Synthesis and Thermal decomposition study of Dysprosium Trifluoroacetate J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-19 Y.A. Opata, J.-C. Grivel
A study of the thermal decomposition process of dysprosium trifluoroacetate hydrate under flowing argon is presented. Thermogravimetry, differential thermal analysis, evolved gas analysis and ex-situ x-ray diffraction techniques have been employed in the investigation. Three main stages were identified: dehydration, decomposition and phase transformation from DyF3 to DyFO. The dehydration takes place in 2 steps and the decomposition also occurs in two stages. The observed residual mass demonstrated a discrepancy with the calculated value for DyF3 formation. Observations on quenched samples at temperatures just above the decomposition step and at 828 °C showed a variation in the sample color, being dark in the first case and rather bright at the higher quenching temperature. Based on this fact, we concluded that some carbon remains in the sample up to 800 °C. With the temperature reaching 1300 °C, a plateau is observed in the TG signal, which mass value agrees with the formation of DyFO as verified by the ex-situ x-ray data of quenched powder. Using the FTIR and MS spectra of released gases during the process and the TG data, a decomposition scheme is suggested.
THERMAL CRACKING OF N-BUTYLBENZENE AT HIGH PRESSURE: EXPERIMENTAL STUDY AND KINETIC MODELLING J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-15 N.C. Leguizamon Guerra, J.C. Lizardo Huerta, C. Lorgeoux, R. Michels, R. Fournet, B. Sirjean, A. Randi, R. Bounaceur, V. Burklé-Vitzthum
Chemical recycling of crosslinked poly(methyl methacrylate) and characterization of polymers produced with the recycled monomer J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-15 Rayany Stôcco Braido, Luiz Eduardo Pizarro Borges, José Carlos Pinto
The chemical recycling of crosslinked poly(methyl methacrylate) wastes, PMMA, used as dental resins, was investigated for recovery and polymerization of the methyl methacrylate monomer, MMA. At temperatures of 400 °C in laboratory and pilot plant installations, PMMA could be depolymerized by pyrolysis to produce more than 90 wt% of liquid, containing more than 98 wt% of MMA. Gas chromatography (GC) and coupled gas chromatography – mass spectrometry (GC–MS) analyses were carried out to characterize the obtained liquid fraction. PMMA powders produced with different quantities of recycled MMA were prepared, after purification of the liquid through distillation, leading to polymer resins with properties that were similar to the ones obtained with virgin commercial MMA, as characterized by particle size, Fourier transform infrared (FT-IR), gel permeation chromatograph (GPC) and scanning electron microscopy (SEM) analyses.
Sludge as a Relinquishing Catalyst in Co-Pyrolysis with Palm Empty Fruit Bunch Fiber J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-13 Li Wen Chow, Shu Anne Tio, Jia Yun Teoh, Chu Gen Lim, Yen Yee Chong, Suchithra Thangalazhy-Gopakumar
Co-cracking of bio-oil distillate bottoms with vacuum gas oil for enhanced production of light compounds ☆ J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-13 Yong S. Choi, Yaseen Elkasabi, Paul C. Tarves, Charles A. Mullen, Akwasi A. Boateng
Seamless co-processing of pyrolysis bio-oil within existing petroleum refineries is the most synergistic and economic way to improve biorefinery output. Coprocessing bio-oil with vacuum gas oil (VGO) is one logical pathway. Bio-oil has a viscosity and molecular weight range similar to that of VGO, and the hydrogen-rich nature of VGO can chemically complement the bio-oil hydrogen deficiency. Distillation of biomass pyrolysis oils produces solid residues with a significant fraction of fixed carbon and heavy volatiles. Maximization of yields of light compounds like olefins and gasoline-range aromatics are crucial for both attainment of desired product output levels as well as to follow methods that mimic petroleum-based methods and chemistries. Herein we discuss a systematic study on the additive coprocessing of specific bio-oil distillation bottoms with VGO. Tail-gas reactive pyrolysis (TGRP) bio-oils from spirulina, switchgrass, and guayule biomasses were distilled, and their bottoms were subject to analytical experiments in mixtures with VGO over different zeolite catalysts (no catalyst, HZSM-5, Y-zeolite). Switchgrass-based bottoms exhibit greater hydrogen deficiency and higher oxygen content compared with that of spirulina or guayule. Switchgrass-based bottoms, with or without VGO, produced more aromatics and less olefins and alkanes, compared with spirulina or guayule bottoms. When compared across different mixing ratios, thermal cracking of a 10:1 guayule/VGO mixture resulted in higher aromatics yields than even the VGO by itself. Addition of more VGO up to a 1:1 ratio of VGO/switchgrass bottoms nearly tripled the production of BTEX compounds. For hydrogen-rich bottoms spirulina and guayule, LPG-range olefins yields increased nearly 50% for 1:1 VGO/bottoms blends, compared with theoretical yields.
Prediction of elemental composition, water content and heating value of upgraded biofuel from the catalytic cracking of pyrolysis bio-oil vapors by infrared spectroscopy and partial least square regression models J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-12 A. Veses, J.M. López, T. García, M.S. Callén
Thermochemical conversion of sugarcane bagasse by fast pyrolysis: High yield of levoglucosan production J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-12 Geraldo F. David, Oselys Rodriguez Justo, Victor Haber Perez, Manuel Garcia-Perez
Ex-situ catalytic microwave pyrolysis of lignin over Co/ZSM-5 to upgrade bio-oil J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-10 Wei Xie, Jianghui Liang, Hervan Marion Morgan Jr., Xiaodong Zhang, Kui Wang, Hanping Mao, Quan Bu
The present study aims to produce bio-fuel from lignin via catalytic upgrading of vapors from lignin microwave pyrolysis. The effects of cobalt modified ZSM-5 catalysts on products yield and chemical selectivity of bio-oils were investigated. A central composite experimental design (CCD) was used to optimize the reaction conditions for bio-fuel production. The effects of the reaction temperature and ratio of catalyst to lignin on products (bio-oil, gas and volatiles) yield distribution and chemical composition of bio-oil were investigated. Response surface analysis indicated that the obtained models were able to predict the products yield distribution and the major chemical compound distribution of the bio-oil. GC/MS analysis revealed that the main chemical compounds were ketones, furans, phenols and guaiacols, which accounted for more than 85% in the detected bio-oil. GC analysis showed that the major components of the gas were H2 and CO (about 60%).
Stability of crude bio-oil and its water-extracted fractions J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-10 Shoujie Ren, X. Philip Ye
Fractionation of crude bio-oil into an organic phase and an aqueous phase by simply adding water and research strategies targeted at producing hydrogen, fuels, or other value-added chemicals from the fractions have been proposed. However, the stability of the bio-oil fractions has not been comprehensively investigated. The objective of this study was to comparatively investigate the stability of crude bio-oil and its two fractions by evaluating their physicochemical properties during long-term storage at room temperature and accelerated aging at 40 °C and 60 °C. Comparing with crude bio-oil, the resulted aqueous phase is more stable; for the organic phase, the stability is also improved in terms of the changes in viscosity and average molecular weight, but not in terms of the increasing water content and total acid number. In overview for all the crude bio-oil and its two fractions, the water content, viscosity, total acid number, and average molecular weight increased with the increase of aging time and temperature; except for acetic acid and propionic acid, which slightly increased in content at all aging conditions, all the other 13 measured chemical contents decreased with the increasing aging time and temperature, indicating that the aging process involved all the six chemical groups of anhydrosugars, carboxylic acids, alcohols, furans, ketones, and phenolics, accelerated at higher temperature.
