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The article presents the results of a comparative analysis and experimental testing of the efficiency of technological processes for the processing of some types of alternative energy sources into fuel for transport engines. The accumulated research experience in the development of on-board conversion systems (reactors) of traditional motor fuels shows that the level of their technical and technological complexity is incomparable with the ecological and economic effect of their use in an RTS power plant. The high temperature level of the processing of these fuels necessitates the need for additional energy expenditure for the organization of the conversion process (for example, burning part of the fuel to support the necessary thermal regime of operation in thermochemical reactors), and the presence of sulfur compounds in motor fuel excludes the possibility of using highly efficient catalysts. In addition, the large relative content of inert (non-combustible) components in the composition of the target conversion products create additional difficulties when they are burned in the engine. In general, the choice of an acceptable alternative energy carrier as a raw product for the production of motor fuel is a compromise that takes into account its energy value, temperature conditions of conversion, the spectrum of gases formed during conversion, cost, availability of raw materials, the possibility of adaptation to the conditions of the RTS, etc. From the set of factors considered above, it can be concluded that today methanol is one of the most energetically beneficial sources of cheap and efficient hydrogen-containing fuel for RTS engines. It should be noted that in the future, in the world of technology development and the corresponding raw material bases, it may be economically justified to use other compounds, which, according to their characteristics, will be able to meet the energetically favorable conditions in the technological structure of the on-board conversion implementation. This will allow creating a stable fuel and energy base , which practically does not depend on the imported hydrocarbon fuel., У статті приводяться результати порівняльного аналізу та досвідченої апробації ефективності технологічних процесів по переробці деяких видів альтернативних енергоносіїв у паливо для транспортних двигунів. Накопичений дослідницький досвід в області розробок бортових систем конверсії (реакторів) традиційних моторних палив показує, що рівень їх технічної та технологічної складності непорівнянний с еколого-економічним ефектом від застосування в енергоустановці АТЗ. Високий температурний рівень процесу переробки цих палив обумовлює необхідність додаткових витрат енергії на організацію конверсійного процесу (наприклад, спалювання частини палива на підтримку необхідного теплового режиму роботи в термохімічних реакторах), а присутність з'єднань сірки в моторному паливі виключає можливість використання високоефективних каталізаторів. Крім того, великий відносний зміст інертних (негорючих) компонентів у складі цільових продуктів конверсії створюють додаткові складності при їх спалюванні у двигуні. У загальному виді, вибір прийнятного альтернативного носія енергії як сировинного продукту для виробництва моторного палива є компромісом, що враховують його енергетичну цінність, температурні умови конверсії, спектр газів, що утворюються при конверсії, вартість, наявність сировинної бази, можливість адаптації до умов АТЗ і ін. З комплексу розглянутих вище факторів можна зробити висновок про те, що на сьогоднішній день метанол є одним з найбільше енергетично вигідних джерел дешевого й ефективного водневмісного палива для двигунів АТЗ. Слід відмітити, що в майбутньому у світі розвитку технологій і відповідних сировинних баз може виявитися економічно виправданим використання й інших з'єднань, які за своїми характеристиками зможуть відповідати енергетично вигідним умовам у технологічній структурі реалізації бортової конверсії. Це дозволить створювати стійку паливно-енергетичну базу, що практично не залежить від вуглеводневого палива, що привозять.

The article considers the possibility of expanding the raw material base of the production of motor fuels, particularly the fuels for shipping due to the use of secondary polymer raw materials. It was established that this raw material, which is represented by various polyolefins, is characterized by the absence or rather low (up to 150–200 ppm) content of sulfur-containing compounds. Therefore, according to such an indicator as the sulfur content, using thermal or catalytic pyrolysis technologies in a reactor-type apparatus, it is possible to obtain fuels from secondary polymer raw materials, which in terms of sulfur content (0.5 % and 0.1 %, respectively) will correspond to marine gasoil (MGO) or low sulfur marine gasoil (LS-MGO). It was experimentally established that the products of thermal pyrolysis of secondary polymer raw materials contain up to 30–40 % of olefinic hydrocarbons, which have low chemical stability and increased hygroscopicity compared to paraffinic and naphthenic hydrocarbons. Given their properties, such products should only be used as components of marine fuels. The products of catalytic pyrolysis (the process was carried out using the ZSM-5 zeolite catalyst) of secondary polymer raw materials, on the contrary, have high chemical stability due to the low (up to 3 %) content of olefinic hydrocarbons. But, at the same time, they contain up to 15 % aromatic hydrocarbons in their composition, which does not exceed the generally accepted restrictions on their content in motor fuels. It has been determined that the initial boiling point of the obtained fractions is the main parameter, which can be used to regulate some quality indicators of the products obtained. Its increase significantly reduces hygroscopicity and increases the flash point of the obtained products. However, it is not advisable to significantly increase this indicator, given the decrease in the yield of the target product (increasing the boiling point of the fraction by only 1 °C leads to a decrease in its yield by 0.275–0.325 %)., В статті розглянуто можливість розширення сировинної бази процесу виробництва моторних палив, зокрема палив для судноплавства, за рахунок використання вторинної полімерної сировини. Встановлено, що дана сировина, яка представлена різними поліолефінами, характеризується відсутністю або досить низьким (до 150–200 ррm) вмістом сірковмісних сполук. Отже, за таким показником як вміст сірки, використовуючи технології термічного або каталітичного піролізу в апараті реакторного типу, з вторинної полімерної сировини можна отримати палива, які за вмістом сірки (0,5 % та 0,1 %, відповідно) будуть відповідати marine gasoil (MGO) або low sulfur marine gasoil (LS-MGO). Експериментально встановлено, що в продуктах термічного піролізу вторинної полімерної сировини міститься до 30–40 % олефінових вуглеводнів, які мають низьку хімічну стабільність та підвищену, у порівнянні з парафіновими та нафтеновими вуглеводнями, гігроскопічність. Такі продукти, з огляду на їх властивості, доцільно використовувати лише як компоненти морських палив. На відміну від цього, продукти каталітичного піролізу (процес відбувався з використанням цеолітного каталізатору ZSM-5) вторинної полімерної сировини навпаки, мають високу хімічну стабільність внаслідок низького (до 3 %) вмісту олефінових вуглеводнів. Але, при цьому, вони містять у своєму складі до 15 % ароматичних вуглеводнів, що не перевищує загально прийняті обмеження на їх вміст у моторних паливах. Визначено, що основним параметром, яким можна регулювати деякі показники якості отриманих продуктів, виступає температура початку кипіння отриманих фракцій. Її збільшення значно знижує гігроскопічність та підвищує температуру спалаху отриманих продуктів. Разом з тим, значно підвищувати цей показник не доцільно, з огляду на зниження виходу цільового продукту (збільшення температури початку кипіння фракції лише на 1 °С призводить до зниження її виходу на 0,275–0,325 %).

