged from 76–85%, free caustic content was 0.1%, and sodium chloride content was 0.3–0.4%. Characteristics of soap blends made for this study were comparable with those from other countries. Quality of the soap obtained was comparable to those produced commercially.     

Synthesis of Na-A and -X zeolites from oil shale ash

The solid by-product of oil shale processing (PETROBRAS-Brazil) was used as a raw material to synthesize Na-A and -X zeolites. Two preparation methods using the same starting material composition were carried out. In Method (1), alkaline fusion was used to prepare a glass, which was then hydrated by refluxing. The largest amount of crystallinity was reached with 2 h 30 min of refluxing. In Method (2), alkaline fusion was followed by hydrothermal treatment. The most crystalline sample was obtained after 12 h of heat treatment, and after 96 h hydroxysodalite zeolite was formed. In both procedures, the synthesis products were mainly composed of Na-X zeolite, whose content was influenced by the crystallization time, and of Na-A zeolite, with a practically constant content.     

Combustion of oil palm stone in a pilot-scale fluidised bed reactor

Biomass is being generated in vast amounts from oil palm plantations particularly in developing countries such as Malaysia, Thailand and Indonesia. Oil palm stone (OPS) is currently considered a waste material and has not previously been considered for energy purposes. The main objective of this study was to investigate the thermochemical conversion of OPS in a pilot-scale fluidised bed combustor. The net heating value of OPS was 24.93 MJ/kg. The effect of primary air flowrate and initial bed temperature were the main parameters investigated. The bed and bed's surface temperature were found to decrease as the primary air flowrate increased. In all tests CO emissions were less than 0.2%. The emissions of SO₂ and HCl ranged from 0.02 ppm to 0.05 ppm, significantly below the permitted levels set by legislation. Stable combustion was observed at a bed temperature of 950 °C. The most abundant elements found in the ash were Al, Ca, Fe, K, Mg, Mn, P, S and Si. However, due to the temperature regime used in the study fouling would not be an issue.     

Investigation of sulphation behavior of two fly ash samples produced from combustion of different fuels in a 165 MWe CFB boiler

Emission of sulphur dioxide (SO₂) from combustion of fossil fuel is an important environmental issue. Circulating fluidized bed combustion (CFBC) technology can use limestone sorbent to achieve in situ SO₂ emissions control. This paper presents the chemical and physical analysis results of two fly ash samples derived from a 165 MWe CFBC boiler burning two different fuels with addition of limestone, as they pertain to sulphation behavior. One of the samples in this study was produced from combustion of a bituminous coal with high iron content, the other from firing of blended coal and petroleum coke fuel. The physical examination was conducted by scanning electron microscope (SEM) coupled with an energy dispersive X-ray (EDX) system for analysis of the surface structure or morphology of the sample, as well as the calcium and sulphur distribution. Some large particles derived from high-iron-content fuel were covered by dense iron shells; however, in general such a dense rim was found to not significantly impede the overall desulphurization performance in FBC in terms of the limestone utilization. The large particles (~ 100 μm in diameter) in both samples typically consisted of a CaSO₄ shell and an almost pure CaO core; however, numerous small particles of diameters of 10-20 μm consisted predominantly of CaO without sulphate shells. In particular, the emphasis of this investigation has been focused on the remaining capacity of the fly ash for reaction with sulphur dioxide and to clarify the effects of iron, both samples have been doped with additional iron content, and their sulphation behavior examined, and while both experienced a small reduction in sulphation capacity, the fly ash with the initial low iron content experienced the lowest reduction of sulphation capacity after doping, which is not supportive of the idea that iron has an important effect on sorbent capacity.     

Investigations into the characteristics of oils produced from co-pyrolysis of biomass and tire

Co-pyrolysis of wood biomass and waste tire with such catalysts as SBA-15, MCM-41 and HZSM-5 was carried out in a fixed-bed reactor. The influences of the mixture composition on liquid yield and characteristics of the oil were investigated. The properties of the oil were determined by gel permeation chromatograph (GPC), elemental analyzer (EA), thermal analyzer (TA), densimeter, ubbelohde viscosimeter and compared with that of diesel oil 0#. The contents of the polycyclic aromatic hydrocarbons (PAHs) in the oils were also determined by gas chromatograph (GC). The result shows that co-pyrolysis is in favor of inhibiting the formation of polycyclic aromatic hydrocarbons (PAHs) produced from tire. There exist a hydrogen transfer and a synthetic effect during co-pyrolysis of the biomass and tire. They improve the quality of the oil. SBA-15 as a catalyst is more significant than MCM-41 or HZSM-5 for reducing the density and viscosity of the oil and it can effectively decompose some large molecular compounds into small ones.     