Sulfur Removal from Petroleum Coke during High- Temperature Pyrolysis. Analysis from TG-MS Data and ReaxFF Simulations J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-10 Qifan Zhong, Qiuyun Mao, Jin Xiao, Adri van Duin, Jonathan P. Mathews
Petroleum coke (petcoke) contains high carbon and low ash qualities, but with an undesirably high sulfur content. High-temperature (>1000 K) calcination produces a coke, suitable for many industrial uses, with an acceptable S content. Here the sulfur removal behavior during high-temperature pyrolysis was evaluated by combining high-temperature thermogravimetric analysis with product gas mass spectrometry (TG-MS), and reactive molecular dynamics (ReaxFF) simulations. From the TG-MS data the pyrolysis temperature of >1000 K significantly affected the S rejection. Three petcokes under 1273–1773 K in six different particle sizes (≤6 mm) were pyrolyzed to determine the desulfurization initiation temperature and desulfurization extent. A non-uniform behavior across the particle size ranges was obtained. Six Qingdao petcoke samples with cut sizes of <0.038, 0.07–0.05, 0.11–0.09, 0.25–0.15, 1.18–0.88, and 5.00–6.00 mm all achieved a similar desulfurization extent (∼80%) at >1673 K. However, considerable variability was shown in larger particles (1.18–0.88 and 5.00–6.00 mm) for Qingdao, Zhenhai, and Qilu petcoke between 1473–1773 K. The products included water (presumably from coke quench, 350–410 K), volatiles (430–550 K), CO2 and H2 (>800 K, mainly), CO and SO2 (>1200 K, mainly), and trace quantities of CS2 (>1400 K). The stable sulfur-containing products of this petcoke during high-temperature pyrolysis were SO2 and trace amounts of CS2. However, COS and H2S pyrolysis products were absent or below the detection limits. The pyrolysis behavior was explored using ReaxFF on a macromolecular petcoke structure with the S atoms in thiophene-like functional groups. The mechanism of S loss, under the simulation conditions, involved molecular rearrangement and thermolysis into intermediate states (C2S and CNS) and COS. These were explored for 250 ps for 3000, 3500, and 4000 K with the constant volume/temperature (NVT) ensemble. The sulfur removal transformation during pyrolysis is generally followed: thiophene sulfur → COS, C2S, or CNS → HS → SO2 or CS2.
Catalytic upgrading of volatile from coal pyrolysis over faujasite zeolites J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-09 Yujie Liu, Lunjing Yan, Yonghui Bai, Fan Li
Catalytic upgrading of volatile from coal pyrolysis is a promising approach to convert heavy components to light aromatic hydrocarbons. In this work, four faujasite zeolites with different porosity and acidity, NaY, HY and two dealuminated Y zeolites including hydrothermal treatment Y (HTY) zeolite and hydrothermal treatment-acid leaching Y (HTY-AL) zeolite, were studied to upgrade coal pyrolysis volatile using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The results show that they can significantly improve the yield of light aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, and naphthalene (BTEXN). Compared to NaY and HY zeolite, HTY and HTY-AL zeolite have better catalytic performance for the formation of light aromatics, with the yield of BTEXN increases from 0.78 wt% (raw coal pyrolysis) to 3.63 wt% and 5.31 wt%, respectively. The polycyclic aromatics are cracked remarkably, especially for anthracene with cracking ratio around 60%. The excellent performance of dealuminated Y zeolites correlates directly with their wider range of pore size distribution and suitable acid properties. This work provides a feasible approach of optimizing the acid and textural properties of catalysts to upgrade coal pyrolysis volatile and obtain a high yield of BTEXN.
Quantitative analysis of the aqueous fraction from the Fe-assisted hydrothermal liquefaction of oil palm empty fruit bunches J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-09 Yoshinori Miyata, Yoshiko Yamazaki, Yoshiaki Hirano, Yuichi Kita
Hydrothermal liquefaction is a promising candidate method for the conversion of biomass resources. To improve economic efficiency, the development of processes that utilize the water-soluble (WS) hydrothermal-liquefaction fraction is critical; consequently, a fundamental method for the analysis of the WS fraction is required. In this study, the quantitative analysis of the WS fraction obtained from the Fe-assisted hydrothermal liquefaction of oil palm empty fruit bunches was comprehensively investigated by combining various separation and analysis methods The volatile components of the WS fraction were analyzed by gas chromatography–mass spectrometry (GC–MS) and gas chromatography–flame ionization detection (GC–FID), and they were quantified using the relative response factors estimated by the effective carbon number method. Heavy components not detectable by GC were isolated by freeze-drying, and their elemental compositions, functional groups, and molecular-weight distributions were analyzed. The results reveal that the addition of Fe during hydrothermal liquefaction alters the types of compounds present in the WS fraction by a large extent, and increases the proportion of volatile compounds. The reactivity of the WS fraction in the zeolite-catalyzed cracking reaction was also investigated, which revealed that the volatile components of the WS fraction are efficiently converted into olefins.
Investigation on the thermal decomposition of hydroxyl terminated polyether based polyurethanes with inert and energetic plasticizers by DSC-TG-MS-FTIR J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-09 Yapeng Ou, Yalun Sun, Xueyong Guo, Qingjie Jiao
Thermal decomposition behavior of hydroxyl terminated polyether (HTPE) based polyurethanes (PUs) containing glycerol triacetate (TA), bis(2,2-dinitropropyl)-acetal/formal (BDNPA/F, also known as A3) and N-butyl-N-(2-nitroxyethyl)nitramine (NENA) respectively as plasticizers were investigated by the combination of differential scanning calorimetry-thermogravimetry-mass spectrometry-Fourier transform infrared spectroscopy (DSC-TG-MS-FTIR) techniques. Instead of DSC, DTG curves were applied to evaluate the compatibility since no intense exothermic effect appears in decomposition of HTPE based PU. Three plasticizers, especially the inert TA, were absolutely compatible with HTPE in perspective of engineering application according to the evaluated standard of compatibility. Decomposition of HTPE based PU after endothermic melting is a two-step process including, exothermic depolymerization succeed by intense decomposition. Influence mechanisms of energetic and inert plasticizers on decomposition of HTPE based PU are different. NO· free radical generated by the pyrolysis of NENA and A3 is the major incentive of chain scission resulting in depolymerization of HTPE based PU, and chain scission temperature are shifted forward with the increasing concentration of NO· as the NENA-PU is more vulnerable. While carbanion and electrophile intermediate resembling CO2 generated by decarboxylation reaction of carboxylic acid are the major reactive products in TA. Furthermore, micro defect caused by migration of TA in TA-PU accelerates the degradation of HTPE based PU under acidic condition.
Speciation and bioavailability of heavy metals in pyrolytic biochar of swine and goat manures J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-09 Xinyi Zeng, Zhihua Xiao, Guolin Zhang, Andong Wang, Zihan Li, Yihan Liu, Hua Wang, Qingru Zeng, Yunshan Liang, Dongsheng Zou
Effects of Nano-sized Boron Nitride on Thermal Decomposition and Water Resistance Behaviour of Epoxy-based Intumescent Coating J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-09 Faiz Ahmad, Eza S.B. Zulkurnain, Sami Ullah, Norlaili Amir
In present research work, the effect of nano-sized boron nitride (BN) was studied on intumescent fire retardant coating (IFRC) for structural application. The coated steel substrates were subjected to furnace fire test at 800 °C for 2 h and fire protection test for 1 h. The coatings were characterized by Thermogravimetric analysis (TGA) while the char from fire test was characterized by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). Furnace fire test showed that IFRC reinforced with 4 mass% of nano-sized BN expanded more than 54.84% compared to the BN-1 formulation. Fire protection test performed for 1 h showed minimum substrate temperature of 140 °C with 4 mass% of BN which proved that the IFRC can successfully protect steel substrates within its critical temperature. A maximum of 44.49% residual mass was also recorded for the same coating. XRD analysis revealed that the remaining char contained boron phosphate, boron nitride and phosphoric nitride which are stable at high temperature. The presence of these compounds was also confirmed by functional group analysis using FTIR. FESEM confirmed that micrograph of char contained hexagonal BN. XPS analysis showed a fraction decrease in carbon contents of char residues of intumescent coating formulations with the increase of BN quantity. Pyrolysis GC-MS confirmed that formulations BN-4 released less gaseous product concentration compared to BN-1. Water immersion test showed that there was no trend of mass gain percentage with increasing amount of nano-sized boron nitride incorporated into the coating. The mass gain remained between 1.74% to 2.82%. Overall concluded that the formulation with 4 mass% BN effectively promoted the amount of char acted as a passive protective layer to the substrate resulting in lower substrate temperature with higher coating residual mass.
Bio-oil production from sequential two-step microwave-assisted catalytic fast pyrolysis of water hyacinth using Ce-doped γ-Al2O3/ZrO2 composite mesoporous catalyst J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-08 Bo Zhang, Zhaoping Zhong, Tong Li, Zeyu Xue, Roger Ruan
A sequential two-step microwave-assisted catalytic fast pyrolysis (MACFP) of water hyacinth for hydrocarbon-rich bio-oil production is studied. This newly developed technique is characterized by microwave-assisted fast pyrolysis followed by catalytic upgrading using an additional catalyst packed bed, and it thus achieves the independent control of pyrolysis and catalytic upgrading. On the other hand, in order to minimize coke formation and promote hydrocarbon production in sequential two-step MACFP of water hyacinth, Ce-doped γ-Al2O3/ZrO2 composite mesoporous catalyst (CAZ) is synthesized and used in this study. The effects of catalyst type, pyrolysis temperature, catalytic upgrading temperature and catalyst reusability on product distribution and chemical compositions in bio-oil are investigated. The results demonstrate that water hyacinth is a good biomass candidate for fuel demand, and CAZ can facilitate the hydrocarbon fuel production in bio-oil and exhibits an excellent catalyst reusability. Meanwhile, it is found that the optimal temperatures for water hyacinth pyrolysis and pyrolytic vapor upgrading are 650 °C and 450 °C, respectively.
