Ash transformation during combustion of phosphorus-rich industrial sludge : Investigation of phosphorus recovery potential, and effects on emissions and deposit formation 

Abstract:

Effective use of resources is essential in the development towards a sustainable industry. Waste products, such as sludge from industrial waste water treatment, often contain valuable reserves of plant nutrients but this resource is nonetheless commonly disposed of as contaminated waste.  Approximately 1 500 ton phosphorus per year is added in biological waste water treatment at the Swedish pulp and paper industries and this non-renewable resource thereby ends up in their so called biosludge. The most common way to discard the sludge is by incineration. Besides the high levels of phosphorus, the biosludge usually contains high levels of moisture and ash forming elements, sulfur and chlorine, which makes it a rather problematic fuel.

The aim with this study was to investigate different aspects on ash transformation chemistry during co-combustion of biosludge, from the pulp and paper mill SCA Packaging Obbola AB, with wood fuels and wheat straw. The phosphorus recovery potential, and the effects on deposit formation and emissions,  were examined by SEM-EDS- and XRD-analysis of ash from co-combustion experiments. The experimental results were complemented with theoretical analysis based on thermochemical equilibrium calculations.

The biosludge from SCA Obbola contained high levels of Ca which had a large impact on the ash transformation reactions. Most of the phosphorus from the fuels stayed in the solid ash during combustion, and in all ash assortments, except for the pure wood fuel, it was primarily found in the crystalline structure whitlockite, Ca₉(K,Mg,Fe)(PO₄)₇. Hydroxyapatite, Ca₅(PO₄)₃OH, was identified in ash from combustion of the pure wood fuel and wheat straw, and in the mixture of biosludge and wood fuels with the lowest proportion of sludge. Of the two phosphorus compounds, hydroxyapatite is more difficult to break down. It is therefore promising from a phosphorus recovery perspective that whitlockite was the main phosphorus compound in most of the ash assortments. Some of the sulfur in the sludge reacted with Ca and formed solid CaSO₄, which stayed in solid ash during combustion, while chlorine generally left the bottom ash by volatilization.

K- and Si-rich agricultural residues, such as wheat straw, are associated with a number of ash-related problems, including deposit formation due to low ash-melting points. During co-combustion of biosludge and wheat straw, the melting tendencies of the wheat straw ash elements were examined. According to the thermochemical equilibrium calculations, the composition of the mixed fuels would result in a significantly higher initial slag formation temperature compared to the pure wheat straw. This trend was also observed in the experimental results. It is likely that the relatively high levels of Ca, Al and P in the sludge all contributed to reduced slag formation in the wheat straw ash, by formation of ash compounds with higher melting temperatures. The high calcium levels may however have reduced some of the positive effects of increased P and Al contents by these elements preferably reacting with Ca instead of capturing alkali in crystalline structures.