Pyrolysis of contaminated energy crops and the characterisation of the gained biochar

The simultaneous use of willow as a vegetation filter and an energy crop can respond both to the increasing energy demand and to the problem of the soil and water contamination. Its characteristics guarantee that the resources are used economically. As a vegetation filter, willow uptakes organic and inorganic contaminants. As a fast growing energy crop it meets the requirements of rural areas without the exploitation of existing forestry. The aim of the research was to gather knowledge on the thermal behaviour of willow, uptaking contaminants and then used as an energy crop. For this reason pyrolysis experiments were performed in two different scales. In analytical scale metal-contaminated wood was investigated and bench scale pyrolysis experiments were performed with nitrogen-enriched willow, originated from a wastewater treatment plant. Results of the pyrolysis showed that 51-81 % of the wastewater derived nitrogen of willow was captured in the char product. Char had low surface area (1.4 to 5.4 m2/g), low bulk density (0.15–0.18 g/cm3), high pH values (7.8–9.4) and high water-holding capacity (1.8 to 4.3 cm3/g) while the bioavailability of char nutrients was low. Links were also established between the pyrolysis temperature and the product properties for maximising the biochar provided benefits for soil applications. Results also showed that the metal binding capacity of wood varied from one metal ion to another, char yield increased and levoglucosan yield decreased in their presence. While char yield was mainly affected by the concentration of the metal ions, levoglucosan yield was more dependent on the type of the ionic species. Combustion experiments were also carried out with metal-enriched char. The burnout temperatures, estimated ignition indices and the conversion indicate that the metal ions type and not the amount were the determining factors during the combustion. Results presented in the Thesis provide better understanding on the thermal behaviour of nitrogen-enriched and metal contaminated biomass which is crucial to design effective pyrolysis units and combustors. These findings are relevant for pyrolysis experiments, where the goal is to yield char for energetic or soil applications.

Characterization of engineered biochar for soil management

Pyrolysis is an energy conversion technology which by heating organic materials in the absence of oxygen, produces liquid, gaseous, and solid fuel products. Biochar, the solid product, can also be used as a soil amendment and, simultaneously, enables us to sequester carbon in the soil. By controlling the pyrolysis process, it is possible to engineer biochar suitable for the remediation of specific soil management problems. This research uses a characterization method more suited to producing biochar for soil amendment purposes than the existing biochar fuel characterization standards. This is the first research to use wastewater irrigated willow as a pyrolysis feedstock. The extensive characterization of biochar produced over a range of temperatures (410-810°C) yielded data on key properties relevant to soil under management: low surface area (1.4 to 5.4 m2/g), low bulk density (0.15-0.18 g/cm3), high pH values (7.8-9.4) and high water-holding capacity (1.8 to 4.3 cm3/g). Extraction experiments demonstrated low bioavailability of char nutrients (N, P, K, Ca, and Mg). This research also studied this artificial nitrogen cycle of pyrolysis: nitrogen accumulated in the wood from the wastewater and high levels of nitrogen remained in the biochar in a stable form not directly available to plants. Copyright © 2013 American Institute of Chemical Engineers Environ Prog.

The development of a sustainable agricultural industry through the application of biochar and pyroligneous acid

This paper marks the first in a series of studies into the potential use of pyrolysis products in the development of more sustainable practices within the agricultural industry. In this study, the immediate benefits of the application of biochar to crop yields of Raphanus sativus (radishes) are assessed. Furthermore, the study reports on the preliminary findings into the potential application of pyroligneous acid (wood vinegar) as a biocidal agent against crop disease. Although germination tests undertaken on biochar/compost blends of up to 1: 2, by weight, showed no significant adverse effect from the addition of the nutrient rich carbonaceous solid, evidence of substantial increases in crop yield through the addition of biochar were not observed. In sharp contrast, zones of inhibition were observed at 3-10 vol. % upon application of pyroligneous acid to two causal agents responsible for certain diseases in vegetable and fruit crops, i.e. Rhizobium radiobacter (agrobacterium tumefaciens) and Xanthomonas campestris, highlighting the versatility in the application of pyrolysis products and avenues for exploration in the development of this biomass conversion technology.

Nitrogen cycle of effluent-irrigated energy crop plantations:from wastewater treatment to thermo-chemical conversion processes

This paper reviews nitrogen (N) cycle of effluent-irrigated energy crop plantations, starting from wastewater treatment to thermo-chemical conversion processes. In wastewater, N compounds contribute to eutrophication and toxicity in water cycle. Removal of N via vegetative filters and specifically in short-rotation energy plantations, is a relatively new approach to managing nitrogenous effluents. Though combustion of energy crops is in principle carbon neutral, in practice, N content may contribute to NOx emissions with significant global warming potential. Intermediate pyrolysis produces advanced fuels while reducing such emissions. By operating at intermediate temperature (500°C), it retains most N in char as pyrrolic-N, pyridinic-N, quaternary-N and amines. In addition, biochar provides long-term sequestration of carbon in soils.

