Bio-induced solid selenium for recovery from water

S.P.W. Hageman

Selenium in the form of selenate or selenite in wastewater needs to be removed due to its potential toxicity in the environment. Also, selenium is a valuable element that is used in several industries and current selenium resources are likely to be exhausted in less than 50 years. Waste streams containing selenium can therefore be used as a source of selenium. This requires conversion of the selenium in wastewater into a form that can be recovered. Biologically induced selenate reduction to recoverable selenium has the advantage that it uses the selective reduction capacities of biomass and a renewable electron donor. To improve the recoverability of selenium the conversion of selenate to selenite was seen as an interesting opportunity. Selenite is more reactive than selenate and can be removed in a second step. As described in Chapter 2, it proved possible to convert selenate to mainly selenite at a low electron donor concentration. Another method which is reviewed in this thesis is direct biological reduction of selenate to elemental selenium. After reduction the solids can be removed by a liquid solid separation process. Previously amorphous selenium particles were produced, which hampered recovery. In this research it is demonstrated that at a higher temperature, around 40 - 50°C, and at a higher pH, around pH 8 - 9, a more hexagonal selenium structure can be produced (Chapter 3). Crystalline acicular selenium particles of different sizes were thus obtained. This implies that selenium particles formation can be controlled and that selenium particles can grow. Large selenium particles make the separation process economic. To grow larger selenium particles, a long-term experiment was performed at 50°C (Chapter 4). The reduction rate was poor, but selenium acicular particles were produced. These particles were also detected as clusters. These clusters open up new recovery opportunities. With Eerbeek sludge the optimal conditions for selenate conversion are around pH=7 and 30°C. To enlarge the selenium particles it is strongly recommended to use a different sludge since the optimal conditions with Eerbeek sludge do not match the conditions needed for acicular particle formation. When selenate is converted to selenite, the selenite can be precipitated by sulphide to form selenium sulphide. Emmtec sludge was used to reduce the sulphur compounds to sulphide, leaving selenium as the sole remaining element. This process was performed at T=30°C and a pH between 6 and 7. The selenium thus recovered had a crystalline hexagonal structure (revealed by x-ray diffraction) and the particles were as large as 125µm3. Future research on the two routes that are explored in this thesis can give insights into selenium reduction mechanisms and the formation of large selenium particles. The recoverability of biological selenium particles has also been improved (as discussed in this thesis). In conclusion, this thesis has resulted in a new, bio-selective, renewable selenium recovery method via selenium sulphide.

Bio-induced solid selenium for recovery from water

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