Characterization of empty fruit bunch for microwave-assisted pyrolysis

Agricultural waste such as oil palm empty fruit bunch (EFB) is of environmental concern to Malaysia as one of the world’s largest oil palm producers. Pyrolysis can be used to treat biomass waste due to its flexibility in producing solid, liquid and gas products. This study attempts to characterize EFB for pyrolysis using microwaves as an alternative heating source. EFB taken from a local oil palm mill was subjected to fuel, chemical and dielectric property analysis. The findings revealed that high moisture and 47% oxygen gave low calorific value of 16 MJ/kg. Notably, high water content is an advantage in microwave heating as water is a good microwave absorber, which results in fast drying. Further, a high volatile content at 70% gave the EFB an advantage of high reactivity. A moderate potassium content of 12.8% could also positively affect microwave absorption. The dielectric properties of EFB were observed to be proportional to the moisture content. Furthermore, the microwave penetration depth was found highest at 20% moisture, i.e. 3.5 cm. However, low values of both dielectric constant and loss of dried EFBs would require the addition of microwave absorbers for pyrolysis reaction. The fuel and chemical characteristics of EFB were found comparable to other biomasses, which indicated a good candidate for microwave pyrolysis treatment.     

Life cycle assessment to evaluate the green house gas emission from oil palm bio-oil based power plant

The objective of this study is to assess the green house gas (GHG) emission for the production of bio-oil from oil palm biomass and its utilization for 10 MW power generation by evaluating the life cycle carbon footprint analysis. The life cycle GHG emission assessment includes four main stages, which cover the oil-palm cultivation, palm oil mill operation, biomass transportation and pyrolysis process for the production of bio-oil and its utilization for 10MW power generation. The results obtained suggest that the palm bio-oil has potential as a carbon neutral renewable energy source in the future. More importantly, it has no negative impact on the environment as the amount of CO₂ emitted to the atmosphere during combustion of this fuel is lower than that of the CO₂ absorbed from the atmosphere during cultivation stage.     

Pyrolysis oil upgrading by high pressure thermal treatment

High pressure thermal treatment (HPTT) is a new process developed by BTG and University of Twente with the potential to economically reduce the oxygen and water content of oil obtained by fast pyrolysis (pyrolysis oil), properties that currently complicate its co-processing in standard refineries. During the HPTT process, pyrolysis oil undergoes a phase split yielding a gas phase, an aqueous phase and an oil phase. In this study, HPTT experiments were carried out at different operating conditions in a continuous tubular reactor. Experimental results showed that, with increasing temperature and residence time, the release of gases (mainly CO₂) and the production of water increased, reducing the oxygen content of the oil phase and hence increasing the energy content (from 14.1 to 28.4 MJ/kg) having the temperature a larger effect when compared to the residence time. Using gel permeation chromatography (GPC), an increase of the molecular weight of the oil phase, probably due to polymerisation of the sugars present in pyrolysis oil, was observed. When water was added as solvent to dilute the feed oil, a decrease of the molecular weight of the resulting oil phase was observed. This indicated that the concentration of organic components had a direct effect on the formation of high molecular weight components. In conclusion, during HPTT an oil with lower oxygen and water content with higher energy value was produced, but adverse formation of high molecular weight components was also detected.     

Production of bio‐crude from forestry waste by hydro‐liquefaction in sub‐/super‐critical methanol

Hydro‐liquefaction of a woody biomass (birch powder) in sub‐/super‐critical methanol without and with catalysts was investigated with an autoclave reactor at temperatures of 473–673 K and an initial pressure of hydrogen varying from 2.0 to 10.0 MPa. The liquid products were separated into water soluble oil and heavy oil (as bio‐crude) by extraction with water and acetone. Without catalyst, the yields of heavy oil and water soluble oil were in the ranges of 2.4–25.5 wt % and 1.2–17.0 wt %, respectively, depending strongly on reaction temperature, reaction time, and initial pressure of hydrogen. The optimum temperature for the production of heavy oil and water soluble oil was found to be at around 623 K, whereas a longer residence time and a lower initial H₂ pressure were found to be favorite conditions for the oil production. Addition of a basic catalyst, such as NaOH, K₂CO₃, and Rb₂CO₃, could significantly promote biomass conversion and increase yields of oily products in the treatments at temperatures less than 573 K. The yield of heavy oil attained about 30 wt % for the liquefaction operation in the presence of 5 wt % Rb₂CO₃ at 573 K and 2 MPa of H₂ for 60 min. The obtained heavy oil products consisted of a high concentration of phenol derivatives, esters, and benzene derivatives, and they also contained a higher concentration of carbon, a much lower concentration of oxygen, and a significantly increased heating value (>30 MJ/kg) when compared with the raw woody biomass. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Characterization of products from slow pyrolysis of palm kernel cake and cassava pulp residue