This study utilized pulp and paper mill sludge as a carbon source to produce activated biochar adsorbents. The response surface methodology (RSM) application for predicting and optimizing the activated biochar preparation conditions was investigated. Biochars were prepared based on a Box–Behnken design (BBD) approach with three independent factors (i.e., pyrolysis temperature, holding time, and KOH:biomass ratio), and the responses evaluated were specific surface area (SSA), micropore area (Smicro), and mesopore area (Smeso). According to the RSM and BBD analysis, a pyrolysis temperature of 800 °C for 3 h of holding and an impregnation ratio of 1:1 (biomass:KOH) are the optimum conditions for obtaining the highest SSA (885 m2 g–1). Maximized Smicro was reached at 800 °C, 1 h and the ratio of 1:1, and for maximizing Smeso (569.16 m2 g–1), 800 °C, 2 h and ratio 1:1.5 (445–473 m2 g–1) were employed. The biochars presented different micro- and mesoporosity characteristics depending on pyrolysis conditions. Elemental analysis showed that biochars exhibited high carbon and oxygen content. Raman analysis indicated that all biochars had disordered carbon structures with structural defects, which can boost their properties, e.g., by improving their adsorption performances. The hydrophobicity–hydrophilicity experiments showed very hydrophobic biochar surfaces. The biochars were used as adsorbents for diclofenac and amoxicillin. They presented very high adsorption performances, which could be explained by the pore filling, hydrophobic surface, and π–π electron–donor–acceptor interactions between aromatic rings of both adsorbent and adsorbate. The biochar with the highest surface area (and highest uptake performance) was subjected to regeneration tests, showing that it can be reused multiple times. peerReviewed

Producing pyrolytic oil via pyrolysis reaction from waste papers containing melamine formaldehyde and urea formaldehyde, which have an economic and environmental value, is the base of this study. In this study gas, liquid and solid products were gained via pyrolysis, and liquid products are put into perspective from the point of energy. In this pilot study, positive results were obtained for comprehensive further experiments, and it?s seen that the results may have meaningful value on sectoral basis with regards to reducing environmental damages of the wastes and energy producing.

The fundamentals of pyrolysis, its latest developments, the different conditions of the process and their relative residues are of great importance to evaluate the applicability of the pyrolysis process within the waste management sector and waste treatments. In particular the type of residues and their further use or treatment is of extreme interest as they could become the source of secondary raw material or generate beneficial influence in waste treatments. The main area of focus of this paper is the investigation of the link between the pyrolysis conditions, the chemical and mineralogical composition of their products and the benefits of pyrolysis in the waste management sector. More specific the paper covers the fast, intermediate and slow pyrolysis of organic and a mixture of inorganic/organic charge from households. The catalysts influence during fast pyrolysis on products yields and composition is not being considered in the review.