Thermo-chemical behaviour and chemical product formation from Polar seaweeds during intermediate pyrolysis

Fundamental analytical pyrolysis studies of biomass from Polar seaweeds, which exhibit a different biomass composition than terrestrial and micro-algae biomass were performed via thermogravimetric analysis (TGA) and pyrolysis-gas chromatography/mass-spectrometry (Py-GC/MS). The main reason for this study is the adaptation of these species to very harsh environments making them an interesting source for thermo-chemical processing for bioenergy generation and production of biochemicals via intermediate pyrolysis. Several macroalgal species from the Arctic region Kongsfjorden, Spitsbergen/Norway (Prasiola crispa, Monostroma arcticum, Polysiphonia arctica, Devaleraea ramentacea, Odonthalia dentata, Phycodrys rubens, Sphacelaria plumosa) and from the Antarctic peninsula, Potter Cove King George Island (Gigartina skottsbergii, Plocamium cartilagineum, Myriogramme manginii, Hymencladiopsis crustigena, Kallymenia antarctica) were investigated under intermediate pyrolysis conditions. TGA of the Polar seaweeds revealed three stages of degradation representing dehydration, devolatilization and decomposition of carbonaceous solids. The maximum degradation temperatures Prasiola crispa were observed within the range of 220-320 C and are lower than typically obtained by terrestrial biomass, due to divergent polysaccharide compositions. Biochar residues accounted for 33-46% and ash contents of 27-45% were obtained. Identification of volatile products by Py-GC/MS revealed a complexity of generated chemical compounds and significant differences between the species. A widespread occurrence of aromatics (toluene, styrene, phenol and 4-methylphenol), acids (acetic acid, benzoic acid alkyl ester derivatives, 2-propenoic acid esters and octadecanoic acid octyl esters) in pyrolysates was detected. Ubiquitous furan-derived products included furfural and 5-methyl-2-furaldehyde. As a pyran-derived compound maltol was obtained by one red algal species (P. rubens) and the monosaccharide d-allose was detected in pyrolysates in one green algal (P. crispa). Further unique chemicals detected were dianhydromannitol from brown algae and isosorbide from green algae biomass. In contrast, the anhydrosugar levoglucosan and the triterpene squalene was detected in a large number of pyrolysates analysed. © 2013 Elsevier B.V. All rights reserved.

Increase of energy recovery from sewage sludge

The use of the pyrolysis process to obtain valuable products from biomass is amongst the technologies being investigated as a source for renewable energy. The pyrolysis process yields products such as biochar, bio-oil and non condensable gases. The main objective of this project is to increase energy recovery from sewage sludge by utilising the intermediate pyrolysis process. The intermediate pyrolysis has a residence time ranging from 5 to 10 minutes. The main product yields from sewage sludge pyrolysis are 50 wt% biochar, 40 wt% bio-oil and 10 wt% non condensable gases. The project was carried out on a pilot plant scale reactor with a load capacity of 20 kg/h. This enabled a high yield of biochar and bio-oil. The characterisation of the products indicated that the organic phase of the bio-oil had good fuel properties such as having high energy content of 39 MJ/kg, low acid number of 21.5, high flash point of 150 and viscosity of 35 cSt. An increase in pyrolysis experiments enabled large quantities of pyrolysis oil production. Co-pyrolysis of sewage sludge was carried out on laboratory scale with mixed wood, rapeseed and straw. It found that there was an increase in bio-oil quantity with rapeseed while co-pyrolysis with wood helped to mask the smell of the sludge pyrolysis oil. Engine test were successfully carried out in an old Lister engine with pyrolysis oil fractions of 30% and 50% blended with biodiesel. This indicates that these pyrolysis oil fractions can be used in similar engine types without any problems however long term effects in ordinary engines are unknown. An economic evaluation was carried out about the implementation of the intermediate pyrolysis process for electricity production in a CHP using the pyrolysis oil. The prices of electricity per kWh were found to be very high.

The potential application of pyroligneous acid in the UK agricultural industry

This paper highlights the potential benefits of smoke recovery from the production of biochar in crop management through it application as an antimicrobial agent against plant disease and as a pesticide. The study reports on the findings of zone inhibition assays on selected plant pathogens (Agrobacterium tumefacien and Xanthomonas campestris), growth studies on selected plants (Raphanus sativus and Vicia faba), and toxicity studies performed on arthropods (Myzus persicae and Tetranychus urticae). The results suggested a strong benefit to crop management in terms of crop protection against selected causal agents responsible for plant disease, with zones of inhibition observed on both Agrobacterium tumefacien and Xanthomonas campestris when inoculated with pyroligneous acid (liquid smoke) at 10% dilution. Similarly, its potential as a bio-pesticide are favorable, with a reported 20%–30% of arthropods affected (knocked out/mortality) after exposure for 48 hours.