Abstract

The application of excessive amounts of manure to soil prompted interest in using alternative approaches for treating slurry. One promising technology is hydrothermal carbonisation (HTC) which can recover nutrients such as phosphorus and nitrogen while simultaneously making a solid fuel. Processing manure under acidic conditions can facilitate nutrient recovery; however, very few studies considered the implications of operating at low pH on the combustion properties of the resulting bio-coal. In this work, swine manure was hydrothermally treated at temperatures ranging from 120 to 250 °C in either water alone or reagents including 0.1 M NaOH, 0.1 M H2SO4, and finally 0.1 M organic acid (CH3COOH and HCOOH). The influence of pH on the HTC process and the combustion properties of the resulting bio-coals was assessed. The results indicate that pH has a strong influence on ash chemistry, with decreasing pH resulting in an increased removal of ash. The reduction in mineral matter influences the volatile content of the bio-coal and its energy content. As the ash content in the final bio-coal reduces, the energy density increases. Treatment at 250 °C results in a more “coal like” bio-coal with fuel properties similar to that of lignite coal and a higher heating value (HHV) ranging between 21 and 23 MJ/kg depending on pH. Processing at low pH results in favourable ash chemistry in terms of slagging and fouling. Operating at low pH also appears to influence the level of dehydration during HTC. The level of dehydration increases with decreasing pH, although this effect is reduced at higher temperatures. At higher-temperature processing (250 °C), operating at lower pH increases the yield of bio-coal; however, at lower temperatures (below 200 °C), the reverse is true. The lower yields obtained below 200 °C in the presence of acid may be due to acid hydrolysis of carbohydrate in the manure, whereas, at the higher temperatures, it may be due to the acid promoting polymerisation.

Highlights

  • Animal manures were returned to land and used in agriculture to increase soil organic matter and provide plant nutrients

  • The results indicated that the feedwater pH influences carbon density and higher heating value (HHV) in wheat straw, with higher carbon densities associated with lower pH

  • The results indicate that operation at low pH increases the carbon content and HHV of the bio-coal

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Summary

Introduction

Animal manures were returned to land and used in agriculture to increase soil organic matter and provide plant nutrients. Leaching of alkaline metals and chlorine during HTC was demonstrated in a number of studies that concluded that slagging, fouling, and corrosion can be reduced by reducing alkali metals [18,19,20,21,22,23,24] This reduction in slagging and fouling propensity following HTC was first demonstrated by Reza et al [25] and later developed by Smith et al [26], who demonstrated the effect of alkali metal removal on ash melting temperatures for HTC bio-coal using ash fusion analysis. This was later validated by subsequent studies [27,28,29,30]. The influence of pH on the on the HTC process was assessed, and the combustion properties of the resulting fuels were assessed

Hydrothermal Processing
Inorganic Analysis
Organic Analysis and Determination of Combustion Properties
Prediction of Slagging and Fouling Propensity
Influence of pH on Bio-Coal Composition
Influence of pH on Fuel Inorganic Chemistry
Influence of pH on Fuel Combustion Chemistry
Conclusions
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