Pyrolysis mechanism and thermal degradation kinetics of poly(bisphenol A carbonate)-based polymers originating in waste electric and electronic equipment J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-08 Mohammad Nahid Siddiqui, Halim Hamid Redhwi, Eleni V. Antonakou, Dimitris S. Achilias
Poly(bisphenol A carbonate) or polycarbonate (PC) constitutes a significant fraction of the Waste Electrical and Electronic Equipment, mainly due to its high production and consumption rate and its variety of applications. Traditional methods for its treatment no longer appear to provide long-term solutions and for this reason, the investigation of thermochemical methods and more specifically pyrolysis as a potential recycling method took place in the current study. In the first part of this study, pyrolysis studies of polycarbonate have been performed in a Pyrolizer equipped with GC–MS, at five different reactor temperatures, in order to facilitate the understanding of the degradation mechanism. Higher pyrolysis temperatures were found to be more suitable for PC pyrolysis, since they increased the volatile fractions (liquid and gaseous). The gaseous fraction consisted mainly of CO2, CH4 and CO, whereas in the liquid fraction a large amount of different phenolic compounds, including the monomer bisphenol A was recorded. Based on the findings, it has been suggested that the main degradation pathway follows a chain scission mechanism and that the scission of the isopropylidene linkage is the first step. Phenols and phenolic compounds were formed through a series of scission and hydrolysis reactions. In the second part, pyrolysis kinetics of PC are investigated in detail using thermogravimetric experimental data, collected at several heating rates and several either model-free (isoconversional) or model-fitting models. From the isoconversional kinetic analysis the effective activation energy was fund to increase with the extent of conversion, ranging from 146 to 189 kJ/mol and from 154 to 215 kJ/mol, when using the integral method of Tang (similar to the KAS) or the differential method of Friedman, respectively. A simple first order kinetic model was found to simulate excellent the experimental data, though predicting different activation energies and pre-exponential factors at each heating rate employed. The random scission and the autocatalytic models were investigated in detail and the best fit to the experimental data at all different heating rates was found to be the autocatalytic model with n = 1.15 and m = 0.46 (values close to those considered for the random scission model with L = 2, i.e. n = 1.119 and m = 0.4) using an average activation energy, E = 195.9 kJ/mol and pre-exponential factor A = 6.06 1012 min−1. Having a detailed knowledge of the PC degradation kinetics and mechanism will help in better design of large scale process for the recycling of such material originating in WEEE and provide targeted value-added products.
Study on the interaction effect of seaweed bio-coke and rice husk volatiles during co-pyrolysis J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-07 Shuang Wang, Ding Jiang, Bin Cao, Yamin Hu, Chuan Yuan, Qian Wang, Zhixia He, Chi-Wai Hui, Abd El-Fatah Abomohra, Xinlin Liu, Yongqiang Feng, Bo Zhang
Novel biomass-derived hybrid TiO2/carbon material using tar-derived secondary char to improve TiO2 bonding to carbon matrix J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-03-02 Paweł Lisowski, Juan Carlos Colmenares, Ondřej Mašek, Dariusz Łomot, Olga Chernyayeva, Dmytro Lisovytskiy
Characterization of Catalytic Fast Pyrolysis Oils: The Importance of Solvent Selection for Analytical Method Development J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-25 Anne E. Harman-Ware, Jack R. Ferrell III
Two catalytic fast pyrolysis (CFP) oils (bottom/heavy fraction) were analyzed in various solvents that are used in common analytical methods (nuclear magnetic resonance – NMR, gas chromatography – GC, gel permeation chromatography – GPC, thermogravimetric analysis – TGA) for oil characterization and speciation. A more accurate analysis of the CFP oils can be obtained by identification and exploitation of solvent miscibility characteristics. Acetone and tetrahydrofuran can be used to completely solubilize CFP oils for analysis by GC and tetrahydrofuran can be used for traditional organic GPC analysis of the oils. DMSO-d6 can be used to solubilize CFP oils for analysis by 13C NMR. The fractionation of oils into solvents that did not completely solubilize the whole oils showed that miscibility can be related to the oil properties. This allows for solvent selection based on physico-chemical properties of the oils. However, based on semi-quantitative comparisons of the GC chromatograms, the organic solvent fractionation schemes did not speciate the oils based on specific analyte type. On the other hand, chlorinated solvents did fractionate the oils based on analyte size to a certain degree. Unfortunately, like raw pyrolysis oil, the matrix of the CFP oils is complicated and is not amenable to simple liquid-liquid extraction (LLE) or solvent fractionation to separate the oils based on the chemical and/or physical properties of individual components. For reliable analyses, for each analytical method used, it is critical that the bio-oil sample is both completely soluble and also not likely to react with the chosen solvent. The adoption of the standardized solvent selection protocols presented here will allow for greater reproducibility of analysis across different users and facilities.
Shrinkage of SU-8 microstructures during carbonization J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-24 Rucha Natu, Monsur Islam, Jordon Gilmore, Rodrigo Martinez-Duarte
SU-8 is a negative photoresist that is widely used as a precursor to carbon in the fabrication of 3D carbon microstructures. These microstructures are used in applications including sensors, manipulators and batteries. The SU-8 structures are usually made using photolithography and heat treated to high temperatures in an inert atmosphere to achieve carbonization. The shrinkage that results during carbonization affects the design of devices where these structures are used. In this work we studied the shrinkage during carbonization. We emphasized the impact of 1) carbonization protocol and 2) geometry and shape of the SU-8 precursor. Using statistical analysis with ANOVA, we concluded that the geometry of the structure, pyrolysis temperature and pyrolysis atmosphere play a major role in determining the shrinkage of the SU-8 structures. We did not observe a statistically-valid impact from changes in dwell times and heating rate. Based on these results, we present a series of relations to help predict the shrinkage of SU-8 microstructures during carbonization, and facilitate the design of carbon 3D microstructures in different fields.
Consistency of biochar properties over time and production scales: A characterisation of standard materials J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-24 Ondřej Mašek, Wolfram Buss, Audrey Roy-Poirier, Walter Lowe, Clare Peters, Peter Brownsort, Dimitri Mignard, Colin Pritchard, Saran Sohi
Users of biochar in the field require this product to reliably meet its declared specifications. For the first time, this work investigated, whether these specifications could be reproducibly obtained as a sole function of the thermal history of the biomass feedstock during slow pyrolysis, irrespective of the type and scale of the production unit. Using volatile matter content as a proxy for a wider set of biochar quality parameters, biochar from units at scales from grams to hundreds of kilograms, representing three main types of slow pyrolysis units (fixed bed, screw reactor and rotary kiln) were investigated. For the first time we showed that comparable biochar could be produced by these very different pyrolysis units, with good reproducibility within individual as well as among separate production runs.
Effect of microwave-assisted organosolv fractionation on the chemical structure and decoupling pyrolysis behaviors of waste biomass J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-21 Anqing Zheng, Kun Zhao, Jiangwei Sun, Liqun Jiang, Zengli Zhao, Zhen Huang, Guoqiang Wei, Fang He, Haibin Li
Fast pyrolysis of waste biomass is a cross-coupling pyrolysis of its components (cellulose, lignin, hemicellulose and ash), resulting in the complex composition of bio-oil. Here, microwave-assisted organosolv fractionation (MOF) of waste biomass combined with decoupling pyrolysis is first proposed to overcome this challenge. MOF of waste eucalyptus was conducted in different solvents (organic acid, glycerol or ethylene glycol (EG)). The derived fractions were first characterized by Fourier transform infrared (FTIR) spectroscopy and two-dimensional heteronuclear single-quantum coherence nuclear magnetic resonance (2D HSQC NMR) and then pyrolyzed via thermogravimetric analyzer-mass spectrometry (TG-MS) and a pyro-probe reactor to exam their pyrolysis behaviors. The experimental results demonstrated that waste eucalyptus can be rapidly divided into xylose, high purity organosolv lignins (OL) and cellulose-rich fractions (CF) by MOF under mild conditions. Compared with the fast pyrolysis of raw waste eucalyptus, the decoupling pyrolysis of CF produced higher yields of levoglucosan, whereas the decoupling pyrolysis of OL can result in decreases in the yields of some phenols. MOF can boost the levoglucosan yields from CF by 464–502% compared to that of raw waste eucalyptus. The rank order of the solvents for the improvement in the levoglucosan yield was organic acid < glycerol < EG. This work proposed an efficient, integrated process for selectively producing platform chemicals from waste biomass that can compete with hydrolysis and catalytic conversion processes.
