A petroleum refinery secondary effluent was treated using two freezing techniques—spray freezing and unidirectional downward freezing (UDF). The freezing processes were effective to remove toxicity and total organic carbon (TOC)- and chemical oxygen demand (COD)-causing materials
in the effluent. Agitation of the liquid during UDF significantly improved the impurity separation efficiency; 85 to 96% removal of TOC and COD was achieved without any pretreatment and freezing only 70% of the feed water. The treatment efficiency of the spray freezing was at
the same level as that of UDF without mixing. The spray ice with longer storage time released more contaminants with early meltwater. The initial contaminant concentration of the feed water and the freezing temperatures (−10°C and −25°C) had no significant influence on
the treatment efficiency. A small fluctuation in effluent TOC concentration caused a dramatic change in effluent toxicity (Microtox). The effective concentration (EC 20) (Microtox) was effective in detecting effluent toxicity.
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