Anaerobic treatment for C and S removal in “zero-discharge” paper mills: effects of process design on S removal efficiencies

Stringent environmental laws in Europe and Northern America lead to the development towards closure of the process water streams in pulp and paper mills. Application of a "zero-discharge" process is already a feasible option for the board and packaging paper industry, provided in-line treatment is applied. Concomitant energy conservation inside the mill results in process water temperatures of 50-60°C. Thermophilic anaerobic treatment complemented with appropriate post-treatment is considered as the most cost-effective solution to meet re-use criteria of the process water and to keep its temperature. In the proposed closed-cycle, the anaerobic treatment step removes the largest fraction of the biodegradable COD and eliminates “S” as H₂S from the process stream, without the use of additional chemicals. The anaerobic step is regarded as the only possible location to bleed "S" from the process water cycle. In laboratory experiments, the effect of upward liquid velocity (V_upw) and the specific gas loading rate (V_gas) on the S removal capacity of thermophilic anaerobic bio-reactors was investigated. Acidifying, sulphate reducing sludge bed reactors were fed with partly acidified synthetic paper mill wastewater and were operated at 55°C and pH 6. The reactors were operated at organic loading rates up to 50 g COD.l⁻¹.day⁻¹ at COD/SO₄^2- ratios of 10. The effect of Vupw was researched by comparing the performance of a UASB reactor operated at 1.0 m.h⁻¹ and an EGSB reactor, operated at 6.8 m.h⁻¹. The V_upw had a strong effect on the fermentation patterns. In the UASB reactor, acidification yielded H₂, acetate and propionate, leading to an accumulation of reducing equivalents. These were partly disposed of by the production of n-butyrate and n-valerate from propionate. In the EGSB reactor net acetate consumption was observed as well as high volumetric gas (CO₂ and CH₄) production rates. The higher gas production rates in the EGSB reactor resulted in higher S-stripping efficiencies. The effect of V_gas was further researched by comparing 2 UASB reactors which were sparged with N₂ gas at a specific gas loading rate of 30 m³.m⁻².day⁻¹. In contrast to the regular UASB reactors, the gas-supplied UASB showed a more stable performance when the organic loading rates were increased. Also, the H₂S stripping efficiency was 3-4 times higher in the gas-supplied UASB, reaching values of 67%. Higher values were not obtained owing to the relatively poor sulphate reduction efficiencies.