The wide occurrence of pharmaceuticals in aquatic environments urges the development of cost-effective solutions for their removal from water. In a circular economy context, primary paper mill sludge (PS) was used to produce activated carbon (AC) aiming the adsorptive removal of these contaminants. The use of low-cost precursors for the preparation of ACs capable of competing with commercial ACs continues to be a challenge. A full factorial design of four factors (pyrolysis temperature, residence time, precursor/activating agent ratio, and type of activating agent) at two levels was applied to the production of AC using PS as precursor. The responses analysed were the yield of production, percentage of adsorption for three pharmaceuticals (sulfamethoxazole, carbamazepine, and paroxetine), specific surface area (S ), and total organic carbon (TOC). Statistical analysis was performed to evaluate influencing factors in the responses and to determine the most favourable production conditions. Four ACs presented very good responses, namely on the adsorption of the pharmaceuticals under study (average adsorption percentage around 78%, which is above that of commercial AC), and S between 1389 and 1627 m g . A desirability analysis pointed out 800 °C for 60 min and a precursor/KOH ratio of 1:1 (w/w) as the optimal production conditions., This work was funded by FEDER through COMPETE 2020 and by national funds through FCT by the research project PTDC/AAG-TEC/ 1762/2014. Thanks are also due for the financial support to CESAM (UID/AMB/50017-POCI-01-0145-FEDER-007638), to FCT/MCTES through national funds (PIDDAC), and the co-funding by the FEDER, within the PT2020 Partnership Agreement and Compete 2020. The work was also developed within the scope of the project CICECO - Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (UID/ CTM/50011/2013), financed by national funds through the FCT/MEC. Vânia Calisto also thanks FCT for her postdoctoral grant (SFRH/BPD/ 78645/2011). Marta Otero and Sérgio Santos thank support by the FCT Investigator Program (IF/00314/2015 and IF/00973/2014, respectively).

Осуществлен учет бумажных отходов в отдельных образовательных структурных подразделениях Кыргызско-Турецкого университета «Манас» (инженерный и естественно-научный факультеты: 760 студентов и 90 человек профессорско-преподавательский состав и административный персонал). Показано, что в течение шести месяцев текущего учебного года собрано 190 кг макулатурной бумаги, и в дальнейшем они возращены для повторного использования, после чего предусмотрен пиролиз при низких (773 К), средних (1073 К) и высоких (1173 К) температурах. Установлена химическая матрица макулатурной бумаги, которая состоит из 70 % целлюлозы, 3,5 % клея, 10 % каолина, 4 % крахмала, смесей 0,5 полигексаметиленгуанидина и 0,5 % диметил-бензилалкиламмония и 11,5 % воды, и составлена химическая формула бумаги: (C6H10O5 70) + + (CCOOH 3,5) + (Al2O3Si2O4H4O2 10) + H 4) + (CyHN 0,5) + + (CH3CH3CH2C6H5NCI 0,5) + (H2O 11,5). Элементный состав бумаги включает (моль/кг): C 30,209, H 64,339, O 32,921, Al 0,775, Si 0,775, N 0,136, Cl 0,029. Осуществлены расчеты при максимуме энтропии системы (давление 0,1 МПа). Определены физико-химические и термодинамические параметры, а также равновесные концентрации низкомолекулярных компонентов и частиц, образующихся при пиролизе макулатурной бумаги. Установлено, что при деструкции бумаги образуются токсичные хлор и азотсодержащие компоненты и частицы типа: Cl, CH3Cl, HClCO, AlCl3, HCl, C2HCl, AlOHCl, ClCO, C2H3Cl, AlCl, AlOHCl2, CH2C, C2H5Cl, AlCl2, NH3, C3HN, C2N2, C5HN, N2, HCN, N2C, NH2, HNC, ClCN; а также образуются простые и сложные углеводороды: метан CH4, этан C2H6, пропан C3H8 этилен C2H4, ацетилен C2H2, муравьиный альдегид CH2O, бензол C6H6. С увеличением температуры процесса пиролиза содержание конденсированного углерода (сажи) в газовой фазе уменьшается, т.е. идет интенсивная газификация (H2, СО) с выгоранием сажи при участии воды. Концентрация диоксида углерода и метана в газовой фазе с увеличением температуры процесса пиролиза бумаги уменьшается, The paper waste was recorded in separate educational departments of Kyrgyz-Turkish University Manas (engineering and natural science faculties: 760 students and 90 teaching staff and administrative staff). It is shown that within six months of the current academic year, 190 kg of recycled paper was collected, and later they were returned for reuse; after the reuse, pyrolysis is provided at low (773 K), medium (1073 K) and high (1173 K) temperatures. In view of the tasks, a common chemical matrix of recycled paper was established, which consists of 70 % cellulose, 3.5 % glue, 10 % kaolin, 4 % starch, a mixture of 0.5 % poly-hexamethyleneguanidine and 0.5 % dimethylbenzylalkylammonium and 11,5 % water, i.e. the paper’s chemical formula was compiled: (C6H10O5 70) + (C19H29COOH 3.5) + (Al2O3Si2O4H4O2 10) + + (C6H10O5 4) + (C7H15N3 0.5) + (CH3CH3CH2C6H5NCl 0.5) + (H2O 11.5). The elemental composition includes (mol / kg): C 30.209, H 64.339, O 32.921, Al 0.775, Si 0.775, N 0.136, Cl 0.029. The calculations were performed at the maximum entropy of the system (pressure 0.1 MPa). The physical-chemical and thermodynamic parameters, as well as the equilibrium concentrations of low molecular weight components and particles formed during the pyrolysis of waste paper, are determined. It has been established that the destruction of paper produces toxic chlorine and nitrogen-containing components and particles of the following types: Cl, CH3O, HClCO, АЮ3, HCl, C2HO, AlOHCl, ClCO, C2H3Cl, AlCl, AlOHCl2, CH2C, C2H5Cl, AlCl2, NH3, C3HN, C2N2, C5HN, N2, HCN, N2C, NH2, HNC, ClCN; and simple and complex hydrocarbons are formed: methane CH4, ethane C2H6, propane C3H8, ethylene C2H4, acetylene C2H2, formic aldehyde CH2O, benzene CgHg. With an increase in the temperature of the pyrolysis process, the amount of condensed carbon (soot) decreases, i.e. intensive gasification (H2, CO) and burnout of soot involving water take place. The concentration of carbon dioxide and methane in the gas phase decreases with increasing temperature of the pyrolysis process of paper.