Slow pyrolysis studies of palm kernel cake (PKC) and cassava pulp residue (CPR) were conducted in a fixed-bed reactor. Maximum liquid yield (54.3 wt%) was obtained from PKC pyrolysis at 700 °C, heating rate of 20 °C/min, N₂ gas flow rate of 200 cm³/min and particle size of 2.03 mm. Fuel properties of bi-oils were in following ranges: density, 1.01–1.16 g/cm³; pH, 2.8–5.6; flash point, 74–110 °C and heating value, 15 MJ/kg for CPR oil and 40 MJ/kg for PKC oil. PKC oil gave main contents of n-C₈–C₁₈ carboxylic acids, phenols, and esters, whereas CPR oil gave the highest amount of methanol soluble fraction consisting of polar and non-volatile compounds. On gas compositions, CPR pyrolysis gave the highest yield of syngas produced, while PKC pyrolysis offered the highest content of CO₂. Pyrolysis chars possessed high calorific values in range from 29–35 MJ/kg with PKC char showing a characteristic of reasonably high porosity material.     

Properties of palm-oil-in-water emulsions: Effect of mixed emulsifiers

Palm-oil-in-water emulsions were prepared with mixtures of Tween 40 and Span 40 in various proportions. Stability and droplet-size distribution of the emulsions were monitored. Interfacial tensions of the palm oil/water interface were also determined in the presence of these emulsifier mixtures. Emulsifying efficiency of the emulsifier mixtures was assessed. No synergistic effect of Tween 40 (sorbitan monopalmitate with 18–22 moles of ethylene oxide) and Span 40 (sorbitan monopalmitate) was found on interfacial tension. Tween 40 alone (hydrophilic-lipophilic balance value 15.6) at 1.0% w/w gave palm oil emulsions that were stable for more than 30 d at 60°C. Emulsifier mixtures of Tween 40 and Span 40 with hydrophilic-lipophilic balance values in the range of 8.0–8.6 produced stable emulsions only at much higher emulsifier-mixture concentrations. The inherent nature of the oil and the accompanying natural surface-active materials present in the oil can influence the prevailing conditions at the oil/water interface and alter composition of the interfacial film and hence its stability.     

Detailed CFD modelling of fast pyrolysis of different biomass types in fluidized bed reactors

In the present study, an Eulerian‐Eulerian computational fluid dynamics (CFD) model, combined with a comprehensive biomass reaction scheme, was used to simulate fast pyrolysis of four different biomass types in the fluidized bed reactors. The study focuses on the influence of biomass components of different biomass types on the yields, formations, and contents of compositions of pyrolysis products. The result showed that the bio‐oil yield of cellulose‐rich biomass was higher than other biomass types, and char was mainly produced by the fast pyrolysis of LIG‐C of biomass. Moreover, the contents of bio‐oil components were affected by the fast pyrolysis of biomass components. Further, the energy recovery coefficient (ERC) of bio‐oil obtained from pyrolysis of different biomass types was also calculated and analyzed in this paper.

     

The effect of the refining process on the interfacial properties of palm oil

The interfacial tension of palm oil against water at 60°C was determined in the presence of monoglycerides with (i) different acyl chain lengths, (ii) the same acyl chain length but with different unsaturation, and (iii) different phospholipids. The interfacial tensions of the oil/water interface were depressed, albeit to different extents, by the presence of these substances, depending on the acyl chain length, unsaturation, and the chemical structure of the species adsorbed. The adsorption of the saturated monoglycerides C12∶0, C14∶0, C16∶0, C18∶0 and the unsaturated monoglycerides of C18∶1 and C18∶3 is consistent with a Langmuir isotherm at the palm oil/water interface. However, fitting of the data for C18∶2, l-α-phosphatidylcholine, and lysophosphatidylcholine to the Langmuir isotherm is less satisfactory. The surface areas of the materials adsorbed at the palm oil/water interface are much larger than those of liquid condensed films and closer to those for liquid expanded films. The influence of the nature of the oil (triglycerides), the minor components in the oil, and thier interactions with the added lipids at the oil/water interface are briefly discussed. The effect of the refining process on the interfacial properties of palm oil against water was also studied. The efficiency of the refining process in minor oil contaminants’ removal and the quality of the oil obtained as reflected by the interfacial properties of the oil is discussed.     

