Hydrothermal Mineralization Treatment of Hazardous Oxoanions in Wastewater for Resource Recovery

"Emission of industrial wastewater containing harmful oxoanions is one of the serious problems on account of its toxicity and the environmental pollution, especially caused by boric, phosphinic, arsenic and antimonic species. In this study, we developed a novel treatment technique of such polluted-water by hydrothermal mineralization. The treatment is “Geomimetic” method for precipitating oxoanions in aqueous media as natural ore resources by using hydrothermal treatment with calcium salts mineralizer. The treatment made it possible not only to detoxify the polluted-water, but also to recover the calcium minerals such as Ca2B2O5·H2O, Ca5(AsO4)3(OH), etc. Concentration of each ion in treated-water was lower than that of effluent standard in Japan. Moreover, the residual concentration of each ion was independent of the initial concentration, but it depends only on the solubility of the formed mineral under hydrothermal condition. Therefore, the hydrothermal treatment could be recommended as one of the treatment techniques of polluted-water.IntroductionVarious oxoanions such as boron and arsenic oxo-anions have high toxicity against human health and the environment. They are important resources, however, for plating or advanced material manufacturing industries[1-3], from which the wastewater containing these oxoanions is generated every day. An appropriate treatment is often required for industrial wastewaters to attain national effluent standards of Japan (NESJ, B: 10 mg/dm3, As: 0.1 mg/dm3). On the other hand, there is no production of arsenic and boric resources in Japan, and they are expected to be recycled. Therefore, the establishment of a system for the removal and recycling of arsenic and boron from wastewaters is of global significance.Several methods to remove them from aqueous media have been already reported by using adsorption[4], electro-coagulation[5], membrane separation[6-8] and biological techniques[9]. However, these methods have the following problems because of their stability in water. (1) Removal yield is low, especially for tri-valent arsenite ion (AsIIIO3 3-) and borate ion. (2) The applicable concentration range is narrow. In addition, the used adsorbents or collected residues after treatments are sill hazardous wastes, so that they must be treated by a proper method. But, it is very difficult to convert them to recyclable resources at most industrial plants. These problems are caused by the difficulty to recover these oxoanions as stable solid precipitates with low solubility in water. The establishment of recycling system of these hazardous compounds will be one of the world-important issues, especially, in Japan, which is poor in natural resources. On the other hand, compounds that contain high arsenic concentrations and are insoluble in water, are often found in natural minerals, for example, as haidinglite (Ca(AsO3OH)·(H2O) or Johnbaumite (Ca5(AsO4)3(OH)). This fact suggests that nature has an ability to produce insoluble As-bearing minerals. Similar phenomena can be found in case of boron, antimony, etc."