Preparation of silica aerogel from oil shale ash by fluidized bed drying

The silica aerogel with high specific surface area and large pore volume was successfully synthesized using oil shale ash (OSA) via ambient pressure drying. The oil shale ash was burned and leached by sulfuric acid solution, and then was extracted using sodium hydroxide solution to produce a sodium silicate solution. The solution was neutralized with sulfuric acid solution to form a silica gel. After washing with water, the solvent exchange with n-hexane, and the surface modification with hexamethyldisilazane (HMDZ), the aged gel was dried by fluidization technique and also using a furnace to yield silica aerogels. The physical and textural properties of the resultant silica aerogels were investigated and discussed. The results have been compared with silica aerogel powders dried in a furnace. From the results, it is clear that the properties of silica powders obtained in fluidized bed are superior to that of powders dried in the furnace. Using fluidization technique, it could produce silica aerogel powders with low tapping density of 0.0775 g/cm³, high specific surface area (789 m²/g) and cumulative pore volume of 2.77 cm³/g.     

Electron microscopy and phase analysis of fly ash from pressurized fluidized bed combustion

The characterization of the typical fly ashes from pressurized fluidized bed combustion system (PFBC) in Japan and Europe was carried out by electron microscopy and phase analysis using energy-dispersive X-ray spectroscopy (EDX). The purity of limestone as in-bed sulfur removal sorbent influences the desulfurization reaction. The high-purity limestone yielded both hydroxyl ellestadite and anhydrite in Japanese PFBC ashes, while dolomite-rich limestone yielded anhydrite in European PFBC ashes. When the high-purity limestone was used, hydroxyl ellestadite particles were observed as the independent particles or the rim around limestone particles. The Al₂O₃ content in the glassy phase was inversely proportional to the CaO content in the glassy phase, suggesting that the glassy phases were formed from metakaoline and calcite as end members. Since hydroxyl ellestadite, glassy phase and metakaoline are reactive under hydrothermal conditions, PFBC ashes are expected to be used as raw materials for autoclaved products.     

Leaching characteristics of fly ash from fluidized bed combustion thermal power plant: Case study: Çan (Çanakkale-Turkey)

It is known that the concentration of elements of fly ash varies due to the used-coal and the used-lime qualities varying in different periods. In the Çan Thermal Power Plant (CTPP) located at northwestern Turkey, Çan (Çanakkale) basin coals, which are classified as lignite to sub-bituminous C coal with high total sulphur (0.4-12.22%) and a broad range of ash contents (3.2-44.6%) are mainly used. Performed studies reveal that some toxic elements exit in the coal, including As, U and V. Also, while the As, Cu, Co and Hg contents in coal increases, the sulphur contents in coal also increase. Additionally, trace elements that have inorganic compounds in coal are mobilized into air during the combustion process. This poses a big risk for human health and keeping the environment when Çan Basins low quality lignite is burned, it's the fly ash that contains several toxic elements which can leach out and contaminate the water resources.In this study, toxicity tests were conducted on the fly ash samples that were obtained from the fluidized bed combustion of Çan Thermal Power Plant. The results showed that water temperature, pH and the quality of the limestone used were the most important factors affecting the leaching properties. Concentration of some toxic elements found in the fly ash, such as; As, Cd, Cr, Pb, Se and Zn were analyzed. Concentration richness of some heavy metals were attributed to the increase of water temperature, especially when pH is lower than 5. At pH = 5 value, there is no clear explanation of each heavy metal presence in the fly ash from fluidized bed combustion thermal power plant.     

Adsorption of endocrine disrupting ethylparaben from aqueous solution by chemically activated biochar developed from oil palm fibre

The activated biochar (ABC) was prepared, characterized and examined the feasibility of removing ethylparaben (EP) from aqueous solution. The characterization results showed that ABC possessed multi-porous structure and high surface area. The adsorption isotherm was well fitted the Langmuir isotherm and the adsorption kinetic followed the pseudo-second-order model. The maximum adsorption capacity of EP onto ABC was 349.65 mg/g at 298 K. The adsorption capacity maintained 90.82% after five successive adsorption/desorption cycles. ABC possessed high adsorption capacity, usability and stability, which indicating that ABC has great potential to be a promising adsorbent for removal of EP from aqueous solution.     

Investigation of oil palm based Kraft and auto-catalyzed organosolv lignin susceptibility as a green wood adhesives

The aim of this study is to highlight the application and potentiality of oil palm based lignins in the synthesis of green phenolic resins. The delignification processes were conducted using Kraft and auto-catalyzed ethanol–water pulping processes. The extracted lignins were characterized using elemental analysis, Fourier transform-infrared, ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy, molecular weight distribution (M_n, M_w and polydispersity), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The obtained FTIR results revealed that the Kraft lignin contained substantial amounts of guaiacyl units with smaller amounts of syringyl units. The molecular weight of Kraft lignin was 1564 g mol⁻¹ which is higher than organosolv lignin at 1231 g mol⁻¹. The activated free ring position (2.99%) of Kraft lignin was comparatively higher than that of organosolv lignin (2.06%) which was measured using Mannich reactivity analysis. Thermal analysis of Kraft lignin showed higher thermal stability compared to organosolv lignin. The structural and thermal characteristics implied that Kraft lignin had higher potential for the production of green phenolic resins when compared with organosolv lignin.     

