Promotion of bio oil,H2 gas from the pyrolysis of rice husk assisted with nano silver catalyst and utilization of bio oil blend in CI engine

This paper reports on the pyrolytic distillation of rice husk with catalyst and its influence on both condensable and non-condensable volatiles. The catalyst used for pyrolysis was nano sized silver particles obtained through chemical reduction method. The structural features of the nano silver particles were explored through X-ray diffraction (XRD) and Field Emission Scanning Electron Microscope (FESEM) with Energy-dispersive-X-ray spectroscope (EDX), and the size of the nano particles was confirmed as 90 nm. After intimately mixing the rice husk (30 g) with the catalyst, the pyrolysis at various temperatures (400 °C, 450 °C, 500 °C, 550 °C) was performed. The products obtained during catalytic pyrolysis like gaseous fuel, bio oil, and bio char were separately collected and characterized through Gas Chromatography-Mass Spectrometer (GC-MS) and Inductively Coupled Plasma – Optical Emission Spectrometer (ICP-OES). About 50% of the solid biomass was converted into more useful liquid and gaseous fuel. It was noticed that during catalytic pyrolysis, the quantity of H₂ obtained was more (19.12%) in contrast to thermal pyrolysis and could be attributable to the influence of silver nano particles towards the enhancement in hydrogen gas production. The liquid hydrocarbon obtained during the catalytic distillation was blended with diesel in the ratio 20:80 in the compression ignition (CI) engine. The quality of the blended bio oil was assessed from brake thermal efficiency (BTE), brake specific fuel consumption (BSFC) and emission of nitrogen oxides (NO_X), carbon monoxide (CO) and unburnt hydrocarbon (UHC). At full load, the diesel fuel emitted 1780 ppm of NO_x while the diesel blended with bio oil emitted only 1510 ppm which was 15.17% less than the diesel oil which proved its eco-friendly nature. In future, the bio oil obtained from catalytic pyrolysis can be used as a blend for diesel oil, since it reduces NO_x emission and replaces 20% of diesel oil.     

Bio‐oil production from rapid pyrolysis of cottonseed cake: product yields and compositions

Fixed‐bed fast pyrolysis experiments have been conducted on a sample of cottonseed cake to determine the effects of pyrolysis temperature, heating rate and sweep gas flow rate on pyrolysis yields and chemical compositions of the product oil. The liquid products and the subfractions of pentane soluble part were characterized by elemental analysis, FT‐IR spectroscopy, ¹H‐NMR spectroscopy and pentane subfraction was analysed by gas chromatography. The maximum oil yield of 34.8% was obtained at final temperature of 550°C with a heating rate of 700°C min^?1 and nitrogen flow rate of 100 cm³ min^?1. Chromatographic and spectroscopic studies on bio‐oil have shown that the oils obtained from cottonseed cake can be used as a renewable fuel and chemical feedstock. Copyright © 2005 John Wiley & Sons, Ltd.     

Comparison of catalytic and noncatalytic pyrolysis and product yields of some waste biomass species

The products obtained by fast pyrolysis of biomass can be used as an energy source or chemical raw material. In this study, samples of hazelnut shells, tea bush, and hazelnut knot selected as waste biomass were from the cities of Trabzon and Rize in the Eastern Black Sea Region. Firstly, the waste biomass samples were granulated into four different particle sizes by milling and sieving operations. Fast pyrolysis of the samples with specific mixing rates was carried out in a fixed bed reactor. Additionally, 2 wt% vanadium (V) oxide (V₂O₅) was used as catalyst to maximize the yield of pyrolysis liquid products. The influence of temperature, heating rate, and particle size on fast pyrolysis yields under both catalytic and noncatalytic conditions were investigated and compared. While the amount of liquid product increased with the addition of catalyst, the amount of solid products decreased. It has been found that the temperature and heating rate parameters are very effective in liquid product yield. In all experiments, the maximum liquid yield was acquired at the same heating rate of 450°C min^?1 and the temperature of 450°C with particle size of 0.5 to 1.0 mm. The maximum pyrolysis liquid (bio‐oil) was obtained with catalytic pyrolysis, and this value was 60.58 wt%.     

