Philip A. Marrone

Salt precipitation and scale control in supercritical water oxidation-Part A: fundamentals and research

Abstract Supercritical water oxidation (SCWO) is an effective technology for treatment of organics and organic components of aqueous wastes. Commercialization of SCWO processes has been hindered by concerns about corrosion and scale buildup/fouling which, when present, must be accommodated by system design and/or operational procedures. Salts are formed during SCWO when acidic solutions are neutralized to reduce corrosion and may also be present in the waste stream itself. Because salts have low solubility in supercritical water (SCW), they precipitate. Precipitated salts often form agglomerates and coat internal surfaces, thereby inhibiting heat transfer from/to exterior surfaces. When scale buildup is left uncontrolled, plugging of transport lines and/or the reactor can occur. The required cleaning can result in substantial and costly downtime in the SCWO process. General principles and research relevant to SCWO have been reviewed elsewhere. A review of the many technologies available to control scale during SCWO is given in the companion paper by Marrone et al. [J. Supercrit. Fluids (in press)]. Presented here is a review of fundamental principles and research pertinent to the precipitation of salts and scale control at the elevated temperatures and pressures found in an SCWO reactor. First, SCWO is introduced and the physics leading to scale buildup during SCWO is discussed. Next, the phase diagrams of model salt–water systems at relevant conditions are presented. Then, the many phenomena which complicate modeling of heat transfer in SCW (buoyancy, rapidly varying thermophysical properties, etc.) are reviewed and a set of correlations to calculate heat transfer coefficients is provided. Finally, the limited number of controlled experimental studies on scale buildup during SCWO are reviewed.

Salt precipitation and scale control in supercritical water oxidation—part B: commercial/full-scale applications

Despite the potential of supercritical water oxidation (SCWO) as a viable technology for organic waste destruction, its commercial development has been hindered by the problems of corrosion and salt precipitation/solids buildup. The extremely low solubility of polar inorganic salts in the supercritical water environment causes salts present in the feed, or formed during reaction, to precipitate inside the reactor. If left unchecked, these salts can rapidly accumulate on reactor walls or process surfaces and form plugs, causing expensive and frequent downtime of the SCWO system. Other solids such as oxides exhibit low solubility in water over the range from ambient to supercritical conditions and, although they have much less tendency to adhere to process surfaces, may still hinder operations if not accommodated. Many wastes will have a combination of salt-type and oxide-type solids, and may have an intermediate tendency to stick to process surfaces. Many of the companies that have attempted to commercialize the SCWO technology over the past two decades have developed innovative approaches to dealing with the corrosion and salt precipitation/solids buildup problems. These are often the distinguishing features of each companys SCWO process. This paper objectively reviews several commercial approaches that have been developed and/or used to control salt precipitation and solids buildup in SCWO systems. The approaches reviewed consist of specific reactor designs and operating techniques, and include the following: reverse flow tank reactor with brine pool, transpiring wall reactor, adsorption/reaction on a fluidized solid phase, reverse flow tubular reactor, centrifuge reactor, high velocity flow, mechanical brushing, rotating scraper, reactor flushing, additives, low turbulence/homogeneous precipitation, crossflow filtration, density separation, and extreme pressure operation. Recent commercial SCWO applications utilizing these approaches are also discussed. A companion paper by Hodes et al. (J. Supercrit. Fluid., see this volume) reviews fundamental principles and research pertinent to scale control in SCWO processes.