Separation of palm carotene from crude palm oil by adsorption chromatography with a synthetic polymer adsorbent

Palm carotene was successfully concentrated from crude palm oil by a single-stage chromatographic process on a synthetic porous polymer. Carotene was concentrated to about 10⁵ ppm solution, which is about 160 times the original concentration in crude palm oil. Carotene recovery varied from 40 to 65% depending upon chromatographic conditions. The fatty acid composition of the palm oil did not change during the carotene recovery process, and the carotene composition was also almost the same as that in palm oil. Adsorption isotherms of the adsorbent differed from other adsorbents. This new recovery method for palm carotene may be suitable as an edible palm oil pretreatment process due to its efficient mass recovery of a valuable bioresource.     

Development of a rigid polyurethane foam from palm oil

The reactions between polymeric diphenyl methane diisocyanate (polymeric MDI) and conventional polyols to produce foamed polyurethane products are well documented and published. Current polyurethane foams are predominantly produced from these reactions whereby the polyol components are usually obtained from petrochemical processes. This article describes a new development in polyurethane foam technology whereby a renewable source of polyol derived from refined–bleached–deodorized (RBD) palm oil is used to produce polyurethane foams. Using very basic foam formulation, rigid polyurethane foams were produced with carbon dioxide as the blowing agent generated from the reaction between excess polymeric MDI with water. The foams produced from this derivatized RBD palm oil have densities in excess of 200 kg/m³ and with compression strengths greater than 1 MPa. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 509–515, 1998     

Enzymatic incorporation of stearic acid into a blend of palm olein and palm kernel oil: Optimization by response surface methodology

Response surface methodology was used to model the incorporation of stearic acid into a blend of palm olein and palm kernel oil in hexane using the sn-1,3-regiospecific lipase Lipozyme RM IM. The factors investigated were incubation time, temperature, and substrate molar ratio. A second-order model with interaction was used to fit the experimental data. The coefficients of determination, R ² and Q ², were 0.96 and 0.90, respectively. The adjusted R ² was 0.95. The regression probability was less than 0.001, and the model showed no lack of fit. Also, a linear relationship was observed between the predicted and observed values. All parameters studied had positive effects on incorporation of stearic acid, with substrate molar ratio having the greatest effect. The interaction terms of substrate molar ratio with temperature and time also had positive effects on incorporation, whereas the effect of the squared term of substrate molar ratio was negative. The quadratic terms of temperature and time, as well as their interaction term, had no significant effect on incorporation at α_0.05. Model verification was done by performing a chi-square test, which showed that there was no significant difference between predicted values and a new set of observed responses.     

Modeling calcium dissolution from oil shale ash: Part 1. Ca dissolution during ash washing in a batch reactor

Batch dissolution experiments were carried out to investigate Ca leachability from oil shale ashes formed in boilers operating with different combustion technologies. The main characteristics of Ca dissolution equilibrium and dynamics, including Ca internal mass transfer through effective diffusion coefficients inside the ash particle were evaluated. Based on the collected data, models allowing simulation of the Ca dissolution process from oil shale ashes during ash washing in a batch reactor were developed. The models are a set of differential equations that describe the changes in Ca content in the solid and liquid phase of the ash-water suspension.     

TG-FTIR在煤灰研究中的应用 ——真实煤灰和模拟灰受热气体释放规律比较

我国的煤炭种类多, 煤灰组成千变万化, 从中找到明确的矿物转变规律并非易事。为探索用模拟灰替代真实煤灰开展高温转变规律研究的可行性, 依据镇雄煤(ZX)煤灰化学成分, 利用FeS₂矿物和Fe₂O₃、SiO₂、Al₂O₃等分析纯化学试剂配制模拟灰, 测试灰熔融温度, 并借助热重红外联用(TG-FTIR)技术比较ZX真实煤灰和模拟灰在氮气气氛下升温过程中的质量变化及气态产物组成。结果表明, 模拟灰的流动温度接近ZX煤灰的流动温度, 最大相差49℃。当温度大于770℃时, 含有FeS₂的模拟灰与真实煤灰的TG-DTG曲线变化趋势一致。FTIR谱图显示两者释放的气体种类相同, 1080℃左右都产生SO₂气体, 此时的硫来源于黄铁矿的部分氧化产物FeS_x。含有FeS₂的模拟灰在高温下的变化更接近真实煤灰。     

Synthesis and characterization of calcium–alumino-silicate hydrates from oil shale ash – Towards industrial applications

The influence of the alkaline medium on the hydrothermal activation of the oil shale fly ash with NaOH and KOH was studied using SEM/EDX, XRD, ²⁹Si and ²⁷Al high-resolution MAS-NMR spectra. In the presence of NaOH the silicon in the original fly ash was completely converted into calcium–aluminum–silicate–hydrates, mainly into 1.1 nm tobermorite structure during 24-h treatment at 160 °C. At similar reaction conditions, the activation with KOH resulted only to the formation of amorphous calcium–silica-hydrate gel on the surface of ash particles at temperature. The results obtained in this study indicate that the oil shale fly ash can be used for production of Al-substituted tobermorites when strongly alkaline media (NaOH) is applied. The synthesized product was used in a catalytic d-lactose isomerization reaction.