International audience; We report a pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) method capable of analyzing traditional East Asian papers. The method proposed is based on rapid and easy single step Py-GC/MS analysis that can be carried out with a minimum amount of matter, in the few g range. Three reference papers manufactured from kozo (Broussonetia kazinoki Siebold & Zucc.), mitsumata (Edgeworthia chrysantha Lindl.) and gampi (Wikstroemia sikokiana Franch. & Sav.) with the traditional hand paper making processes were examined. The method allows discrimination between terpenic and steroid compounds, which were revealed as chemical markers of origin of the plant fibers. Each paper investigated was found to have characteristic pyrolysis fingerprints that were unique to the traditional handmade paper, demonstrating the potential for differentiation of these biochemical components of fiber plants on East Asian papers towards identification and conservation of cultural heritage. The investigation on Py-GC/MS was extended to liquid extraction followed by GC/MS analysis to characterize the biochemical components of fiber plants. The main contribution of this study is to provide molecular criteria for discriminating plant species used for traditional East Asian hand papermaking. Py-GC/MS complements efficiently microscope identification especially for adverse cases. A case study of archaeological Chinese paper painting artefacts was thereafter successfully investigated to address informative potential and efficiency of the criteria of identification on ancient and degraded East Asian paperworks.

Biochar microparticles were prepared from three different types of biochar, derived from waste materials, such as pine wood (BC-PW), pig manure (BC-PM) and cardboard (BC-PD) under various pyrolysis conditions. The microparticles were prepared by dry grinding and sequential sieving through various ASTM sieves. Particle size and specific surface area were analyzed using laser particle size analyzer. The particles were further characterized using scanning electron microscope (SEM). The adsorption capacity of each class of adsorbent was determined by methylene blue adsorption tests in comparison with commercially available activated carbon. Experimental results showed that dye adsorption increased with initial concentration of the adsorbate and biochar dosage. Biochar microparticles prepared from different sources exhibited improvement in adsorption capacity (7.8±0.5 mg g(-1) to 25±1.3 mg g(-1)) in comparison with raw biochar and commercially available activated carbon. The adsorption capacity varied with source material and method of production of biochar. The maximum adsorption capacity was 25 mg g(-1) for BC-PM microparticles at 25°C for an adsorbate concentration of 500 mg L(-1) in comparison with 48.30±3.6 mg g(-1) for activated carbon. The equilibrium adsorption data were best described by Langmuir model for BC-PM and BC-PD and Freundlich model for BC-PW.

This article details the study of electrochemical behavior of new carbon electrodes based on pyrolysis of different paper sources to be used in biosensor applications. The resistivity of the pyrolyzed papers was initially used as screening parameters to select the best three paper samples (imaging card paper, multipurpose printing paper, and 3MM chromatography paper) and assemble working electrodes that were further characterized by a combination of microscopy, electrochemistry, and spectroscopy. Although slight differences in performance were observed, all carbon substrates fabricated from pyrolysis of paper allowed the development of competitive biosensors for uric acid. The presented results demonstrate the potential of these electrodes for sensing applications and highlight the potential advantages of 3MM chromatography paper as a substrate to fabricate electrodes by pyrolysis. Fil: Giuliani, Jason G.. University of Texas; Estados Unidos Fil: Benavidez, Tomás Enrique. Clemson University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Duran, Gema M.. Universidad de Castilla-La Mancha; España Fil: Vinogradova, Ekaterina. University of Texas; Estados Unidos Fil: Rios, Angel. Universidad de Castilla-La Mancha; España Fil: Garcia, Carlos D.. Clemson University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina

Carbon-based aerogel fabricated from waste biomass is a potential absorbent material for solving organic pollution. Herein, the lightweight, hydrophobic and porous carbon aerogels (CAs) have been synthesized through freezing-drying and post-pyrolysis by using waste newspaper as the only raw materials. The as-prepared CAs exhibited a low density of 18.5 mg cm(-3) and excellent hydrophobicity with a water contact angle of 132° and selective absorption for organic reagents. The absorption capacity of CA for organic compounds can be 29-51 times its own weight. Moreover, three methods (e.g., squeezing, combustion, and distillation) can be employed to recycle CA and harvest organic pollutants. Combined with waste biomass as raw materials, green and facile fabrication process, excellent hydrophobicity and oleophilicity, CA used as an absorbent material has great potential in application of organic pollutant solvents absorption and environmental protection.