Sugarcane bagasse ex-situ catalytic fast pyrolysis for the production of Benzene, Toluene and Xylenes (BTX) J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-21 Payam Ghorbannezhad, Mohammadreza Dehghani Firouzabadi, Ali Ghasemian, Paul J. de Wild, H.J. Heeres
The ex-situ catalytic pyrolysis of sugarcane bagasse with various HZSM-5 (23, 50, and 80) catalysts was studied in a tandem micro reactor-GC/MS at 400 °C, 450 °C, 500 °C and 550 °C with a catalyst to biomass (C/B) ratios ranging from 2 to 23. The yields of benzene, toluene and xylenes (BTX) were significantly affected by pyrolysis temperature and C/B ratio. The highest BTX yield of 22% was obtained for the HZSM-5 (23) catalyst at C/B ratio of 12.5 and a temperature of 475 °C. Finally, an experimental design was performed to determine the optimal process conditions for BTX yields.
Thermochemical characterization of brown seaweed, Laminaria digitata from UK shores J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-21 Membere Edward, Paul Sallis
Brown algae, Laminaria digitata samples were collected over six-month intervals within a year (January, July and December 2015) and assessed for a range of thermochemical properties. Initial pyrolysis rates using thermo-gravimetric analysis (TGA) were carried out to assess their proximate characteristics, ranging from moisture content (MC) (3.48%–4.10%), volatile content (VC) (56.64–56.23%), char (11.80–12.76%) and fixed carbon (27.87–29.95%). Analysis by pyrolysis gas chromatography–mass spectrometry (Py–GC/MS) identified sixty four compounds present in all samples, twenty which have been previously reported as major pyrolysis products of Laminaria digitata.1H NMR analysis of sodium alginate fractions extracted from the samples was used to characterise the monad, diad, triad frequencies and average block length of the alginate. Results of the monad frequencies FM (0.36–0.46) and FG (0.54–0.64) are consistent with reported values in literature. The Laminaria digitata alginate also showed values that are in agreement with most reported literature for both diad frequencies, homopolymeric mannuronic (FGG = 0.19–0.25) and guluronic (FMM = 0.33–0.47) blocks with alternating block fractions of (FGM = 0.17–0.21) and (FMG = 0.17–0.21), respectively. The M/G ratio value of 1.17–1.80 has been stated for alginates that can be used to produce soft and elastic gels rather than brittle ones. Furthermore, the computed triad frequencies results are (FGGG = 0.14k0.17, FMGM = 0.11–0.13, FGGM = FMGG = 0.05–0.09) and the average block lengths are (NG = 2.15k2.22 and NM = 2.61–3.85).
Direct and indirect approaches based on paper analysis by Py-GC/MS for estimating the age of documents J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-21 L. Ortiz-Herrero, M.E. Blanco, C. García-Ruiz, L. Bartolomé
The age of a relatively old document is one of the pending issues to be resolved in the field of forensic documentary examination. Although nowadays there are a variety of analytical methodologies focused in the analysis of inks for dating documents, the paper analysis has attained little attention. This work aims to develop two complementary approaches for estimating the age of documents based on paper analysis employing the pyrolysis technique coupled to gas chromatography with detection by mass spectrometry (Py-GC/MS): (i) a direct approach using the pyrolytic fingerprints and multivariate regression with artificially aged samples, and (ii) an indirect approach based on the identification of compounds characteristic of the document period. The direct approach has successfully allowed the age estimation of relatively old documents under police custody (up to 30 years of age) and the determination of a relation between the natural and the accelerated aging of paper under the used conditions. This approach is applicable to papers that have the same (or similar) composition and have been stored under comparable storage conditions. Additionally, the indirect approach is presented as an interesting perspective to ratify valuable information of the document age.
Preparation of multipurpose bio-oil from rice husk by pyrolysis and fractional condensation J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-20 Shanwei Ma, Liqiang Zhang, Liang Zhu, Xifeng Zhu
A set of fixed-bed biomass pyrolysis reactor incorporated with three-stage condensation columns was constructed in this study, and the effects of pyrolysis temperature, carrier gas flow rate and condensation temperature on biomass pyrolysis products were discussed systematically. Results show that as the pyrolysis temperature increased, the yield of liquid products initially increased with a maximum yield at 550 °C and then decreased. When the temperatures of the three-stage condensers were 110 °C, 0 °C, and −196 °C, the highest yields of bio-oil in each condenser were accordingly obtained at 550 °C, 450 °C, and 500 °C, respectively. Carrier gas flow rate and fractional condensation temperature indicated minimal influence on the total yield of liquid products. However, fractional condensation temperature had an obvious effect on the yields of the fractions. Gas chromatography/mass spectrometry revealed that the first fraction contained abundant phenolic compounds, the second fraction contained medium-boiling compounds with relatively high concentrations of water, acids, and ketones and the last fraction contained a minimal amount of hydrocarbons and water. Furthermore, higher pyrolysis temperature resulted in a higher yield of phenol products, whereas higher condensation temperature led to a higher concentration of phenols and dehydrated carbohydrates.
Comparative research on deoxy-liquefaction of marine and terrestrial biomasses J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-19 Jiping Wang, Bin Su, Yulin Xie, Min Du, Wenying Dai, Yuan Wen, Xiangyu Sun, Jinhua Li
Marine biomass and terrestrial biomass have distinct compositions and structures. In order to understand the effect of feedstock difference on deoxy-liquefaction products, the experiments were performed with marine biomass (Enteromorpha prolifera, Giant kelp, Undaria pinnatifida) and terrestrial biomass (cotton stalk, sweet potato vine, plane leaves) for comparison of product yields and compositions. GC–MS results showed that the liquid oils from marine biomass were rich in alkanes (36.64–39.18%) and nitrogenous compounds (7.07–11.61%). While, the terrestrial biomass oils were rich in phenolic compounds (36.02–40.55%) and aromatic hydrocarbons (6.36–12.31%). The solid char properties were further characterized by FTIR, XRD and SEM analysis, respectively and their potential applications were also discussed. All the results suggested that the types of feedstock have a significant effect on the biomass deoxy-liquefaction products.
A technical review on semi-continuous and continuous pyrolysis process of biomass to bio-oil J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-15 Khan Muhammad Qureshi, Andrew Ng Kay Lup, Saima Khan, Faisal Abnisa, Wan Mohd Ashri Wan Daud
Co-pyrolysis of wet torrefied bamboo sawdust and soapstock J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-13 Yunpu Wang, Qiuhao Wu, Leilei Dai, Zihong Zeng, Yuhuan Liu, Roger Ruan, Guiming Fu, Zhenting Yu, Lin Jiang
In the present study, effect of wet torrefaction on biomass properties and co-pyrolysis of wet torrefied biomass and soapstock were investigated. Experimental results indicated that the ash and volatile contents decreased after wet torrefaction. Obvious decrease of hydrogen and oxygen and an increase of carbon were observed at the same time, which resulted in the augment of higher heating value (HHV). Although lower mass yield was observed under a higher temperature, corresponding energy yield was relatively higher. X-ray diffraction (XRD) analysis revealed that wet torrefaction (below 240 °C) can improve the crystallinity degree of bamboo sawdust. Fourier transfer infrared spectrometry (FTIR) analysis showed that wet torrefaction can significantly remove the acetyl groups in hemicellulose. In thermogravimetric (TG) analysis, the thermal properties of wet torrefied samples and soapstock were altered by co-pyrolysis. Pyrolysis-gas chromatography/mass spectroscopy (Py-GC/MS) analysis showed that co-pyrolysis can produce less oxygen-containing compounds and more hydrocarbons after wet torrefaction. Kinetic analysis showed that the addition of soapstock can obtain a lower activation energy compared with biomass pyrolysis individually. The activation energy for co-pyrolysis of pretreated biomass and soapstock was lower than co-pyrolysis of raw biomass and soapstock, suggesting that wet torrefaction has a positive influence on the co-pyrolysis. The results indicated that the combination of wet torrefaction and co-pyrolysis was a feasible technology for obtaining high-grade oil from biomass.