Catalytic co‐pyrolysis of Eichhornia Crassipes biomaѕѕ and polyethylene using waste Fe and CaCO3 catalysts

A wild aquatic plant, Eichhornia Crassipes, and polyethylene have been converted into liquid product thermo‐catalytically and cost effectively through co‐pyrolysis using batch steel pyrolyzer. The Fe and CaCO₃ catalysts were obtained as wastes from various mechanical processes. The catalytic process was compared with non‐catalytic pyrolysis. The effect of various reaction conditions was investigated in order to find out the optimized process conditions. It was found that the favorable reaction conditions were 450 °C temperature and 1‐h reaction time at a heating rate of 1 °C/s and 0.4‐mm biomass particle size. The bio‐oil yield was found to be 34.4% and 26.6% using Fe and CaCO₃ respectively with catalysts particle size of 0.4 mm at the optimized reaction conditions and 5 wt% of biomass. The non‐catalytic and catalytic co‐pyrolysis using Fe as catalyst produced 23.9% and 28.7% oil respectively. Thus the efficiency of processes in terms of bio‐oil production was found in order of: Fe > CaCO₃ > non‐catalytic pyrolysis. The GC/MS analysis of n‐hexane extract of bio‐oil shows that Fe catalyst favors formation of aliphatic hydrocarbons while CaCO₃ and non‐catalytic pyrolysis favors formation of aromatic hydrocarbons. Mostly unsaturated aliphatic hydrocarbons were formed in case of co‐pyrolysis reactions. The calorific value of bio‐oil was also measured in order to find out the fuel properties of the products. Copyright © 2016 John Wiley & Sons, Ltd.     

Fast pyrolysis of date palm biomass using Py-GCMS

Pyrolysis of Date Palm Petiole (DPP) and Date Palm Seed (DPS) biomass was conducted by fast pyrolysis and on-line analysis of the outlet stream by gas chromatography connected to mass spectrometry (Py-GCMS) at different temperatures (450, 500 and 600 °C) in order to study the effect of this variable on the product distribution. The concentration of the components in the volatile stream (bio-oil and non-condensable gases) was greatly influenced by temperature and, to a minor extent, by the content of the biomass components (cellulose, hemicellulose and lignin). The most abundant compound families quantified are acids, anhydrosugars, ketones, furans and phenols. The most abundant compound identified was levoglucosan, which is mainly derived from the degradation of cellulose, with its relative content being as high as 18.3% for DPS pyrolysis at 450 °C and considerably lower for DPP pyrolysis (12.2%). The relative content of acetic acid was as higher as 10.2% at 450 °C for DPP pyrolysis. The knowledge of product composition is crucial for the development of large scale fast pyrolysis units for the valorization of these Tunisian agricultural wastes.     

Experimental investigation of the pyrolysis of biomass to produce green fuels

This work aims to utilise the experimental approach to perform the analysis of three-biomass feed stocks – bamboo, mustard and camellia and to provide insight into the operation and design of pyrolysis processes. Experiments on biomass fast pyrolysis were performed in a fixed bed (tubular) reactor at a temperature of 500°C and a residence time of 2?min under the constant flow of nitrogen. The analysis of pyrolysis gases and bio oil produced by pyrolysis was done using GC-MS and GC-TCD. Hydrous pyrolysis of biomasses was performed in a high-pressure autoclave for the temperature range 250–400°C and at a pressure of 20?bar with 30?min of residence time. Experiments were conducted both with and without the use of a catalyst. The pyrolysis vapour is made to pass through the catalyst bed of ZSM-5 (Si/Al?=?35). The results for all the biomass samples are then compared.     