Pulp and paper industry produces massive amounts of sludge from wastewater treatment, which constitute an enormous environmental challenge. A possible management option is the conversion of sludge into carbon-based adsorbents to be applied in water remediation. For such utilization it is important to investigate if sludge is a consistent raw material originating reproducible final materials (either over time or from different manufacturing processes), which is the main goal of this work. For that purpose, different primary (PS) and biological sludge (BS) batches from two factories with different operation modes were sampled and subjected to pyrolysis (P materials) and to pyrolysis followed by acid washing (PW materials). All the materials were characterized by proximate analysis, total organic carbon (TOC) and inorganic carbon (IC), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and N2 adsorption isotherms (specific surface area (SBET)and porosity determination). Sludge from the two factories proved to have distinct physicochemical properties, mainly in what concerns IC. After pyrolysis, the washing step was essential to reduce IC and to considerably increase SBET, yet with high impact in the final production yield. Among the materials here produced, PW materials from PS were those having the highest SBET values (387-488 m2 g-1). Overall, it was found that precursors from different factories might originate final materials with distinct characteristics, being essential to take into account this source of variability when considering paper mill sludge as a raw material. Nevertheless, for PS, low variability was found between batches, which points out to the reliability of such residues to be used as precursors of carbon adsorbents. L'Oreal Portugal published

The fundamentals of pyrolysis, its latest developments, the different conditions of the process and its residues are of great importance in evaluating the applicability of the pyrolysis process within the waste management sector and in waste treatment. In particular the types of residue and their further use or treatment is of extreme interest as they could become the source of secondary raw materials or be used for energy generation in waste treatments. The main area of focus of this paper is the investigation of the link between the pyrolysis conditions, the chemical and mineralogical composition of their products and the benefits of pyrolysis in the waste management sector. More specifically the paper covers the fast, intermediate and slow pyrolysis of organic waste and mixtures of inorganic and organic waste from households. The influence of catalysts during fast pyrolysis on the product yield and composition is not being considered in this review. This reported work was conducted as part of the “Design Optimisation of the HERU Waste Treatment System” project in Brunel University London that was funded by Manik Ventures Limited.

This work describes the production of alternative adsorbents from industrial residues and their application for the removal of a highly consumed antidepressant (citalopram) from water. The adsorbents were produced by pyrolysis of both primary and biological paper mill sludge at different temperatures and residence times. The original sludge and the produced chars were fully characterized by elemental and proximate analyses, total organic carbon, specific surface area (BET), N-2 isotherms, FTIR, C-13 and H-1 solid state NMR and SEM. Batch kinetic and equilibrium experiments were carried out to describe the adsorption of citalopram onto the produced materials. The fastest kinetics and the highest adsorption capacity were obtained using primary sludge pyrolysed at 800 degrees C during 150 min. The use of pyrolysed paper mill sludge for the remediation of contaminated waters might constitute an interesting application for the valorization of those wastes. (C) 2014 Elsevier Ltd. All rights reserved.

Pyrolysis and steam gasification of woody biomass chip (WBC) obtained from construction and demolition wastes, refuse-derived fuel (RDF), and refuse paper and plastic fuel (RPF) were performed at various temperatures using a lab-scale instrument. The gas, liquid, and solid products were examined to determine their generation amounts, properties, and the carbon balance between raw material and products. The amount of product gas and its hydrogen concentration showed a considerable difference depending on pyrolysis and steam gasification at higher temperature. The reaction of steam and solid product, char, contributed to an increase in gas amount and hydrogen concentration. The amount of liquid products generated greatly depended on temperature rather than pyrolysis or steam gasification. The compositions of liquid product varied relying on raw materials used at 500 °C but the polycyclic aromatic hydrocarbons became the major compounds at 900 °C irrespective of the raw materials used. Almost fixed carbon (FC) of raw materials remained as solid products under pyrolysis condition whereas FC started to decompose at 700 °C under steam gasification condition. For WBC, both char utilization by pyrolysis at low temperature (500 °C) and syngas recovery by steam gasification at higher temperature (900 °C) might be practical options. From the results of carbon balance of RDF and RPF, it was confirmed that the carbon conversion to liquid products conspicuously increased as the amount of plastic increased in the raw material. To recover feedstock from RPF, pyrolysis for oil recovery at low temperature (500 °C) might be one of viable options. Steam gasification at 900 °C could be an option but the method of tar reforming (e.g. catalyst utilization) should be considered.

Aim of the study was to investigate how hydrothermal carbonization changes adsorption efficiency toward metal ions of typical sludges. Hydrothermal carbonization is a novel and green method of treating biomasses. Reactions take place in an aqueous environment at relatively mild temperature and high pressure resulting a different end biomass structure than obtained from traditional pyrolysis. Anaerobically digested sludge (ADS) and pulp and paper industry sludge (INS) were utilized as a feedstock. Adsorption behavior of ADS and INS was examined towards Pb(II), Cr(III), Cr(VI), As(III) and As(V). Both ADS and INS were found to remove Pb(II) effectively and followed Sips adsorption isotherm. Adsorption kinetics was fast and followed pseudo-second order model. Furthermore, intraparticle diffusion was observed to be partly responsible in the adsorption process. Hydrothermal carbonization indicated high potential for the production of novel carbonaceous materials for metal removal from waters.