Energy recovery analysis from sugar cane bagasse pyrolysis and gasification using thermogravimetry, mass spectrometry and kinetic models J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-13 Jayaraman Kandasamy, Iskender Gokalp, Sebastien Petrus, Veronica Belandria, Stephane Bostyn
The energy recovery from biomass and it’s utilisation as fuels and chemicals has been gained interest in recent years. The production of syngas from sugarcane pyrolysis and gasification is investigated. Pyrolysis studies of sugar cane bagasse are performed using thermogravimetry (TG) at different heating rates (10, 20, 40, 100, 250 K/min). A mass spectrometry (MS) coupled with TG is used to detect the evolved gases. The effect of pyrolysis heating rate on char yield and evolved gases are examined. The resultant char is gasified in steam ambience under isothermal and non-isothermal conditions. The results are shown that sugarcane pyrolysis and char-gasification and gas release (H2, H2O, CO, CO2 and hydrocarbons) process are influenced by the heating rate. Char gasification kinetics are estimated using volumetric, grain and random pore models under isothermal conditions. Similarly, sugarcane bagasse pyrolysis and gasification kinetics under non-isothermal conditions in steam and air ambience is estimated using Friedman, KAS (Kissinger−Akahira−Sunose) and FWO (Flynn−Wall−Ozawa) methods for all the mass conversion levels. The activation energy of steam gasification is more than twice when compare to air gasification (partial combustion) process while using FWO and KAS methods Altogether, these results contribute to better understanding of the sugarcane bagasse pyrolysis and gasification features for gasifier process modelling.
Release of Ca during coal pyrolysis and char gasification in H2O, CO2 and their mixtures J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-12 Xuhao Yang, Peng Lv, Shenghua Zhu, Lunjing Yan, Yonghui Bai, Fan Li
The release characteristics of Ca during a Chinese bituminous coal pyrolysis and char gasification in different gasifying agents was studied. Residual chars with different carbon conversion levels were obtained by gasifying in a quartz fixed-bed reactor under H2O, CO2, and H2O/CO2 atmospheres at 800–1000 °C. Sequential chemical extraction and microwave digestion were used to determine the modes of occurrence of Ca in chars. X-ray diffraction and scanning electron microscopy were used to analyze the ash composition and the morphology of minerals. The contents of Ca in chars were measured by atomic absorption spectroscopy. The results indicate that water-soluble form and HCl-soluble form Ca transforms mainly into gas phase during pyrolysis. The release ratio of Ca at 800 °C under different atmospheres is H2O/CO2 >H2O > CO2. The main reason is that minerals are more prone to sintering in CO2 atmosphere. The interaction of H2O and CO2 can expand pores, which precipitate the minerals to the char surface and release into the gas phase. Increasing temperature induces the collapse of the pore structure which changed the release rule of Ca. The composition of the ash obtained from gasification at 1000 °C in CO2, H2O and H2O/CO2 are nearly same.
Biofuel production from distillers dried grains with solubles (DDGS) co-fed with waste agricultural plastic mulching films via microwave-assisted catalytic fast pyrolysis using microwave absorbent and hierarchical ZSM-5/MCM-41 catalyst J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-12 Bo Zhang, Zhaoping Zhong, Tong Li, Zeyu Xue, Xiaojia Wang, Roger Ruan
Microwave-assisted catalytic fast co-pyrolysis (co-MACFP) of distillers dried grains with solubles (DDGS) and waste agricultural plastic mulching films (WAPMFs) with SiC as microwave absorbent and hierarchical ZSM-5/MCM-41 as catalyst are implemented in a microwave-induced reactor. MCM-41 mesoporous structure is formed in hierarchical ZSM-5/MCM-41 catalyst as the outer shell layer coupled with ZSM-5 as the inside core. Experimental results show that the use of both microwave absorbent and hierarchical ZSM-5/MCM-41 catalyst significantly increase the carbon yield of hydrocarbons in bio-oil. The influence of co-MACFP temperature and the mass ratio of WAPMFs to DDGS (W/D ratio) on product distribution and hydrocarbon composition is investigated. The total liquid yield and total hydrocarbon carbon yield in bio-oil first increase with the augment of temperature from 500 to 650 °C, and then decrease when temperature continues to rise. Besides, a higher W/D ratio can favor bio-oil production and retard coke formation, and a significant synergy between DDGS and WAPMFs is observed during co-MACFP. Additionally, from the perspective of hydrocarbon carbon yield in bio-oil, W/D ratio of 1.0 is the best option.
Catalytic Fast Pyrolysis of Rice Straw to Aromatic Compounds over Hierarchical HZSM-5 Produced by Alkali Treatment and Metal-modification J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-12 Hao Chen, Hao Cheng, Feng Zhou, Kequan Chen, Kai Qiao, Xiuyang Lu, Pingkai Ouyang, Jie Fu
Behavior of Stable Carbon and Stable Nitrogen Isotopes during Hydrothermal Carbonization of biomass J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-11 M. Toufiq Reza, Simon R. Poulson, Silvia Román, Charles J. Coronella
This work studied the changes of stable isotope compositions (C and N) of diverse biomass feedstocks (loblolly pine, cow manure, and sewage biosolids) as a result of hydrothermal carbonization (HTC), and provides insight into degradation pathways based on these changes. HTC was conducted at different times (5 and 30 min) and temperatures (180, 220, and 260 °C) and produced hydrochars were characterized in terms of ultimate, proximate, stable carbon isotope (δ13C), and stable nitrogen isotope (δ15N) compositions. In addition to reaction conditions, results showed that the differences in feedstock composition, closely related to reactivity, determined in large part isotope behavior. In general, the carbon densification associated with HTC corresponded to a small but consistent decrease of δ13C values. In contrast, there were significant increases of δ15N values during HTC, with larger shifts associated with increased HTC reaction severity. These trends in isotopic compositions, related to changes of characteristic elemental indices (O/C, H/C, O/N, H/N), allowed for the identification of particular reaction pathways for individual feedstocks.
Ru incorporation Enhanced electrochemical performance of spray deposited Mn: Co3O4 nano-composite: Electrochemical approach J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-10 R.C. Ambare, B.J. Lokhande
Paper highlights, enhanced electrochemical performance of spray pyrolysed ruthenium (Ru) incorporated manganese-cobalt oxide (Mn: Co3O4) thin films, prepared via non aqueous route on to stainless-steel at 623 ± 2 K. In the 1st phase of the work, prepared samples were characterized by XRD, SEM, TEM, SAED, EDAX and XPS and in the 2nd phase, samples were analyzed electrochemical characterizations. CV study shows mixed capacitive behaviour for all electrodes. For optimized Ru-incorporation, prepared electrode exhibits maximum specific capacitance 1440.0 F/g at 1 mV/s scan rate in 1 M KOH. Excellent electrochemical stability is observed at 100 mV/s scan rate. Using charge-discharge study, the calculated values of specific energy, specific power and columbic efficiency were found as 1.1 Wh/kg, 2.80 kW/kg and 96.72% respectively. Electrochemical impedance measurement is scanned in the frequency range 1 mHz to 1 MHz. The internal resistance exhibited by the electrode as observed using Nyquist plot is ∼1.12 Ω. By using ZsimpWin software, equivalent circuit was searched.
Thermal degradation and compositional changes of wood treated in a semi-industrial scale reactor in vacuum J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-07 Bo-Jhih Lin, Baptiste Colin, Wei-Hsin Chen, Anélie Pétrissans, Patrick Rousset, Mathieu Pétrissans
Temperature influence and distribution of bio-oil from pyrolysis of granular sewage sludge J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-07 Fei Huang, Yang Yu, He Huang
Catalytic Fast Pyrolysis of Cellulose for Increasing Contents of Furans and Aromatics in Biofuel Production J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-07 Wenliang Wang, Yujie Shi, Yong Cui, Xinping Li
Pyrolysis behaviors of deacetylated poly(ethylene-co-vinyl acetate) depending on pyrolysis temperature J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-07 Sung-Seen Choi, Eunha Kim
Pyrolysis behaviors of poly(ethylene-co-vinyl acetate) (EVA) depending on pyrolysis temperature were investigated. EVA was pre-pyrolyzed at 400 °C to remove acetic acid before main pyrolysis. The deacetylated EVA was pyrolyzed at 550–800 °C and variations of the major pyrolysis products with the pyrolysis temperature were examined. The major pyrolysis products were alkanes, alkenes, alkadienes, and cyclic compounds including aromatic species. Most of the major pyrolysis products increased as the pyrolysis temperature increased except for the alkanes. Relative abundances of the alkadienes and aromatic compounds were notably increased by increasing the pyrolysis temperature. By increasing the pyrolysis temperature, relative intensity ratios of butadiene/1-butene and styrene/1-butene linearly increased whereas those of cycloheptadiene (or vinylcyclopentene)/1-butene and vinylcyclohexene/1-butene linearly decreased. From Arrhenius plots for the principal pyrolysis products, relative activation energies for the formations of butadiene, cycloheptadiene (or vinylcyclopentene), vinylcyclohexene, and styrene were obtained. Pyrolysis behaviors of the deacetylated EVA were explained by formation mechanisms including ethylene-vinyl acetate heterosequence and dehydrogenation reactions.
