Fast pyrolysis and nitrogenolysis of biomass and biogenic residues:production of a sustainable slow release fertiliser

The production of agricultural and horticultural products requires the use of nitrogenous fertiliser that can cause pollution of surface and ground water and has a large carbon footprint as it is mainly produced from fossil fuels. The overall objective of this research project was to investigate fast pyrolysis and in-situ nitrogenolysis of biomass and biogenic residues as an alternative route to produce a sustainable solid slow release fertiliser mitigating the above stated problems. A variety of biomasses and biogenic residues were characterized by proximate analysis, ultimate analysis, thermogravimetric analysis (TGA) and Pyrolysis – Gas chromatography – Mass Spectroscopy (Py–GC–MS) for their potential use as feedstocks using beech wood as a reference material. Beech wood was virtually nitrogen free and therefore suitable as a reference material as added nitrogen can be identified as such while Dried Distillers Grains with Solubles (DDGS) and rape meal had a nitrogen content between 5.5wt.% and 6.1wt.% qualifying them as high nitrogen feedstocks. Fast pyrolysis and in-situ nitrogenolysis experiments were carried out in a continuously fed 1kg/h bubbling fluidized bed reactor at around 500°C quenching the pyrolysis vapours with isoparaffin. In-situ nitrogenolysis experiments were performed by adding ammonia gas to the fast pyrolysis reactor at nominal nitrogen addition rates between 5wt.%C and 20wt.%C based on the dry feedstock’s carbon content basis. Mass balances were established for the processing experiments. The fast pyrolysis and in-situ nitrogenolysis products were characterized by proximate analysis, ultimate analysis and GC– MS. High liquid yields and good mass balance closures of over 92% were obtained. The most suitable nitrogen addition rate for the in-situ nitrogenolysis experiments was determined to be 12wt.%C on dry feedstock carbon content basis. However, only a few nitrogen compounds that were formed during in-situ nitrogenolysis could be identified by GC–MS. A batch reactor process was developed to thermally solidify the fast pyrolysis and in-situ nitrogenolysis liquids of beech wood and Barley DDGS producing a brittle solid product. This was obtained at 150°C with an addition of 2.5wt% char (as catalyst) after a processing time of 1h. The batch reactor was also used for modifying and solidifying fast pyrolysis liquids derived from beech wood by adding urea or ammonium phosphate as post processing nitrogenolysis. The results showed that this type of combined approach was not suitable to produce a slow release fertiliser, because the solid product contained up to 65wt.% of highly water soluble nitrogen compounds that would be released instantly by rain. To complement the processing experiments a comparative study via Py–GC–MS with inert and reactive gas was performed with cellulose, hemicellulose, lignin and beech wood. This revealed that the presence of ammonia gas during analytical pyrolysis did not appear to have any direct impact on the decomposition products of the tested materials. The chromatograms obtained showed almost no differences between inert and ammonia gas experiments indicating that the reaction between ammonia and pyrolysis vapours does not occur instantly. A comparative study via Fourier Transformed Infrared Spectroscopy of solidified fast pyrolysis and in-situ nitrogenolysis products showed that there were some alterations in the spectra obtained. A shift in frequencies indicating C=O stretches typically related to the presence of carboxylic acids to C=O stretches related to amides was observed and no double or triple bonded nitrogen was detected. This indicates that organic acids reacted with ammonia and that no potentially harmful or non-biodegradable triple bonded nitrogen compounds were formed. The impact of solid slow release fertiliser (SRF) derived from pyrolysis and in-situ nitrogenolysis products from beech wood and Barley DDGS on microbial life in soils and plant growth was tested in cooperation with Rothamsted Research. The microbial incubation tests indicated that microbes can thrive on the SRFs produced, although some microbial species seem to have a reduced activity at very high concentrations of beech wood and Barley DDGS derived SRF. The plant tests (pot trials) showed that the application of SRF derived from beech wood and barley DDGS had no negative impact on germination or plant growth of rye grass. The fertilizing effect was proven by the dry matter yields in three harvests after 47 days, 89 days and 131 days. The findings of this research indicate that in general a slow release fertiliser can be produced from biomass and biogenic residues by in-situ nitrogenolysis. Nevertheless the findings also show that additional research is necessary to identify which compounds are formed during this process