Structural characteristics of benzene-ethanol-extracted lignin (BEL) and acetone-extracted lignin (AL) precipitated from black liquor were identified by elemental analysis, FTIR, (13)C NMR, and (1)H NMR, while the thermal behaviors were examined with thermogravimetric-Fourier transform infrared spectroscopy (TG-FTIR). The frequency of β-O-4 bonds per 100 C9 monomeric units was 28 and 17 for BEL and AL. Two-stage pyrolysis processes were observed for the two lignins. The mass loss rate of the initial solvent evolution stage (110-180 °C) of BEL was greater than that of AL. The two lignins presented slightly different mass loss curves and evolution profiles of gases in the main pyrolysis stage (280-500 °C). A global kinetic model was proposed for lignin pyrolysis and activation energies of 39.5 and 38.8 kJ/mol was obtained for BEL and AL. The results enhance understanding of lignin pyrolysis and facilitate commercial utilization of black-liquor lignin.

By using thermogravimetric analysis (TGA), the effects of different additives (MgO, Al2O3 and ZnO) on the pyrolysis characteristics and activation energy of municipal solid waste (MSW), paper sludge (PS) and their blends in N2 atmosphere had been investigated in this study. The experiments resulted that these additives were effective in reducing the initial temperature and activation energy. However, not all the additives were beneficial to reduce the residue mass and enhance the index D. For the different ratios of MSW and PS, the same additive even had the different influences. The catalytic effects of additives were not obvious and the pyrolysis became difficult with the increase of the proportion of PS. Based on all the contrast of the pyrolysis characteristics, MgO was the best additive and 70M30P was the best ratio, respectively.

Eucalyptus globulus sapwood and heartwood showed no differences in lignin content (23.0% vs. 23.7%) and composition: syringyl-lignin (17.9% vs. 18.0%) and guaiacyl-lignin (4.8% vs. 5.2%). Delignification kinetics of S- and G-units in heartwood and sapwood was investigated by Py-GC–MS/FID at 130, 150 and 170 °C and modeled as double first-order reactions. Reactivity differences between S and G-units were small during the main pulping phase and the higher reactivity of S over G units was better expressed in the later pulping stage. The residual lignin composition in pulps was different from wood or from samples in the initial delignification stages, with more G and H-units. S/G ratio ranged from 3 to 4.5 when pulp residual lignin was higher than 10%, decreasing rapidly to less than 1. The S/H was initially around 20 (until 15% residual lignin), decreasing to 4 when residual lignin was about 3%.

In the present study the interactions between the main constituents of the refuse derived fuel (plastics, paper, and wood) during pyrolysis were studied. Binary mixtures of polyethylene-paper and polyethylene/sawdust have been transformed into pellets and pyrolyzed. Various mixtures with different composition were analyzed and pyrolysis products (tar, gas, and char) were collected. The mixtures of wood/PE and paper/PE have a different behavior. The wood/PE mixtures showed a much reduced interaction of the various compounds because the yields of pyrolysis products of the mixture can be predicted as linear combination of those of the pure components. On the contrary, a strong char yield increase was found at a low heating rate for paper/PE mixtures. In order to explain the results, the ability of wood and paper char to adsorb and convert the products of PE pyrolysis into was studied. Adsorption and desorption tests were performed on the char obtained by paper and wood by using n-hexadecane as a model compound for the heavy products of PE pyrolysis.

Hesperaloe funifera was characterizedin terms of its contents of holocellulose, α-cellulose, and lignin (74.1, 52.3, and 7.9%, respectively). Also, an experimental factor design was used to examine the influence of operational variables in the diethanolamine pulping of this material (viz. diethanolamine concentration (50-80%), cooking temperature (155-185 ºC), and time (30-90 minutes)) on the contents of holocellulose, α-cellulose, and lignin, as well as the yield, kappa number, and viscosity of the resulting pulps, and also on the brightness, tensile index, stretch, burst index, and tear index of paper sheets made from it. The predictions for these dependent variables departed by less than 1, 7, 6, 2, 2, 4, 15, 11, 12, 10, and 37% from their respective experimental values. Black liquors obtained from the pulping runs were characterized by determining pH, density, TDS, (total dissolved solids), MI (inorganic matter), MO (organic matter), and lignin content; lignin samples were characterized by different techniques (FTIR and TGA). Finally, the black liquors were acidified to separate solid fractions that were subjected to pyrolysis and gasification in order to obtain synthesis and fuel gases.

