**The Influence of pH on the Combustion Properties of Bio-Coal Following Hydrothermal Treatment of Swine Manure**

### **Aidan Mark Smith 1,\*, Ugochinyere Ekpo 2 and Andrew Barry Ross 2**

1 School of Biological and Chemical Engineering, Aarhus University, 8200 Aarhus, Denmark


Received: 29 November 2019; Accepted: 6 January 2020; Published: 9 January 2020

**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.

**Keywords:** HTC; bio-coal; manure; slagging; fouling; corrosion; process chemistry; combustion; waste to energy