Fast pyrolysis and nitrogenolysis of biomass and biogenic residues : production of a sustainable slow release fertiliser

The production of agricultural and horticultural products requires the use of nitrogenous fertiliser that can cause pollution of surface and ground water and has a large carbon footprint as it is mainly produced from fossil fuels. The overall objective of this research project was to investigate fast pyrolysis and in-situ nitrogenolysis of biomass and biogenic residues as an alternative route to produce a sustainable solid slow release fertiliser mitigating the above stated problems. A variety of biomasses and biogenic residues were characterized by proximate analysis, ultimate analysis, thermogravimetric analysis (TGA) and Pyrolysis – Gas chromatography – Mass Spectroscopy (Py–GC–MS) for their potential use as feedstocks using beech wood as a reference material. Beech wood was virtually nitrogen free and therefore suitable as a reference material as added nitrogen can be identified as such while Dried Distillers Grains with Solubles (DDGS) and rape meal had a nitrogen content between 5.5wt.% and 6.1wt.% qualifying them as high nitrogen feedstocks. Fast pyrolysis and in-situ nitrogenolysis experiments were carried out in a continuously fed 1kg/h bubbling fluidized bed reactor at around 500°C quenching the pyrolysis vapours with isoparaffin. In-situ nitrogenolysis experiments were performed by adding ammonia gas to the fast pyrolysis reactor at nominal nitrogen addition rates between 5wt.%C and 20wt.%C based on the dry feedstock’s carbon content basis. Mass balances were established for the processing experiments. The fast pyrolysis and in-situ nitrogenolysis products were characterized by proximate analysis, ultimate analysis and GC– MS. High liquid yields and good mass balance closures of over 92% were obtained. The most suitable nitrogen addition rate for the in-situ nitrogenolysis experiments was determined to be 12wt.%C on dry feedstock carbon content basis. However, only a few nitrogen compounds that were formed during in-situ nitrogenolysis could be identified by GC–MS. A batch reactor process was developed to thermally solidify the fast pyrolysis and in-situ nitrogenolysis liquids of beech wood and Barley DDGS producing a brittle solid product. This was obtained at 150°C with an addition of 2.5wt% char (as catalyst) after a processing time of 1h. The batch reactor was also used for modifying and solidifying fast pyrolysis liquids derived from beech wood by adding urea or ammonium phosphate as post processing nitrogenolysis. The results showed that this type of combined approach was not suitable to produce a slow release fertiliser, because the solid product contained up to 65wt.% of highly water soluble nitrogen compounds that would be released instantly by rain. To complement the processing experiments a comparative study via Py–GC–MS with inert and reactive gas was performed with cellulose, hemicellulose, lignin and beech wood. This revealed that the presence of ammonia gas during analytical pyrolysis did not appear to have any direct impact on the decomposition products of the tested materials. The chromatograms obtained showed almost no differences between inert and ammonia gas experiments indicating that the reaction between ammonia and pyrolysis vapours does not occur instantly. A comparative study via Fourier Transformed Infrared Spectroscopy of solidified fast pyrolysis and in-situ nitrogenolysis products showed that there were some alterations in the spectra obtained. A shift in frequencies indicating C=O stretches typically related to the presence of carboxylic acids to C=O stretches related to amides was observed and no double or triple bonded nitrogen was detected. This indicates that organic acids reacted with ammonia and that no potentially harmful or non-biodegradable triple bonded nitrogen compounds were formed. The impact of solid slow release fertiliser (SRF) derived from pyrolysis and in-situ nitrogenolysis products from beech wood and Barley DDGS on microbial life in soils and plant growth was tested in cooperation with Rothamsted Research. The microbial incubation tests indicated that microbes can thrive on the SRFs produced, although some microbial species seem to have a reduced activity at very high concentrations of beech wood and Barley DDGS derived SRF. The plant tests (pot trials) showed that the application of SRF derived from beech wood and barley DDGS had no negative impact on germination or plant growth of rye grass. The fertilizing effect was proven by the dry matter yields in three harvests after 47 days, 89 days and 131 days. The findings of this research indicate that in general a slow release fertiliser can be produced from biomass and biogenic residues by in-situ nitrogenolysis. Nevertheless the findings also show that additional research is necessary to identify which compounds are formed during this process.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Design of a material surface for rapid biofilm formation and application to a membrane-aerated biofilm reactor for simultaneous nitrification and denitrification