This work seeks the integral use of all major components of Hesperaloe funifera , separating hemicelluose by hydrothermal treatments; cellulose by pulping processes; and exploitation of lignin of pulping liquor by pyrolysis and gasification processes. By using sulfuric acid in the hydrothermal treatment (150–190 °C, 0–20 min after reaching operating temperature, 6–10 liquid/solid ratio, 0.1–0.5% sulfuric acid), the glucose and xylose of liquid fraction increase from 1.5% to 5.9%, and 4.0% to 12.4%, respectively; the yields of solid fraction decrease from 91.6% to 79.5%, and the lignin content increase from 23% to 32%. Pulps and paper sheets obtained from solid fractions hydrothermal treatments and from raw material pulped with diethanolamine, are worse than those obtained with soda–anthraquinone (Yield 57.8%; kappa number 24.9; Viscosity 711 mL/g; Brightness 54.8%; Tensile index 73.6 Nm/g; Stretch 2.84%; Burst index 6.13 kN/g and Tear index 1.69 mNm 2 /g). By acidification (pH 6) of soda pulping liquor it separate lignin-rich solids, which by pyrolysis gave a gas containing 1.13% H 2 , 31.79% CO and 1.86% CH 4 by weight. Gasification of the same sample provided a gas containing 0.18% H 2 , 24.50% CO and 17.75% CH 4 .

Lignin is a key component in the biomass with a complex polymeric structure of the phenyl-C(3) alkyl units. The kraft lignin from the wood pulping process is tested in TG-FTIR and Py-GC-MS. The samples are pyrolyzed in TGA coupled with FTIR from 30 to 900 degrees C at the heating rate of 20 and 40K/min. The evolution of phenolic compounds in the initial pyrolysis stage of lignin is determined by FTIR, while the second stage is mainly attributed to the production of the low molecular weight species. A bench-scale fast pyrolysis unit is employed to investigate the effect of temperature on the product yield and composition. It is found that the guaiacol-type and syringol-type compounds as the primary products of lignin pyrolysis are predominant in bio-oil, acting as the significant precursors for the formation of the derivatives such as the phenol-, cresol- and catechol-types. A series of free-radical chain-reactions, concerning the cracking of different side-chain structures and the methoxy groups on aromatic ring, are proposed to demonstrate the formation pathways for the typical compounds in bio-oil by closely relating lignin structure to the pyrolytic mechanisms. The methoxy group (-OCH(3)) is suggested to work as an important source for the formation of the small volatile species (CO, CO(2) and CH(4)) through the relevant free radical coupling reactions.

The thermogravimetric and calorimetric characteristics during pyrolysis of wood, paper, textile and polyethylene terephthalate (PET) plastic in municipal solid wastes (MSW), and co-pyrolysis of biomass-derived and plastic components with and without torrefaction were investigated. The active pyrolysis of the PET plastic occurred at a much higher temperature range between 360 °C and 480 °C than 220–380 °C for the biomass derived components. The plastic pyrolyzed at a heating rate of 10 °C/min had the highest maximum weight loss rate of 18.5 wt%/min occurred at 420 °C, followed by 10.8 wt%/min at 340 °C for both paper and textile, and 9.9 wt%/min at 360 °C for wood. At the end of the active pyrolysis stage, the final mass of paper, wood, textile and PET was 28.77%, 26.78%, 21.62% and 18.31%, respectively. During pyrolysis of individual MSW components at 500 °C, the wood required the least amount of heat at 665.2 J/g, compared to 2483.2 J/g for textile, 2059.4 J/g for paper and 2256.1 J/g for PET plastic. The PET plastic had much higher activation energy of 181.86 kJ/mol, compared to 41.47 kJ/mol for wood, 50.01 kJ/mol for paper and 36.65 kJ/mol for textile during pyrolysis at a heating rate of 10 °C/min. H2O and H2 peaks were observed on the MS curves for the pyrolysis of three biomass-derived materials but there was no obvious H2O and H2 peaks on the MS curves of PET plastic. There was a significant interaction between biomass and PET plastic during co-pyrolysis if the biomass fraction was dominant. The amount of heat required for the co-pyrolysis of the biomass and plastic mixture increased with the increase of plastic mass fraction in the mixture. Torrefaction at a proper temperature and time could improve the grindability of PET plastic. The increase of torrefaction temperature and time did not affect the temperature where the maximum pyrolytic rates occurred for both biomass and plastic but decreased the maximum pyrolysis rate of biomass and increased the maximum pyrolysis rate of PET plastic. The amount of heat for the pyrolysis of biomass and PET mixture co-torrefied at 280 °C for 30 min was 4365 J/g at 500 °C, compared to 1138 J/g for the pyrolysis of raw 50% wood and 50% PET mixture at the same condition.

The polycyclic aromatic hydrocarbons (PAHs) toxicity and sorption behaviour of biochars prepared from pyrolysis of paper mill effluent treatment plant (ETP) sludge in temperature range 200–700 °C was studied. The sorption behaviour was found to depend on the degree of carbonization where the fractions of carbonized and uncarbonized organic content in the biochar act as an adsorption media and partition media, respectively. The sorption and partition fractions were quantified by isotherm separation method and isotherm parameters were correlated with biochar properties (aromaticity, polarity, surface area, pore volume and ash content). The risk assessment for the 16 priority EPA PAHs present in the biochar matrix was performed and it was found that the concentrations of the PAHs in the biochar were within the permissible limits prescribed by US EPA (except BC400 and BC500 for high molecular weight PAHs).