Microwave-induced pyrolysis of waste truck tyres with carbonaceous susceptor for the production of diesel-like fuel

Microwave-induced pyrolysis technique was utilised to pyrolyse waste truck tyres (TT) into useful pyrolysis oil with the aid of activated carbon. The effect of temperature was studied to determine the truck-tyre pyrolysis oil (TTPO) yield, hydrocarbon fractions, chemicals composition, energy yield and fuel properties. The activated carbon functions as microwave absorber to elevate the pyrolysis temperature for enhancing production of pyrolysis oil. The optimal pyrolysis temperature of 500 °C produces highest TTPO yield of 38.12 wt% with calorific value of 42.39 MJkg^?1 and energy yield of 40.55 wt%. Detailed analysis shows the TTPO contained large amount of aromatic hydrocarbons and limonene (14.29%) compared to pyrolysis oil from personal car tyre. Among the important chemical compounds also discovered in TTPO are benzene, toluene, xylene (BTX). The relative yields of toluene obtained at 400 °C is 14.85%, whereas the relative yields of benzene and xylene at 450 °C were 0.85 and 7.60%, respectively. The physiochemical properties of TTPO500 are rather similar to conventional diesel, except the slightly lower flash point and calorific value for the former. This work shows that microwave-induced pyrolysis is a promising technique to recover diesel-like fuel for use as supplemental alternative fuel.     

Experimental study of the pyrolysis of waste bitumen for oil production

This work focuses on bitumen slow pyrolysis. Mass and energy yields of oil, solid and gas were obtained from pyrolysis experiments using a semi-batch reactor in a nitrogen atmosphere, under three non-isothermal conditions (maximum temperature: 450 °C, 500 °C and 550 °C). The effect of temperature on the product yields was discussed. The gas compositions were analysed using gas chromatography (GC) and the heating value of oil and solid residue was also measured. Using a thermo-gravimetric analyser, kinetic parameters were evaluated through Ozawa-Flynn-Wall (OFW) method. Results showed that oil yield is maximum at 500 °C (50%). Moreover, gas yield increased with increasing pyrolysis temperature from 18% to 36%. On the other hand, solid yield showed an opposite trend: it decreased from 39% to 32%. As regard energy yields, they showed a similar trend with the mass ones. H_2, CH₄, C₂H₄, C₂H₆ and C₃H₈ are the main components of the produced gas phase. It has been noticed that the recovery of bitumen to liquid oil through pyrolysis process had a great potential since the oil produced had high calorific value comparable with commercial fuels.     

Influence of feedstock properties and pyrolysis conditions on biochar carbon stability as determined by hydrogen pyrolysis

We produced 18 thermosequences of biochar from common feedstocks at ten temperatures from 300 to 900 °C to investigate their influence on carbon stabilization in biochar. Using hydrogen pyrolysis we were able to isolate the stable polycyclic aromatic carbon (SPAC) fraction that is likely to be resistant to mineralization on centennial timescales. SPAC formation was generally <20% of total organic carbon (TOC) at temperatures <450 °C and rises to >80% of TOC at temperatures above 600–700 °C depending on feedstock type. SPAC formation was retarded in feedstocks with high ash contents, and further retarded in those feedstocks when the final hold time at maximum pyrolysis temperature was reduced from one hour to 10 min. Given that aromatization of organic material in many feedstocks is usually completed by ca. 450 °C, the data suggests that a significant pool of aromatic biochar carbon exists in a ‘semi-labile’ form that may not be persistent on centennial timescales. For most feedstocks biochar yield and SPAC content are optimized at pyrolysis temperatures of 500–700 °C.     

Influence of temperature and steam on the products from the flash pyrolysis of Jordan oil shale

Oil shale samples from the Sultani deposit in the south of Jordan, were pyrolysed in a semi‐continuous fluidized bed reactor under nitrogen and nitrogen/steam atmosphere. The pyrolysis temperature between 400 and 650°C were investigated. Increasing the pyrolysis temperature from 400 to 520°C caused a large increase in the oil yield. Further increase of the pyrolysis temperature resulted in a decrease in oil yield and a large increase in the evolved gases. This increase in the hydrocarbon gas yield was attributed to oil thermal cracking reactions. The evolved gases were composed of H₂, CO, CO₂, and hydrocarbons from C₁ to C₄. The presence of steam improved the oil yield which may be a result of reducing the degree of decomposition. The derived oils were fractionated into chemical classes using mini‐column liquid chromatography. Copyright © 2002 John Wiley & Sons, Ltd.     