制度:新 ; 文部省報告番号:甲2149号 ; 学位の種類:博士(工学) ; 授与年月日:2006/3/15 ; 早大学位記番号:新414

Recent Perspectives in Pyrolysis Research

Recent Perspectives in Pyrolysis Research presents and discusses different routes of pyrolytic conversions. It contains exhaustive and comprehensive reports and studies of the use of pyrolysis for energy and materials production and waste management

Book of abstracts of the 10th International Chemical and Biological Engineering Conference: CHEMPOR 2008

This book contains the extended abstracts presented at the 10th International Chemical and Biological Engineering Conference - CHEMPOR 2008, held in Braga, Portugal, over 3 days, from the 4th to the 6th of September, 2008. Previous editions took place in Lisboa (1975, 1889, 1998), Braga (1978), Póvoa de Varzim (1981), Coimbra (1985, 2005), Porto (1993), and Aveiro (2001). The conference was jointly organized by the University of Minho, “Ordem dos Engenheiros”, and the IBB - Institute for Biotechnology and Bioengineering with the usual support of the “Sociedade Portuguesa de Química” and, by the first time, of the “Sociedade Portuguesa de Biotecnologia”. Thirty years elapsed since CHEMPOR was held at the University of Minho, organized by T.R. Bott, D. Allen, A. Bridgwater, J.J.B. Romero, L.J.S. Soares and J.D.R.S. Pinheiro. We are fortunate to have Profs. Bott, Soares and Pinheiro in the Honor Committee of this 10th edition, under the high Patronage of his Excellency the President of the Portuguese Republic, Prof. Aníbal Cavaco Silva. The opening ceremony will confer Prof. Bott with a “Long Term Achievement” award acknowledging the important contribution Prof. Bott brought along more than 30 years to the development of the Chemical Engineering science, to the launch of CHEMPOR series and specially to the University of Minho. Prof. Bott’s inaugural lecture will address the importance of effective energy management in processing operations, particularly in the effectiveness of heat recovery and the associated reduction in greenhouse gas emission from combustion processes. The CHEMPOR series traditionally brings together both young and established researchers and end users to discuss recent developments in different areas of Chemical Engineering. The scope of this edition is broadening out by including the Biological Engineering research. One of the major core areas of the conference program is life quality, due to the importance that Chemical and Biological Engineering plays in this area. “Integration of Life Sciences & Engineering” and “Sustainable Process-Product Development through Green Chemistry” are two of the leading themes with papers addressing such important issues. This is complemented with additional leading themes including “Advancing the Chemical and Biological Engineering Fundamentals”, “Multi-Scale and/or Multi-Disciplinary Approach to Process-Product Innovation”, “Systematic Methods and Tools for Managing the Complexity”, and “Educating Chemical and Biological Engineers for Coming Challenges” which define the extended abstracts arrangements along this book. A total of 516 extended abstracts are included in the book, consisting of 7 invited lecturers, 15 keynote, 105 short oral presentations given in 5 parallel sessions, along with 6 slots for viewing 389 poster presentations. Full papers are jointly included in the companion Proceedings in CD-ROM. All papers have been reviewed and we are grateful to the members of scientific and organizing committees for their evaluations. It was an intensive task since 610 submitted abstracts from 45 countries were received. It has been an honor for us to contribute to setting up CHEMPOR 2008 during almost two years. We wish to thank the authors who have contributed to yield a high scientific standard to the program. We are thankful to the sponsors who have contributed decisively to this event. We also extend our gratefulness to all those who, through their dedicated efforts, have assisted us in this task. On behalf of the Scientific and Organizing Committees we wish you that together with an interesting reading, the scientific program and the social moments organized will be memorable for all.Fundação para a Ciência e a Tecnologia (FCT