生物质热解制生物油及其提质研究现状

生物质能源作为可再生能源的重要组成部分,其综合高效利用在能源替代与补充、保护生态环境等方面具有重要的战略意义。生物油是生物质通过热裂解技术获得的液体产物,具有能量密度较高、环境友好、可再生及可直接输送等优点,可替代传统化石燃料推广使用,解决日益严重的能源紧缺与环境污染等问题。生物质热解制油技术的开发与利用,已成为新世纪可持续能源研究领域的重要课题之一。总结了近年来生物质热解制油技术的主要研究进展,重点关注热解反应器、催化热解技术与生物油的提质利用方面的研究,介绍了碱金属、氧化物和分子筛3种生物质热解催化剂,以及乳化、催化加氢、催化裂解、催化酯化和重整制氢5种生物质提质方法,最后对生物质热解技术的现状及发展趋势进行了总结和概括。     

Direct catalytic upgrading of biomass pyrolysis vapors by a dual function Ru/TiO2 catalyst

The results of catalytic treatment of vapors exiting a g/min pyrolysis unit before product condensation to the liquid phase using a Ru/TiO₂ catalyst for oak and switchgrass pyrolysis are reported. The pyrolysis is conducted at 500°C and the catalysis at 400°C at atmospheric pressure with a hydrogen partial pressure of 0.58 atm. It is found that the catalytic treatment provides significant conversion of light oxygenates to larger, less oxygenated, molecules and, simultaneously, bio‐oil phenolics are also converted to less oxygenated phenolics with methoxy methyl groups transferred to the ring. The activity of the catalyst gradually diminished with increasing biomass fed to the system. Untreated pyrolysis oil forms a single liquid phase with some tarry material, consistent with the literature, whereas the treated liquid product forms separate oil and aqueous phases, the latter of which is about 80% water. The oil from the treated vapors has a lower initial viscosity with only a small increase upon accelerated aging compared to the untreated product oil, which has a dramatic increase in viscosity after aging. This is indicative of poor oil stability for untreated oil that is further confirmed by large increases in molecular weight, while the treated oil has a small increase in molecular weight after accelerated aging. In an effort to understand compatibility with refinery streams, the solubility of the oils in tetralin was examined. The untreated oil was found to have very limited solubility in tetralin, whereas the treated oil phase was completely soluble except for a small aqueous phase that appeared. There are a number of challenges in developing a high yield process for pyrolysis based conversion of biomass to transportation fuels. The Ru/TiO₂ catalyst used here shows promise for conducting multiple types of favorable reactions in the presence of the full spectrum of primary pyrolysis products that creates significant product stability under mild conditions. This could lead to higher liquid yields of stable, refinery compatible, product oil. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2275–2285, 2013     

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.     

Evaluation of catalytic pyrolysis of cassava rhizome by principal component analysis

Rhizome of cassava plants (Manihot esculenta Crantz) was catalytically pyrolysed at 500 °C using analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) method in order to investigate the relative effect of various catalysts on pyrolysis products. Selected catalysts expected to affect bio-oil properties were used in this study. These include zeolites and related materials (ZSM-5, Al-MCM-41 and Al-MSU-F type), metal oxides (zinc oxide, zirconium (IV) oxide, cerium (IV) oxide and copper chromite) catalysts, proprietary commercial catalysts (Criterion-534 and alumina-stabilised ceria-MI-575) and natural catalysts (slate, char and ashes derived from char and biomass). The pyrolysis product distributions were monitored using models in principal components analysis (PCA) technique. The results showed that the zeolites, proprietary commercial catalysts, copper chromite and biomass-derived ash were selective to the reduction of most oxygenated lignin derivatives. The use of ZSM-5, Criterion-534 and Al-MSU-F catalysts enhanced the formation of aromatic hydrocarbons and phenols. No single catalyst was found to selectively reduce all carbonyl products. Instead, most of the carbonyl compounds containing hydroxyl group were reduced by zeolite and related materials, proprietary catalysts and copper chromite. The PCA model for carboxylic acids showed that zeolite ZSM-5 and Al-MSU-F tend to produce significant amounts of acetic and formic acids.     