Potentiality of “orujillo” (olive oil solid waste) to produce hydrogen by means of pyrolysis

The extraction of olive oil generates great amounts of solid waste and wastewater. The objective of this work is to evaluate the potentiality of slow pyrolysis of the solid oil waste, known as “orujillo”, to produce hydrogen rich gases. The effect of temperature and of different treatments of pyrolysis vapors on the yield and composition of the gases has been experimentally studied. “Orujillo” was pyrolyzed at 500 °C and 700 °C, and the pyrolysis vapors produced were directly fed to a second reactor where they were treated at 800 °C in different ways: just thermally, thermally treated through a refractory alumina bed and thermo-catalytically treated through a three layer bed (alumina + SiC mixed with Ni catalyst + alumina). The catalyst used was a commercial prereduced nickel-catalyst which contains 44 wt% Ni over calcium aluminate support (CaO/Al₂O₃). Concerning the effect of temperature, it has been proved that the raise in temperature leads to a decrease in the liquid yields and an increase in the gas yields, as well as to an increase in H₂ and a decrease in CO₂ content of the gases. With respect to the vapors treatments it has been observed that as a general rule any of the treatments reduces liquid and increases gas yields, and concerning gas composition, H₂ content increases, CO slightly increases and CO₂ decreases. These effects are more pronounced when the Ni-catalyst is used. With the Ni-catalyst about 50 wt% gas yield is obtained, with ≈ 50 vol% H₂ both at 500 and at 700 °C.     

Olive residues (cuttings and kernels) rapid pyrolysis product yields and kinetics

A study of pyrolysis of olive residues (cuttings and kernels) at a temperature range from 300 to 600°C, has been carried out. The experiments were performed in a captive sample reactor at atmospheric pressure under helium. The yields of the derived gases, pyrolytic liquids and char were determined in relation to pyrolysis temperature, at heating rates of about 200°C/s.As the pyrolysis temperature was increased the percentage mass of char decreased whilst gas and oil products increased. The oil products increased to a maximum value of ∼30 wt% of dry biomass at about 450–550°C. The major gaseous products are CO and CO₂.A simple first order kinetic model has been applied to the evolution of total losses and gases. Kinetic parameters have been estimated and compared with other reported similar data.     

Bio-oil Production from an Oilseed By-product: Fixed-bed Pyrolysis of Olive Cake

Abstract

A study of pyrolysis of olive cake at the temperature range from 400°C to 700°C has been carried out. The experiments were performed in a laboratory scale tubular reactor under nitrogen atmosphere. The yields of derived gases, liquids, and char were determined in relation to pyrolysis temperature and sweeping gas flow rates, at heating rates of about 300°C min^?1. As the pyrolysis temperature was increased, the percentage mass of char decreased whilst gas product increased. The oil products increased to a maximum value of ～39.4 wt% of dry ash free biomass at a pyrolysis temperature of about 550°C in a nitrogen atmosphere with flow rate of 100 mL min^?1 and with a heating rate of 300°C min^?1. Results showed that the bio-oil obtained under the optimum conditions is a useful substitute for fossil fuels or chemicals.     

Biofuel production using Pd/Zn synergistically catalyzed hydrodeoxygenation applied at bio oil extracted in biomass pyrolysis process

Raw bio oil includes multicomponents. In order to avoid the interference between complex reactions, the model compounds, instead of the real bio oil, have been widely used for the study of raw bio‐oil upgrade. In this work, the hydrodeoxygenation (HDO) of raw pine pyrolysis bio oil was investigated at 200 °C using Pd/Zn synergistic catalysis under hydrogen pressures of 200, 300, and 400 psi, separately. The resulting product included gas, liquid, and coke. The gas was characterized using a gas chromatography. The liquid was characterized using a gas chromatography–mass spectrometry. The results showed that the HDO performance achieved promotion to some extent by the Pd/Zn synergistic catalysis compared with use of Pd/C or Zn²⁺, independently. The HDO also gave rise to improvements on physicochemical properties of bio oils. Notably, the highest water content (13.16 wt%) revealed that deoxygenation reaction could be promoted by Pd/Zn synergistic catalysis compared with use of Pd/C or Zn²⁺, independently. More importantly, the highest hydrocarbon yield (19.15% on the base of liquid part) could be obtained by the treatment of 300 psi pressure and 200 °C temperature over Zn/Pd/C synergistic catalysis. Copyright © 2016 John Wiley & Sons, Ltd.     

