Impurity Effects on the Synthesis of Crystalline Scorodite

"The synthesis of large scorodite particles in non-ferrous metallurgical industries usually requires a high-cost operation involving heating and high-pressure autoclaving. To overcome these obstacles, an atmospheric-pressure process for scorodite synthesis (DMSP®) was developed, in which ferrous ions were oxidized by oxygen gas in the presence of pentavalent arsenic ions. This process gives scorodite of good crystallinity with particle sizes as large as 15-20 µm. The solutions used for scorodite synthesis in the DMSP® are prepared from various residues containing arsenic from non-ferrous smelters. The solutions may be contaminated with Cu, Sb, and Bi, for example, and therefore the effects of such impurities on the formation of crystalline scorodite need to be investigated. In this study, the effects of Cu, Sb, and Bi contaminants on the formation behaviors of scorodite particles in the DMSP® were investigated systematically.INTRODUCTIONThe synthesis of crystalline scorodite (FeAsO4·2H2O) is a suitable method for arsenic (As) stabilization and storage of As-containing by-products such as flue gas dusts in non-ferrous smelters. It is expected that the formation of large, highly-crystalline scorodite particles would be an ideal method for avoiding the release of arsenic to the environment. Generally, autoclave methods under pressurized oxidation conditions at temperatures above 100°C have been used for the formation of arsenic minerals such as scorodite. However, the autoclave method requires sealed vessels that are resistant to high pressure, heat and acids. This process is also unfavorable on account of the high construction expenses, and high running costs as a result of vapor heat loss. Processes for synthesizing scorodite under atmospheric conditions at temperatures below 100°C which do not need an autoclave have therefore been extensively investigated (Demopoulos, Droppert, & VanWeert, 1994; Demopoulos, 1996; Demopoulos, Lagno, Wang, & Singhania, 2003; Droppert, Demopoulos, & Harris, 1996; Filippou & Demopoulos, 1997).Recently, Fujita et al. (Fujita, Taguchi, Abumiya, Matsumoto, Shibata, & Nakamura, 2008a, 2008b, 2009; Fujita, Taguchi, Kubo, Shibata, & Nakamura, 2009; Fujita, Taguchi, Shibata, & Nakamura, 2009) developed a new method for producing large scorodite crystalline particles with improved filtration and washability properties at normal atmospheric pressure and temperatures below 100°C. In the new method, oxygen gas (O2) is blown into solutions containing a high concentration of arsenic ions (As(V)) and ferrous ions (Fe(II)). The Fe(II) ions were subsequently oxidized to ferric ions (Fe(III)), resulting in the formation of large scorodite particles. High supersaturation of solutes such as Fe(III) will result in excessive nucleation, and the formation of poorly crystalline phases. The scorodite formation must therefore be conducted in a manner that avoids the critical supersaturation level being exceeded. It is supposed that the oxidation of Fe(II) to Fe(III) by O2 gas in the new method suppressed the supersaturation of Fe(III) during scorodite formation. The low Fe(III) supersaturation resulted in formations of highly crystalline scorodite particles of size of around 20 µm. In June 2008, based on the developed process described above, DOWA began experiments to verify the industrial capability of a plant with a capacity of 30 MT/month of As. It was successfully proven that it is possible to produce crystalline scorodite industrially on a commercial scale. This process was named and trademarked as DMSP® (Kubo, Abumiya, & Matsumoto, 2010)."