The production of paper pulp by the Kraft method generates considerable amounts of wastes. Namely, lime mud generated in the recovery circuit of chemical reagents, biological sludge from the wastewater treatment of wood digestion process and fly ash collected in the fluidized bed combustor used to generate electricity from biomass burning. The final destination of such wastes is an important concern, since environmental regulations are becoming stricter regarding their landfill. Driven by this fact, industries are looking for more sustainable solutions, such as the recycling in distinct products. This work tested these wastes as secondary raw materials to produce clinker/cement that was then experienced in mortar formulations. The first step involved the residues detailed characterization and a generated amounts survey. Then, specific but simple steps were suggested, aiming to facilitate transport and manipulation. Distinct blends were prepared and fired in order to get belitic and Portland clinkers. The Portland clinkers were processed at lower temperatures than the normally used in the industry due to the presence of mineralizing impurities in some wastes. Belite-based cements were used to produce mortars that developed satisfactory mechanical strength and did not reveal signs of deterioration or durability weaknesses. (C) 2014 Elsevier B.V. All rights reserved.

This chapter is aimed to thoroughly describe the thermal degradation of cellulose and cellulosic substrates (like cotton and paper), investigating the involved reaction mechanisms. After a brief introduction about the real reasons that motivated the study on cellulose degradation, a first general introduction on cellulose thermal degradation (namely, pyrolysis) and thermooxidation will be presented, followed by a detailed description of the related mechanisms with particular attention to the main degradation products consisting of volatile species and char (carbonaceous residue). To this aim, some of the most important factors affecting the volatilisation and charring balance (i.e. heating rate, presence of humidity, metals and flame retardants) are considered and thoroughly discussed in order to provide a complete scenario about the cellulose degradation phenomenon

The application of low-temperature pyrolysis mass spectrometry to the identification of some commercial and synthetic polymers using a direct insertion probe and electron ionization has been studied. The polymers were analyzed directly in the solid probe of a mass spectrometer within the ion source at 70 eV electron impact. The quadrupole mass spectrometer, equipped with gas chromatogram software and a library of low molecular weight compounds, was used to characterize the polymers by measuring the chemical structure of the repeat units and the end groups and to examine the thermal degradation pathways. The polymers investigated show different degradation pathways. Investigation of sequences and determination of the composition of co-polymers were studied. Total ion pyrogram and spectrum subtractions were used to separate and measure spectra of pyrolysis steps at distinctly different temperatures.

This study aims to underline the huge potential in Canada of adding value to cardboard and compost as a renewable fuel with a low ecological footprint. The slow pyrolysis process of lined cardboard and compost blend was investigated. Thermal behavior was investigated by thermogravimetric analysis coupled with mass spectrometry (TGA-MS). The thermal profiles are presented in the form of TGA/DTG curves. With a constant heating rate of 10 °C/min, two parameters, temperature and time were varied. Cardboard decomposition occurred mostly between 203 °C and 436 °C, where 77% of the sample weight was decomposed. Compost blend decomposition occurred mostly between 209 °C and 373 °C, with 23% of weight. The principal gaseous products that evolved during the pyrolysis were H2O, CO and CO2. As a result, slow pyrolysis led to the formation of biochar. High yield of biochar from cardboard was found at 250 °C for a duration of 60 min (87.5%) while the biochar yield from the compost blend was maintained constant at about 31%. Finally, kinetic parameters and a statistical analysis for the pyrolysis process of the cardboard and compost samples have been investigated. Both materials showed a favorable thermochemical behavior. However, unlike cardboard, compost pyrolysis does not seem a promising process because of the low superior calorific and biochar values.

The risk analysis was performed to study the bioavailability and eco-toxicity of heavy metals in biochar obtained from pyrolysis of sludge of pulp and paper mill effluent treatment plant. The sludge was pyrolyzed at different temperatures (200-700°C) and the resultant biochar were analyzed for fractionation of heavy metals by sequential extraction procedure. It was observed that all the heavy metals get enriched in biochar matrix after pyrolysis, but the bioavailability and eco-toxicity of the heavy metals in biochar were significantly reduced as the mobile and bioavailable heavy metal fractions were transformed into the relatively stable fractions. Moreover, it was observed that the leaching potential of heavy metals decreased after pyrolysis and the best results were obtained for biochar pyrolyzed at 700°C.

The paper-making process can produce large amounts of wastewater (WW) with high particulate and dissolved organic loads. Generally, in developed countries, stringent international regulations for environmental protection require pulp and paper mill WW to be treated to reduce the organic load prior to discharge into the receiving environment. This can be achieved by primary and secondary treatments involving both chemical and biological processes. These processes result in complex changes in the nature of the organic material, as some components are mineralised and others are transformed. In this study, changes in the nature of organics through different stages of secondary treatment of pulp and paper mill WW were followed using three advanced characterisation techniques: solid-state 13C nuclear magnetic resonance (NMR) spectroscopy, pyrolysis-gas chromatography mass spectrometry (py-GCMS) and high-performance size-exclusion chromatography (HPSEC). Each technique provided a different perspective on the changes that occurred. To compare the different chemical perspectives in terms of the degree of similarity/difference between samples, we employed non-metric multidimensional scaling. Results indicate that NMR and HPSEC provided strongly correlated perspectives, with 86 % of the discrimination between the organic samples common to both techniques. Conversely, py-GCMS was found to provide a unique, and thus complementary, perspective. Refereed/Peer-reviewed