Multifunctional Inorganic Hollow Fibre Membranes for Chemical Reactions

Over the last few decades, the availability of inorganic membranes which can withstand high temperatures and harsh chemical environments has resulted in a wide range of opportunities for the application of membranes in chemical reactions. In particular, the combination of membrane separation and catalytic reaction in a single operating unit is an attractive way to increase conversions, to achieve better yields and to make more efficient use of natural resources in many reactions. In this work, a highly compact multifunctional Pd and Pd-Ag/alumina hollow fibre membrane reactor (HFMR) have been developed and applied to catalytic chemical reactions. The developed HFMR consists of a thin and defect free Pd-based membrane coated onto the outer surface of an alumina hollow fibre substrate with a unique asymmetric pore structure, i.e. a sponge-like outer layer and a finger-like inner layer where catalyst is deposited. In one study, a Pd-Ag layer was coated onto the outer surface of the substrate followed by deposition of sub-micron sized Pt(0.5wt.%)/γ-alumina catalysts into the finger-like voids of the substrates. This design achieved propane conversion as high as 42 % at the initial stage of the reaction at 723 K and space-time yields (STY) of the HFMR were approximately 60 times higher than that of a fixed bed reactor (FBR). In order to further increase catalytic surface area in the reaction zone, a sol-gel method was used to deposit Pt(1 wt.%)/SBA-15 catalysts into the finger-like voids of a substrate to develop a Pd/alumina HFMR. Benefiting from this novel design, the functionalized alumina hollow fibre substrates with surface area/volume values of up to 1918.4 m2/m3 possess a specific surface area of about 31.8 m2/g for catalysts. It was observed that in comparison with a conventional FBR, greater propene selectivity and propene yield was achieved by using the HFMR for propane dehydrogenation. The generic advantages of the design of these compact HFMR systems can be applied to further applications such as the water-gas shift reaction, which was also carried out in this study

Towards the integration of oxidative and reductive activities: application to nitrogen removal by co-immobilized microorganisms

BackgroundComplete degradation of many pollutants requires sequenced anaerobic-aerobic biotreatment steps. Many compounds that are difficult to degrade aerobically are readily biotransformed anaerobically. The products of anaerobic biotransformation, however, will frequently resist to further mineralization; yet, they will be good substrates for aerobic biodegradation. Examples of this are the sequential biodegradation of highly chlorinated aromatics and aliphatics, azo-dyes, TNT, inorganic nitrogen compounds (NH 4+ , NO 2- and NO 3- ) and pesticides such as DDT, HCH's or methoxychlor. In waste-and groundwater treatment, these sequenced biotransformations are commonly achieved either by using aerobic and anaerobic (anoxic) reactors in series or by alternating periods of aerobiosis and anaerobiosis in a treatment unit. Ideally, however, these biodegradation processes would take place in a single, compact continuous-reactor system under carefully controlled conditions. In many instances, the benefits of such an integrated system would be clearly greater than the mere sum of the advantages of each individual process.Magic beads: an advanced engineering concept for process integrationThis work addresses the possibilities of integrating oxidative and reductive complementary biodegradation processes in compact systems by using co-immobilized mixed-culture systems. The central idea throughout the book is that aerobic and anaerobic niches will eventually develop and coexist within a single biocatalytic particle so that oxidative and reductive activities (e.g nitrification and denitrification, respectively) can be accomplished simultaneously (Magic-beads). Therefore, multiple-step complementary biodegradation and biotransformation processes could be conducted as single staged (Figure 1). The rationale behind this idea relies on sound experimental evidence (e.g. time-dependent measurements of oxygen gradients across biocatalyst particles or biofilms) that shows that such niches do indeed establish under aerobic process conditions.Figure 1 - Schematic representation of the "Magic-bead Concept".Case study: Integrated nitrification and denitrificationThe potential of the general concept outlined above for combining oxidative and reductive processes with relevance to the biodegadation of recalcitrant compounds is assessed in this work by studying in detail coupled nitrification and denitrification within (double-layered) gel beads for high-rate removal of nitrogen from wastewaters. In such beads, the nitrifying microorganisms (aerobes) immobilized in an outer layer would oxidize ammonium into nitrite that would then diffuse inwards, where immobilized denitrifiers (either facultative heterotrophs or obligate anaerobic ammonium oxidizers) would reduce this nitrite into the harmless gaseous nitrogen. The biocatalyst particle is used optimally because both the external layers and core are active. The beads are placed in a common airlift reactor through which the waste streams can flow at almost any rate, without the need of recirculation to or from any anoxic compartment or reactor.Aims of the dissertation and outlineThis research project aimed at a) the development and characterization of a coupled system for integrated nitrogen removal, b) understanding the mechanisms underlying the processes involved and; c) providing knowledge for the integration of oxidative and reductive activities in a single compact system. With these aims in mind, the stepwise strategy depicted in Figure 2 was developed. Every stage of the project was comprised by a series of self-contained studies addressing different aspects of the proposed system.Figure 2 - Structured contents of this dissertation.In the first stage (chapter 2) the scope of the problem was defined (apparent incompatibility of oxidative and reductive activities of environmental relevance), the needs were addressed (urge to integrate processes and reduce reactor size) and the state-of- the-art of the field (conventional systems and emerging technologies) was presented. In the following phase (chapters 3 to 6), a compact process was proposed and the procedures for biocatalyst production, and its characterization and mechanical stability were assessed. In the next stage (chapter 7 to 9), achievement of in-depth insight into the system's behavior was pursued by means of mathematical modeling and concomitant experimental validation using specific microelectrodes. The knowledge gathered up to this point was subsequently used successfully for the design of a fully autotrophic system for nitrogen removal (chapters 10 and 11). Finally, the possibilities of integrating other oxidative and reductive complementary biodegradation processes in compact systems by using co-immobilized mixed-culture systems were discussed in Chapter 12.</p