Pyrolysis of arsenic-bearing gypsum sludge being substituted for calcium flux in smelting process J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-05 Xun Li, Xing Zhu, Xianjin Qi, Kongzhai Li, Yonggang Wei, Hua Wang, Jianhang Hu, Xinghuan Hui, Xin Zhang
Arsenic-bearing gypsum (ABG) sludge, one of the biggest hazardous waste in the nonferrous metals industry, greatly threatens the ecological safety due to possible leakage and diffusion risks. However, the state-of-the-art techniques suffer great challenges for the disposal of ABG sludge due to its properties including worthless constituents, high arsenic leaching toxicity, and tremendous output. In this work, the pyrolysis of ABG sludge is studied aiming to propose a flexible and facile co-disposal method by using ABG sludge as calcium flux instead of limestone in smelting processes. The pyrolysis behavior and arsenic migration are investigated in the TG-FTIR and the fixed-bed reactor by means of XRD, chemical analysis, and Chinese standard leaching tests. The sludge can be converted into environmentally friendly residue via the both direct and reductive pyrolysises at the temperatures ≥800 °C due to the release of leachable arsenic in the form arsenic-bearing dust. The direct pyrolysis is favorable for the sulphur releasing through the transformation of CaSO4 → CaO/SO2. While this transformation is depressed in the anthracite-driven reductive pyrolysis because of the reducing agent and being largely replaced by the CaSO4/C → CaS/CO2 pathway. In addition, the arsenic releasing is significantly promoted in this reducing environment by the further reduction of arsenates. The proposed co-disposal model of ABG sludge being substituted for calcium flux in ISASMELT copper smelting process renders the good compatibility and flexibility.
Catalytic conversion of beech wood pyrolytic vapors J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-03 Alexandre Margeriat, Alissa Bouzeggane, Chantal Lorentz, Dorothée Laurenti, Nolven Guilhaume, Claude Mirodatos, Christophe Geantet, Yves Schuurman
Catalytic fast pyrolysis (CFP) of beech wood chips was undertaken in a laboratory-scale fixed bed reactor equipped with a biomass semi-continuous dispenser. During pyrolysis, chars are retained on a quartz frit and the pyrolytic vapors are entrained through a fixed-bed catalyst to be converted. Several acidic catalysts such as zeolites H-Beta, zeolite HMFI and 5% Ni supported on HMFI were screened in this equipment. The Ni/HMFI catalyst was also tested in the presence of 1 vol.% of hydrogen in the feed stream. Mass and carbon balances were carefully checked and the gas, liquids and solids fractions were analyzed in-depth to evaluate the impact of the catalyst compared to thermal conversion. In the presence of a catalyst, with a low catalyst-to-biomass ratio of 0.1, a lower amount of bio-oil was formed but it contained less oxygen. The bio-oils were characterized by bi-dimensional GC (GCxGC) coupled with MS and FID detectors. The amount of gaseous products also increased in the presence of all catalysts. In addition of the deoxygenation, gel-permeation chromatography (GPC) showed a decrease of the highest molecular masses in the bio-oil after catalytic treatment, which confirms the conversion of some oligomers. The presence of Ni enhanced the deoxygenation reactions while the addition of H2 is also beneficial to the bio-oil composition.
Molecular characterization of biochar from five Brazilian agricultural residues obtained at different charring temperatures J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-03 Judith Schellekens, Carlos Alberto Silva, Peter Buurman, Tatiana F. Rittl, Rimena R. Domingues, Marina Justi, Pablo Vidal-Torrado, Paulo Fernando Trugilho
Important parameters that influence biochar properties include charring temperature and biomass type. We characterized the molecular properties of biochars from five agricultural residues with pyrolysis gas chromatography mass/spectrometry (pyrolysis-GC/MS) in comparison with atomic H/C and N/C ratios. Feedstocks included chicken manure, eucalyptus sawdust, coffee husk, sugarcane bagasse and pine bark. Biochars produced at three different temperatures (Tchar) were analyzed, including 350, 450 and 750 °C, as well as the uncharred materials. The optimum temperature during analysis with pyrolysis-GC/MS (Tpy) was examined. Tpy 600 °C gave the best results for all Tchar by showing a larger diversity of pyrolysis products compared to Tpy 700 °C and 800 °C; Tpy 600 °C was therefore used for qualitative and quantitative comparison of the samples. Charring temperature was the dominant factor that determined the chemical composition of the biochar pyrolysates. Uncharred feedstocks had the largest contribution from carbohydrates, lignin phenols and long chain n-alkanes, all of which rapidly decreased with charring; biochars produced at Tchar 350 and 450 °C showed the largest contribution from phenols, mid-chain n-alkanes, benzofurans, indenes, biphenyls and PAHs, from which the benzofurans, indenes, biphenyls and PAHs were particular abundant in samples produced at Tchar 450 °C; pyrolysates of biochars produced at Tchar 750 °C were characterized by branched aliphatics, short chain n-alkanes/n-alkenes and low molecular weight (LMW) benzenes. Factor analysis showed that the variation of products differed largely within some chemical groups. For the N-containing compounds, caffeine, C16 alkylnitrile and diketopiperazines were associated with uncharred materials, benzonitriles and quinolines were associated with Tchar 350–450 °C. Another part of the variation of N-containing compounds was associated with chicken manure, and to a lesser extend also coffee husk, independently of Tchar. For all five agricultural residues, the highest chemical diversity was found for biochar produced at Tchar 350 °C. As the charring temperature increased, the diversity of pyrolysis products diminished.
Identification and quantification of polycyclic aromatic hydrocarbons generated during pyrolysis of sewage sludge: effect of hydrothermal carbonization pretreatment J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-02 Tingting Liu, Yanchuan Guo, Nana Peng, Qianqian Lang, Yu Xia, Chao Gai, Qingfu Zheng, Zhengang Liu
Fast pyrolysis of coal particles in a novel hot plate reactor: Implications of the reaction atmosphere on the reactivity and char chemical structure J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-02 Carlos F. Valdés, Farid Chejne
Fast pyrolysis of pulverized coals (Highly Volatile Bituminous C-(HVBC) and Semi-anthracites (SA) were studied in a novel hot plate reactor (HPR). The combined effect of the heating rate (HR) and the reaction environment inside the reactor on chars structure were detailed analyzed. The iso-conversional Flynn–Wall–Ozawa (FWO) methodology was utilized to study mass loss during fast pyrolysis of both coals. It was found that, at high HR, the mass loss rate during pyrolysis and the degree of microstructural ordering reached by the chars strongly depend on secondary reactions between carbonaceous structures, the volatiles and the reaction atmosphere.
Development of a microwave thermogravimetric analyzer and its application on polystyrene microwave pyrolysis kinetics J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-01-31 Philippe Leclerc, Jocelyn Doucet, Jamal Chaouki
To study pyrolysis kinetics inside a microwave environment, a microwave thermogravimetric analyzer was developed. A sample mass as low as 0.3 g can be studied along with silicon carbide as the microwave receptor. The temperature is measured with a custom-made infrared thermopile equipped with different optical filters specific to this application. Validation of the microwave thermogravimetric analyzer features showed that the measured data can be used as is for kinetic development. Different heating profiles can be achieved by modulating the microwave power. The microwave thermogravimetric analyzer was then used for the kinetic development of polystyrene microwave pyrolysis. Polystyrene was chosen because of its low recycling rate and its great potential to produce high-valued products, like styrene. Three heating rates (24.5, 38.5 and 49.5 °C min−1) were used to estimate the kinetic parameters. By comparing several reaction models, a random scission model was found to best explain the experimental data. The choice of the reaction model was made based on two statistical tests: the coefficient of determination R2 and the residual sum of squares RSS. With this reaction model, an activation energy of E = 45 kJ mol−1 and a pre-exponential constant of ln(A) = 3.6 were found for polystyrene microwave pyrolysis.