Pyrolysis and Pt(IV)- and Ru(III)-ion catalyzed pyrolysis of asphaltenes in organic geochemical investigation of a biodegraded crude oil (Gaj, Serbia)

This paper is aimed at investigating the origin and geological history of the biodegraded Gaj (Serbia) crude oil, based on comparison of biomarkers, particularly alkylaromatics, in crude oil maltene fraction, with those in the liquid raw asphaltene pyrolysis products. The content of asphaltenes in crude oils being generally very low, expecting a higher yield of pyrolysate, pyrolysis of raw asphaltenes was also carried out in the presence of Pt(IV)- and Ru(III)-ions. The used metal ions demonstrated positive effects on the yields of total liquid pyrolysate and corresponding hydrocarbons. Occluded maltene and asphaltene pyrolysis products showed that metal ions had considerably stronger effect on maturation changes in naphthalene and phenanthrene rings than in polycyclic alkanes. The values of maturity parameters observed in maltenes and pyrolysates suggested this crude oil to have been expelled from the source before the “oil window” maximum. The investigated sample of the Gaj crude oil was shown to be in the 4th stage of biodegradation scale and to have originated from source rocks poor in clays, most probably carbonates, with significant contribution of algae to oil precursor biomass, deposited under a stratified saline water column.     

Aqueous Dispersion and Slip Casting of Boron Carbide Powder: Effect of pH and Oxygen Content

The effect of pH and oxygen content on the zeta potential, viscosity, and casting performance of fine (>3 μm) boron carbide powder is presented. X-ray photoelectron spectroscopy of the powder revealed a surface layer of adsorbed water and oxides of boron and carbon. The soluble boric acid impurity was removed by washing the powder with water or alcohols. Electrophoresis indicated that the B₄C surface was negatively charged in water above pH 1, but the presence of dissolved boric acid suppressed the zeta potential at high pH. Stable, low-viscosity dispersions of >30 vol% solids were prepared and slip cast at pH >6, but boric acid was destabilizing for dispersions prepared above pH 7. The green density of slip-cast parts was more reproducible and about 3% to 5% higher for washed powders than for high-oxygen-content powders.     

Biomass pyrolysis in a circulating fluid bed reactor for the production of fuels and chemicals

An approach for biomass flash pyrolysis in a circulating fluid bed (CFB) reactor with continuous solids regeneration is described in this study. The unit is capable of performing conventional and catalytic biomass pyrolysis with the proper solid selection. The production of improved quality liquid products in a direct step through catalytic pyrolysis is investigated in this work. Both conventional and catalytic biomass pyrolysis can be effectively performed in this CFB unit. Flash pyrolysis conditions were achieved and liquid product yields of ∼70 wt% (on biomass feed) were obtained. The effect of specific operating variables including the type of inorganic solid material and the solid/biomass ratio was established on the final liquid product quality and yield. Solid materials considered included silica sand, a commercial fluid catalytic cracking catalyst and a ZSM-5 additive. Catalytic biomass pyrolysis generally leads to the production of additional water, coke and gases compared to conventional pyrolysis. However, the obtained liquid product quality and composition is improved.     

Fractional Isolation and Structural Characterization of Lignins from Oil Palm Trunk and Empty Fruit Bunch Fibers

Abstract

The lignins from dewaxed oil palm trunk and empty fruit bunch (EFB) fibers were fractionated into 95% ethanol soluble, cold and hot water soluble, and 1% NaOH soluble lignins, respectively. The chemical and structural composition of the lignin preparations was determined by using UV, GPC, FT-IR, ¹³C-NMR spectroscopy and nitrobenzene oxidation. The alkali soluble and 95% ethanol soluble lignin fractions were found to contain low amounts of chemically linked polysaccharides, 2.9-3.9% and 7.5-8.0%, respectively, while the water soluble lignin fractions showed significant amounts of bound polysaccharides (16.2-23.3%). All of the lignin fractions contained a high proportion of non-condensed syringyl units, together with small amounts of non-condensed guaiacyl and fewer p-hydroxyphenyl units. The lignin from oil palm EFB fiber contained a significant amount of esterified p-hydroxybenzoic acid and a minor quantity of esterified glucuronic acid. Trace of ferulic acids was both esterified and etherified to lignin side chains in the EFB fiber cell walls.     