Influence of reaction conditions on bio-oil production from pyrolysis of construction waste wood

The pyrolysis characteristics of construction waste wood were investigated for conversion into renewable liquid fuels. The activation energy of pyrolysis derived from thermogravimetric analysis increased gradually with temperature, from 149.41 kJ/mol to 590.22 kJ/mol, as the decomposition of cellulose and hemicellulose was completed and only lignin remained to be decomposed slowly. The yield and properties of pyrolysis oil were studied using two types of reactors, a batch reactor and a fluidized-bed reactor, for a temperature range of 400–550 °C. While both reactors revealed the maximum oil yield at 500 °C, the fluidized-bed reactor consistently gave larger and less temperature-dependent oil yields than the batch reactor. This type of reactor also reduced the moisture content of the oil and improved the oil quality by minimizing the secondary condensation and dehydration. The oil from the fluidized-bed reactor resulted in a larger phenolic content than from the batch reactor, indicating more effective decomposition of lignin. The catalytic pyrolysis over HZSM-5 in the batch reactor increased the proportion of light phenolics and aromatics, which was helpful in upgrading the oil quality.     

Effect of temperature on the fast pyrolysis of organic-acid leached pinewood; the potential of low temperature pyrolysis

In this paper, we have evaluated the potential of organic acid (mixture of acetic, formic and propionic acid) leaching of biomass and subsequent fast pyrolysis to increase the organic oil, sugars and phenols yield by varying the fluidized bed temperature between 360 °C and 580 °C (360 °C, 430 °C, 480 °C, 530 °C, and 580 °C). The pyrolysis of acid leached pinewood resulted in more organic oil and less water and residue compared to untreated pinewood over the whole temperature range. Below 500 °C the difference was most profound; for acid leached pinewood at 360 °C the organic oil was already 650 g kg⁻¹ pine with a sugar yield of 230 g kg⁻¹ pine. At this low pyrolysis temperature no bed agglomeration was observed for acid leached pine whereas at the higher temperatures tested agglomerates were found, which were identified to be clusters of fluidization sand glued together by sticky pyrolysis products (melt). Low reactor temperatures also favored the production of monomeric phenols, though their absolute yields remained low for both untreated and leached pine (maximum: 23 g kg⁻¹ pine, 80 g kg⁻¹ lignin). GPC, GC/MS and UV-fluorescence spectroscopy showed that acid leaching did not influence significantly the yield and molecular size of the aromatic fraction in the produced pyrolysis oils. Back impregnation of the removed AAEMs into leached biomass revealed that the effects of the applied acid leaching, both with respect to the product yields and bed agglomeration, can be mainly assigned to the removal of AAEMs.     

Pyrolysis of giant mullein (Verbascum thapsus L.) in a fixed-bed reactor: Effects of pyrolysis parameters on product yields and character

Slow pyrolysis of giant mullein (Verbascum thapsus L.) stalks have been carried out in a fixed-bed tubular reactor with (Al₂O₃, ZnO) and without catalyst at four different temperatures between 400 to 550°C with a constant heating rate of 50°C/min and with a constant sweeping gas (N₂) flow rate of 100 cm³/min. The amounts of bio-char, bio-oil, and gas produced were calculated and the compositions of the obtained bio-oils were determined by gas chromatography-mass spectrometry. The effects of pyrolysis parameters, such as temperature and catalyst, on the product yields were investigated. The results show that both temperature and catalyst have significant effects on the conversion of Verbascum thapsus L. into solid, liquid, and gaseous products. The highest liquid yield of 40.43% by weight including the aqeous phase was obtained with 10% zinc oxide catalyst at 500°C temperature. Sixty-seven different products were identified by gas chromatography-mass spectrometry in the bio-oils obtained at 500°C temperature.     