Analytical pyrolysis of ovalbumin J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-01-31 Sibilla Orsini, Celia Duce, Ilaria Bonaduce
In this study the thermal degradation of ovalbumin (OVA) under nitrogen atmosphere was investigated. For this scope, a multi instrumental approach based on thermogravimetry (TG), thermogravimetry coupled with infrared spectroscopy (TG/FTIR) and pyrolysis coupled with mass spectrometric detection, i.e. flash pyrolysis-coupled with gas chromatography-mass spectrometry (Py/GC/MS), evolved gas analysis coupled with mass spectrometry (EGA/MS) and double shot pyrolysis-coupled with gas chromatography-mass spectrometry (DSP/GC/MS), was used. The pyrolysis of a protein involves a combination of several complex mechanisms resulting in a very high number of products. The study highlighted that pyrolysis of OVA produces low-molecular weight gasses, such as CO2, H2O, HCNO, NH3 and CO, as main compounds. In addition, a series of organic compounds containing heteroatoms and unsaturations were also identified, whose formation occurred at different temperatures over the pyrolytic process. Among these, cyclic pyrolysis products were identified: dialkyl substituted 2,5-diketopiperazines (DKPs) and, for the first time, unsaturated-DKPs (un-DKPs), 3,5-alkyl-3,4-dihydro-2H-pyrrole-2,4-diones (ADPDs) and 3-alkenyl-5-alkyl-pyrrolidine-2,4-diones (AAPDs). These compounds are formed below 350°, and are produced by cyclisation reactions of two neighbouring amino acids. Pyroglutamic acid was also found among the main pyrolysis products of OVA, obtained as pyrolytic product of Glu, which is the most abundant amino acid in OVA. Aromatic compounds, such as pyridine, pyrrole, toluene, alkyl-benzenes and alkyl-pyrroles, phenol and alkyl-phenols, benzeneacetonitrile, benzenepropanenitrile, indole and alkyl-indoles, were detected, produced over a wide range of temperatures. This study highlighted for the first time that aromatic compounds produced below 320 °C are associated to the pyrolysis of specific amino acid side chains, while at higher temperatures, they are the pyrolysis products of the residual material remaining after condensation reactions, pyrolytic scissions and cyclization reactions.
Catalytic effect of montmorillonite nanoparticles on thermal decomposition of coal tar pitch to carbon J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-01-31 Maciej Gubernat, Aneta Fraczek-Szczypta, Janusz Tomala, Stanislaw Blazewicz
Direct synthesis of hollow carbon nanofibers on bio-char during microwave pyrolysis of pine nut shell J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-01-31 Jian Zhang, Arash Tahmasebi, Joy Esohe Omoriyekomwan, Jianglong Yu
Hollow carbon nanofibers (HCNFs) were formed on the bio-char surface during microwave pyrolysis of pine nut shell in the temperatures range of 400–700 °C without the use of any additional catalyst, except activated carbon added as a microwave absorber. Scanning electron microscopy (SEM) analysis showed that HCNFs were only formed on microwave pyrolysis chars and not fixed-bed chars, suggesting that microwave irradiation had a major influence on their formation. High resolution transmission electron microscope (HRTEM) results showed that the synthesized HCNFs at 500 °C and 600 °C had a diameter of about 400 nm and length of 1400–5000 nm. HCNFs had multi-walled structure with a d-spacing of about 0.35 nm. Unlike fixed-bed bio-chars, the X-ray diffraction (XRD) analysis of the microwave bio-chars showed typical graphite peak at around 2θ = 26.3° with the strongest peak observed in 600 °C bio-char. Raman spectroscopy analysis revealed that the highest degree of carbon order of HCNFs was achieved at 600 °C, which agreed well with XRD analysis results. Detailed analysis of the volatiles evolved during microwave pyrolysis suggested that hydrocarbons in bio-oil such as benzene and alkenes and CO, CO2, methane, and ethane in bio-gas acted as the carbon source during formation of HCNFs.
Long time, low temperature pyrolysis of El-Lajjun oil shale J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-01-31 Jameel S. Aljariri Alhesan, Yi Fei, Marc Marshall, W. Roy Jackson, Ying Qi, Alan L. Chaffee, Peter J. Cassidy
Advanced characterization unravels the structure and reactivity of wood-based chars J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-01-31 Sarah Berhanu, Maxime Hervy, Elsa Weiss-Hortala, Henry Proudhon, Marie-Hélène Berger, Anthony Chesnaud, Matthieu Faessel, Andrew King, Doan Pham Minh, Audrey Villot, Claire Gérente, Alain Thorel, Laurence Le Coq, Ange Nzihou
This study aims at understanding the structural changes occurring in the carbonaceous matrix of wood-based chars during their thermal conversion. Although chars are routinely characterized by porosity measurements or scanning electron microscopy, the composition and structure of the carbonaceous matrix is often not investigated. Here, advanced characterization using X-ray synchrotron microtomography, transmission electron microscopy, Raman spectroscopy and X-ray diffraction provided a precise description of the char properties, allowing for an accurate discussion of their catalytic properties. Two chars were produced by slow pyrolysis of wood waste (400 and 700 °C) and a third one was fabricated by activation under steam at 850 °C of the char obtained at 700 °C. The results show that the pyrolysis temperature and the activation performed did not affect the macrostructure of the chars and that the pores were interconnected at the macroscopic scale. However, at 700 °C, the micro- and nanostructures were modified: short-range organized graphene fringes were observed. The activated char showed a homogeneous microstructure similar to that of its precursor. Besides, the ratio of graphene-like structures, the local organization of graphene sheets, and the imperfections in graphene-like sheets were clearly improved by the post-treatment. To our knowledge, this is the first time that such an approach, combining various tools, is applied for the study of pyrolysis chars.
Study of the effects of temperature on syngas composition from pyrolysis of wood pellets using a nitrogen plasma torch reactor J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-01-31 Ralph Farai Muvhiiwa, Baraka Sempuga, Diane Hildebrandt, Xiaojun Lu, Jaco van der Walt
This work shows work flows supported by experimental work to analyse the efficiency of a plasma system in biomass conversion processes. The most common set of problems encountered when using biomass-to-energy (BTE) processes relate to tar formation and product gas composition. However, using plasma technology to convert biomass provides a solution because it unlocks more energy than can be achieved by other BTE systems by using a heat supply derived from electricity. The research presented in this paper focuses on the conversion of biomass to chemical energy (in gaseous form) with the aid of the electrical energy supplied by a water-cooled nitrogen plasma torch. The authors conducted a series of experiments in a pyrolysis set up in which wood pellets were converted to syngas in a small-scale laboratory nitrogen plasma torch reactor with a maximum power supply of 15 kW. The efficiency of the process was measured in terms of the carbon conversion to all product gases which changed from 43 to 77%, at temperatures ranging from 400 °C to 1000 °C respectively. The combined carbon monoxide and hydrogen mole concentration in the product gas (without nitrogen) was 86% at 1:1 ratio for all temperatures studied. Syngas yield increased with increase in temperature. The overall biomass conversion obtained increased from 46% to 82% for the temperatures 400 °C to 1000 °C respectively, with the balance comprising carbon-rich solid residue and liquid. The work flow shows that a plasma system can get to high temperatures but work is also degraded in the overall process. Exergy analysis shows that the work lost by the overall process decreases with increase in process temperature.
PRODUCTION OF BAMBOO-TYPE CARBON NANOTUBES DOPED WITH NITROGEN FROM POLYAMIDE PYROLYSIS GAS J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-01-31 Noelia Arnaiz, Ignacio Martin-Gullon, Rafael Font, M. Francisca Gomez-Rico
Bamboo-type carbon nanotubes (BCNTs) doped with nitrogen were produced by catalytic chemical vapor deposition from the effluent gases resulting from pyrolysis of polyamide 6.6. This polymer provides the carbon and nitrogen source and allows to obtain enough hydrogen during its decomposition for the carbon nanotubes (CNTs) production without prior catalyst reduction. The influence of pyrolysis and growth temperatures was studied in order to obtain the best quality CNTs. Transmission electron microscopy, X-ray diffraction, and Raman spectrometry showed that the best results were obtained at 900 °C pyrolysis temperature and 750 °C growth temperature, since the presence of amorphous carbon was negligible and the best crystalline degree was obtained. These BCNTs had from 5 to 20 layers and their arcs of bamboo-like compartments had from 3 to 15 layers. They had 20 nm in diameter and lengths typically on the order of micrometers.