Partial oxidation of methane to synthesis gas over a Pt/10% Rh gauze

The techniques of environmental scanning electron microscopy (ESEM) and Raman microscopy have been used to respectively elucidate the morphological changes and nature of the adsorbed species on silver(I) oxide powder, during methanol oxidation conditions. Heating Ag₂O in either water vapour or oxygen resulted firstly in the decomposition of silver(I) oxide to polycrystalline silver at 578 K followed by sintering of the particles at higher temperature. Raman spectroscopy revealed the presence of subsurface oxygen and hydroxyl species in addition to surface hydroxyl groups after interaction with water vapour. Similar species were identified following exposure to oxygen in an ambient atmosphere. This behaviour indicated that the polycrystalline silver formed from Ag₂O decomposition was substantially more reactive than silver produced by electrochemical methods. The interaction of water at elevated temperatures subsequent to heating silver(I) oxide in oxygen resulted in a significantly enhanced concentration of subsurface hydroxyl species. The reaction of methanol with Ag₂O at high temperatures was interesting in that an inhibition in silver grain growth was noted. Substantial structural modification of the silver(I) oxide material was induced by catalytic etching in a methanol/air mixture. In particular, "pin-hole" formation was observed to occur at temperatures in excess of 773 K, and it was also recorded that these "pin-holes" coalesced to form large-scale defects under typical industrial reaction conditions. Raman spectroscopy revealed that the working surface consisted mainly of subsurface oxygen and surface Ag=O species. The relative lack of subsurface hydroxyl species suggested that it was the desorption of such moieties which was the cause of the "pin-hole" formation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermodynamic,spectroscopic, and molecular characterization of rice straw biomass for use as biofuel feedstock

India is one of the leading producers of rice in the world. Gasification and pyrolysis are two thermochemical processes. In the gasification process, biomass is transformed into syngas, which serves as an energy source. This conversion occurs under high temperatures with a carefully regulated and restricted air supply. On the other hand, pyrolysis, which transpires at lower temperatures without the presence of air, generates pyrolysis oil as a by-product. This oil can be further refined into liquid fuels. For the purpose of investigating the feasibility of biofuel production, the current study involved the characterization of rice straw biomass using various techniques such as thermogravimetry differential thermal analysis (TG/DTA), Fourier transform infrared (FTIR), carbon, hydrogen, nitrogen, sulphur and oxygen (CHNS/O), inductively coupled plasma optical emission spectroscopy (ICP-OES), among others. These analytical methods were employed to assess the potential of rice straw biomass for the production of biofuels. The existence of a significant amount of cellulose (32.1%), volatiles (approximately 67.06%), and high heating value (HHV) (13.18 MJKg⁻¹) in rice straw inferred their capability to be used as feedstocks in the production of biofuel. The activation energy of approximately 173.20 KJ/Mol (Flynn Wall Ozawa [FWO]) indicated the viability of the burning process. From master plot (Z(α)) analysis, the experimental curve was seen passing through different theoretical curves, indicating the complex nature of the pyrolysis process for rice straw.     

Effect of antioxidants on refined palm oil

Alkali refined palm oil and hydrogenated cotton-seed oil were stabilized with butylated hydroxytoluene, butylated hydroxyanisole, and tertiary butylhydroquinone. Under bulk storage temperatures significant reductions in the peroxide formation of palm oil were obtained only with tertiary butyl-hydroquinone. The reduction in peroxide formation with tertiary butylhydroquinone was much greater than anticipated from the active oxygen method results. The stability improvement of a snack product fried in palm oil stabilized with tertiary butylhydroquinone depended greatly on the frying conditions used. Under mild frying conditions tertiary butyl-hydroquinone had somewhat greater carry-through than butylated hydroxytoluene. Under more severe frying conditions tertiary butylhydroquinone provided less protection than butylated hydroxytoluene. Both palm oil and hydrogenated cottonseed oil stabilized with only butylated hydroanisole had higher active oxygen stabilities than the unstabilized controls; however, no reduction in peroxide formation of the butylated hydroxyanisole oils compared to the controls was found during storage of the oil or the snack product at 50–60 C.     

Prediction of Biomass Pyrolysis Mechanisms and Kinetics: Application of the Kalman Filter

In order to predict the pyrolysis mechanisms of four different biomasses (Asbos (Psilocaulon utile), Kraalbos (Galenia africane), Scholtzbos (Pteronia pallens), and palm shell), a novel method called Kalman filter was investigated and the results were compared by regression analysis. Both analyses were applied to five different generalized biomass pyrolysis models consisting of parallel and serial irreversible-reversible reaction steps. The models consisting of reversible reactions in addition to parallel pyrolysis steps demonstrated a better fit with the experimental results. The pyrolysis step from biomass to bio-oil has the highest reaction rates compared with the other pyrolysis steps defined in the models. The Kalman filter is thus defined as a promising filtering and prediction method for the estimation of detailed pyrolysis mechanisms and model parameters, using minimum experimental data.