Catalytic hydrodeoxygenation of dehydrated liquid phase pyrolysis oil

Biomass has been considered as promising energy source that should be able to suffice the increasing energy demand in the future. Therefore, new biomass utilization technologies and concepts are highly desirable. This paper contributes to the understanding of liquid phase pyrolysis oil upgrading that differs from the intensively investigated fast pyrolysis oil. Two new approaches, which were never reported in literature before, where investigated in this paper. At first, the liquid phase pyrolysis oil was dehydrated to lower transportation costs and increase energy density and efficiency of further upgrading steps. At second, a catalyst screening for hydrodeoxygenation (HDO) of dehydrated liquid phase pyrolysis oil was conducted in a batch reactor. Neither the dehydration nor the HDO of dehydrated liquid phase pyrolysis oil were reported in literature by now. The activity of the HDO catalysts Ru/C, Pt/C, and Pd/C as well as a Ni‐based catalyst was compared. HDO was investigated at 250 °C and 100 bar and at 300 °C and 150 bar. HDO of dehydrated liquid phase pyrolysis oil was observed with all catalysts. The Pt/C catalyst was found to be most promising with respect to the oil yield (56 wt.%), the deoxygenation ratio (65%), and hydrogen content (8.6 wt.%). Copyright © 2014 John Wiley & Sons, Ltd.     

Valorisation of lignocellulosic biomass investigating different pyrolysis temperatures

Presently, sugarcane bagasse (SB) and oat hulls (OH) have a distinctive potential as a renewable source of biomass, due to its global availability, which is advantageous for producing liquid and gaseous fuels by thermochemical processes. Thermo-Catalytic Reforming (TCR) is a pyrolysis based technology for generating energy vectors (char, bio-oil and syngas) from biomass wastes. This work aims to study the conversion of SB and OH into fuels, using TCR in a 2 kg/h continuous pilot-scale reactor at different pyrolysis temperatures. The pyrolysis temperatures were studied at 400, 450 and 500 °C, while the subsequent reforming temperature remained constant at 500 °C. The bio-oil contained the highest calorific value of 33.4 and 33.5 MJ/kg for SB and OH, respectively at 500 °C pyrolysis temperature, which represented a notable increase compared to the raw material calorific value of SB and OH (16.4 and 16.0 MJ/kg, respectively), this was the result of deoxygenation reactions occurring. Furthermore, the increment of the pyrolysis temperature improved the water content, total acid number (TAN), viscosity and density of the bio-oil. The syngas and the biochar properties did not change significantly with the increase of the pyrolysis temperature. In order to use TCR bio-oil as an engine fuel, it is necessary to carry out some upgrading treatments; or blend it with fossil fuels if it is to be used as a transportation fuel. Overall, TCR is a promising future route for the valorisation of lignocellulosic residues to produce energy vectors.     

Evaluating the effect of potassium on cellulose pyrolysis reaction kinetics

This paper proposes modifications to an existing cellulose pyrolysis mechanism in order to include the effect of potassium on product yields and composition. The changes in activation energies and pre-exponential factors due to potassium were evaluated based on the experimental data collected from pyrolysis of cellulose samples treated with different levels of potassium (0–1% mass fraction). The experiments were performed in a pyrolysis reactor coupled to a molecular beam mass spectrometer (MBMS). Principal component analysis (PCA) performed on the collected data revealed that cellulose pyrolysis products could be divided into two groups: anhydrosugars and other fragmentation products (hydroxyacetaldehyde, 5-hydroxymethylfurfural, acetyl compounds). Multivariate curve resolution (MCR) was used to extract the time resolved concentration score profiles of principal components. Kinetic tests revealed that potassium apparently inhibits the formation of anhydrosugars and catalyzes char formation. Therefore, the oil yield predicted at 500 ^°C decreased from 87.9% from cellulose to 54.0% from cellulose with 0.5% mass fraction potassium treatment. The decrease in oil yield was accompanied by increased yield of char and gases produced via a catalyzed dehydration reaction. The predicted char and gas yield from cellulose were 3.7% and 8.4%, respectively. Introducing 0.5% mass fraction potassium treatment resulted in an increase of char yield to 12.1% and gas yield to 33.9%. The validation of the cellulose pyrolysis mechanism with experimental data from a fluidized-bed reactor, after this correction for potassium, showed good agreement with our results, with differences in product yields of up to 5%.