Thermal conversion of aspen wood in supercritical ethanol in the presence of high-silica zeolite catalysts J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-01-31 B.N. Kuznetsov, V.I. Sharypov, N.G. Beregovtsova, S.V. Baryshnikov, A.V. Pestunov, А.V. Vosmerikov, L. Djakovitch
Pyrolysis and combustion characteristics of corncob hydrolysis residue J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-01-31 Cui Quan, Zhengzhao Ma, Ningbo Gao, Chi He
Corncob hydrolysis residue (CHR) is a by-product of the furfural industry. In this paper, the thermal behavior of CHR was determined with the aim to promote its application as fuels or chemicals. Firstly, the pyrolysis and combustion of CHR in nitrogen and air, were respectively investigated by thermogravimetric analyzer coupled with Fourier transform infrared spectrometer (TG-FTIR). The TG and DTG (differential thermos-gravimetric) curves revealed that both the pyrolysis and combustion of CHR included three distinct stages. The main evolving gaseous products during pyrolysis were H2O, CH4, CO, CO2 and oxygenated compounds, while combustion yielded considerable amounts of CO2 in the temperature range of 345–500 °C. The presence of oxygen can increase the volatilization rate of organic matter in CHR and accelerate thermal decomposition of CHR. A total weight loss of 57.29 wt% and 77.53 wt% was observed for pyrolysis and combustion, respectively. The non-isothermal kinetic was used to analyze the activation energy (E) of combustion and pyrolysis processes. The E of CHR pyrolysis reaction is 135.45 kJ mol−1 in temperature of 200–500 °C, while under the combustion process the value of E is 121.57 kJ mol−1 and 135.45 kJ mol−1 in 200–345 °C and 345–500 °C temperature ranges, respectively. In addition to it, the types of products and their proportions in pyrolysis process of CHR were studied by Py-GC/MS and the results indicated that the oxygenated compound produced from CHR pyrolysis mainly included acids, aldehyde, phenolics and anhydrides.
Influence of temperature and particle size on structural characteristics of chars from Beechwood pyrolysis J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-01-31 Jie Yu, Lushi Sun, César Berrueco, Beatriz Fidalgo, Nigel Paterson, Marcos Millan
This work investigates the effect of temperature and particle size on the product yields and structure of chars obtained from the pyrolysis of Beechwood Chips (BWC), a lignocellulosic biomass. BWC of three different size fractions (0.21–0.50 mm, 0.85–1.70 mm and 2.06–3.15 mm) were pyrolyzed at atmospheric pressure and temperatures ranging from 300 to 900 °C in a fixed bed reactor. Tar and gas yields increased with increasing temperature, while char yield decreased, particularly between 300 and 450 °C. The effect of particle size was mostly observed at temperatures lower than 400 °C as a larger char yield for larger particles due to intraparticle reactions. At higher temperatures the larger surface area in the char fixed bed favoured reactions increasing char and gas yields from the smaller particles. Pyrolysis chars were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and Raman spectroscopy. Loss in oxygenated functional groups and aliphatic side chains with increasing temperature was revealed, along with an increase in the concentration of large aromatic systems, leading to a more ordered char structure but no significant graphitization. The changes in char nature at high temperature led to a loss in their combustion reactivity. Raman spectra indicated that the temperature needed to completely decompose the cellulose structure increased with biomass particle size and the enhanced intraparticle reactions in pyrolysis of large particles was likely to give rise to amorphous carbon structures with small fused ring systems.
Thermal decomposition mechanism and kinetics of gemcitabine J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-01 Chengjie Wu, Jinzong You, Xuejie Wang
Gemcitabine (GTB) is a nucleoside drug used in chemotherapy for various carcinomas. In order to know why does GTB have good thermal stability, and to further understand the relationship between thermal stability and molecular structure. The thermal decomposition of GTB was measured with various thermal analytical techniques, the gaseous products and the residues of thermal decomposition were determined and identified. The molecular bond orders were calculated. The thermal decomposition mechanism of GTB was discussed. The thermal decomposition kinetics and the prospective lifetime of GTB were studied using the ATSM method. The results indicated that two strong electronegative fluorine atoms on furan ring make the strong charge-transfer (CT) structure to be formed, this strong CT structure remarkably enhance the N-glycosidic bond and the weakest bond, and lead to higher thermal stability and distinctive thermal decomposition mechanism. The thermal decomposition of GTB is a three-stage process. The initial step of decomposition is likely due to the loss of a furan ring. Most of GTB decompose and carbonizes directly to form insoluble substance and small molecules and just part of GTB decompose by way of cytosine stage. The initial decomposition temperature in either nitrogen or air is 235 °C. For decomposition in nitrogen, the apparent activation energy Ea and pre-exponential factor A for the initial thermal decomposition are 123.4 kJ mol−1 and 3.80 × 1010 min−1, respectively. For decomposition in air, the corresponding Ea and A are 126.3 kJ mol−1 and 7.94 × 1010 min−1, respectively. GTB has very good thermal stability under routine temperature and dry air atmosphere.
The mechanisms and consequences of inorganic reactions during the production of ferrous sulphate enriched bamboo biochars J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-02-01 Ben Pace, Paul Munroe, Christopher E. Marjo, Paul Thomas, Bin Gong, Jessica Shepherd, Wolfram Buss, Stephen Joseph
Magnetic biochars are implicated in graphene micro-crystallite formation, soil redox processes and highly adsorbent chars. This study investigates the mechanisms of bamboo charring − when impregnated with FeSO4.7H2O − at 250, 350, 450 and 550 °C, using thermal and static techniques. Impregnation resulted in the oxidation of Fe2+ to mixed Fe3+/Fe2+ (magnetite) oxide forms during pyrolysis. A reaction sequence was proposed in which Fe-sulphates were incorporated with an ammonia catalyst. Sulphur became ubiquitous in both inorganic and organic forms, and additional minerals also formed. Stable aromatics and separation of holo-cellulosic and degraded lignin volatilisation phases were catalysed, and carboxylation was inhibited. Concentrations of C fluctuated more substantially, before stabilising at high HTTs. Pyrolysis temperatures of 450 °C and above appear to maximise stable C concentrations.These observations indicated that this treatment may yield agriculturally engineered chars with enhanced redox potential, more neutral pH, and a range of nutrients.
Study on the synthesis and thermal degradation of Vinylphenylpolysilsesquioxane J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-01-12 Liu Tao, Sun Chao, Ma Fengguo
Vinylphenylpolysilsesquioxane is synthesized through hydrolysis and condensation method, using phenyltrimethoxysilane and dimethylvinylethyoxysilane as raw materials. Its structure is confirmed by Fourier-transformed infrared (FTIR) and nuclear magnetic resonance (NMR) spectra. The degradation of vinylphenylpolysilsesquioxane under nitrogen atmosphere is investigated by thermal analysis techniques combined with infrared spectroscopy (TGA-FTIR) and TGA combined with gas chromatograph-mass spectrometer (TG-GC-MS). Its thermal degradation kinetics and thermal degradation mechanism is inferred from TGA under nitrogen atmosphere. In the light of these analyses, the degradation process is divided into two stages. In the first stage from 170 °C to 465 °C, the thermal degradation products are oligomer polysilsesquioxane, a little CO2 and H2O. Its thermal degradation mechanism is nucleation and growth process, its reaction order was 4. Its thermal degradation kinetics equation is d α d t = 3.25 × 10 17 ( 1 − α ) [ − ln ( 1 − α ) ] − 3 exp ( − 2.73 × 10 4 / T ) .In the second stage, the thermal degradation products are benzene and its derivatives. Its thermal degradation mechanism is nucleation and growth process, its reaction order was 4. Its thermal degradation kinetics equation is d α d t = 5.37 × 10 15 ( 1 − α ) [ − ln ( 1 − α ) ] − 3 exp ( − 3.60 × 10 4 / T ) .
Catalytic hydroliquefaction of rice straw for bio-oil production using Ni/CeO2 catalysts J. Anal. Appl. Pyrol. (IF 3.471) Pub Date : 2018-01-11 Dongdong Chen, Quanhong Ma, Lingfei Wei, Naixu Li, Quanhao Shen, Wei Tian, Jiancheng Zhou, Jieyu Long
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