Biomass Processing for Biofuels, Bioenergy and Chemicals

Biomass can be used to produce renewable electricity, thermal energy, transportation fuels (biofuels), and high-value functional chemicals. As an energy source, biomass can be used either directly via combustion to produce heat or indirectly after it is converted to one of many forms of bioenergy and biofuel via thermochemical or biochemical pathways. The conversion of biomass can be achieved using various advanced methods, which are broadly classified into thermochemical conversion, biochemical conversion, electrochemical conversion, and so on. Advanced development technologies and processes are able to convert biomass into alternative energy sources in solid (e.g., charcoal, biochar, and RDF), liquid (biodiesel, algae biofuel, bioethanol, and pyrolysis and liquefaction bio-oils), and gaseous (e.g., biogas, syngas, and biohydrogen) forms. Because of the merits of biomass energy for environmental sustainability, biofuel and bioenergy technologies play a crucial role in renewable energy development and the replacement of chemicals by highly functional biomass. This book provides a comprehensive overview and in-depth technical research addressing recent progress in biomass conversion processes. It also covers studies on advanced techniques and methods for bioenergy and biofuel production

The Recovery of uranium from seawater.

This report is the proceedings of a topical meeting on the recovery of uranium from seawater, held at the Massachusetts Institute of Technology on December 1-2, 1980. The meeting was sponsored by the United States Department of Energy and hosted by the MIT Energy Laboratory and Nuclear Engineering Department.Workers from six different countries presented a total of sixteen papers in three major categories: the state-ofthe art resulting from past efforts; detailed results from sorber preparation and performance experiments; and overall system design aspects.Sorbers discussed include hydrous titanium oxide, ion exchange resins, chitosan, humic acids and activated carbon. Systems for contacting seawater with the sorber include actively pumped, current and wave-powered concepts. Filter configurations include thin multilayer stacks, fluidized beds and free falling particles.Several of the researchers estimated eventual production costs in the 200-400 $/lb U308 range, although values as high as 2000$/lb were also quoted.The bulk of the proceedings is comprised of the unedited papers, as provided by the authors. The proceedings also include edited transcripts of the discussions on all papers and the panel and concluding discussions