Diffusion dialysis for HCl and heavy metals separation from highly concentrated pickling solutions

Disposal of pickling waste solutions strongly affects hot-dip galvanizing industries’ economics and environmental footprint. Thus, the recovery of acid is an important step to enhance the process sustainability. Diffusion dialysis (DD) can be used to separate acids and heavy metals (e.g. iron and zinc) from pickling waters, promoting the circular use of such raw materials. In the present work, two DD modules, a laboratory scale unit operating in batch and a continuous operated large unit, equipped with Fumasep anionic exchange membranes were tested. Results obtained show that zinc and iron affect HCl recovery in opposite way, however reaching high recovery values. In particular, zinc consid…

Modeling and Design of Membrane Integrated Processes for HCl and Metals Recovery from Pickling Solutions

Hydrochloric acid pickling is a common practice in steel manufacturing industry. During the process, acid is consumed to dissolve surface oxides and metals are accumulated in the solution. This fact leads to a process efficiency decrease. Continuous regeneration of pickling solutions enhances process rate and performance, but also minimises the highly expensive and environmentally risky wastewater disposal. The recovery of valuable substances (e.g. acid and metals) can be accomplished by coupling diffusion dialysis (DD) and membrane distillation (MD) technologies. In the present work, a steady state process simulator for the integrated process has been developed. The aim is to analyze and p…

Modeling and Design of Membrane Process Recovery of HCl and Metals from Pickling Solutions

Abstract Hydrochloric acid pickling is one of the key steps in the hot-dip galvanizing process. It is a process widely used as a chemical pre-treatment method for cleaning, where metal surfaces with oxides are immersed into an acid solution. During the pickling process, the acid concentration decreases with time while the metal is accumulated. Thus, the efficiency of the pickling solution decreases and fresh solution must be used. Continuous regeneration of pickling solutions enhances pickling rate and process performance, but also minimises industrial wastewater disposal and chemicals consumption. The recovery and recycling process of valuable substances (e.g. acid and metals) can be accom…

Treatment of electroplating wastewater by combining membrane technologies and reactive precipitation process at pilot scale

Recovery of pickling acid solutions by membrane technology: the EU REWACEM Project

Resource recovery from industrial waste water by cutting edge membrane technologies

Effective recovery of HCl and metals from pickling solutions by cutting-edge membrane technologies

The pickling process is an essential step in the hot-dip galvanizing process.It is performed by immersing manufacturedsteel pieces inacid bathsin order todissolve the oxidized layers. During the pickling process, acid attacks metal oxides on the surface, dissolving them in the pickling bath. Thus, the efficiency of the pickling liquor decreases due to the accumulation of metal salts and the consumption of free acid in the solution. When hydrochloric acid is used,ferrous chloride is producedduring the pickling treatment, reaching concentrations up to 250 g/l, while the acid concentration decreases by 75-85%. A pickling bath in this condition is considered spent [1] due to thevery low picklin…

Experimental investigation and modelling for sulphuric acid recovery by diffusion dialysis

Sulphuric acid is known to be one of the key inorganic acid and has been widely used in chemical reaction and metal industries for surface treatments as in the copper electroplating process. During these processes, large amounts of waste sulphuric acid solution are generally generated, containing high concentrations of metals and acid. The possibility of recover and reuse the sulphuric acid in the process could avoid environmental contamination and reduce costs of the disposal. Among several separation methods, diffusion dialysis (DD) is becoming more and more attractive thanks to the recent important advances in ion exchange membranes (IEMs) field and because of its clean nature and operat…

An integrated approach for HCl and metals recovery from waste pickling solutions: pilot plant design and operations

Continuous regeneration of industrial pickling solutions and recovery of valuable materials are implemented in a pilot-scale plant including diffusion dialysis, membrane distillation and reactive precipitation units. The main results of the preliminary assessment of on site operation are presented. Different hydrochloric acid concentration and metals composition were investigated and the performance of the system were analysed in terms of quality of recovered compounds, energy efficiency and environmental footprint.

Donnan dialysis for tap-water softening

In this presentation, Abdusalam Alhadid, started by introducing the problem of hard water in both domestic and industrial applications,caused by an excess of calcium and magnesium ions. It significantly decreases thelifetime and efficiency of equipment which has negative technical and economic consequences. Existing water softening technologies have several disadvantages, such as a high chemical use (crystallization, ion exchange), water and energy consumption (nanofiltration)

Experimental investigation and modelling of diffusion dialysis process for regeneration of acidic pickling solutions

Pickling is one of the key steps in metal finishing industries, where HCl solutions are largely used thus generating significant amounts of spent waste solutions containing high concentrations of metals and acid. The recovery of acid from such waste solutions is thus one of the most beneficial steps for reducing the environmental and economical impact of these processes. Among several separation methods, diffusion dialysis (DD) is becoming more and more attractive thanks to the recent important advances in ion exchange membranes (IEMs) field and because of its clean nature and operational simplicity, low installation and operating costs and low energy consumption [1,2]. In the present work,…

Design, construction and operational results of a pilot plant for the treatment and valorization of pickling waste solutions

An innovative hybrid technology for both minimizing the waste production and optimizing the pickling process through the continuous control of pickling baths composition has been proposed by means of a pilot-plant installed at the Tecnozinco Srl, Carini (PA) hot-dip galvanizing plant. The recovery process has been accomplished by coupling a diffusion dialysis (DD), where HCl is recovered, a membrane distillation (MD), where HCl is concentrated, and a reactive precipitation (RP), where metal ions are recovered as iron hydroxide and ammonium/zinc chloride solution, to be used in the fluxing baths of the plant. The pilot plant was commissioned and operated using synthetic HCl solutions first a…

Application of diffusion dialysis in separation of sulfuric acid and copper from electroplating wastewater

Electroplating industry creates large volumes of wastewater that contain acids and heavy metallic ions which are toxic but valuable. Diffusion dialysis (DD) can be used to separate acids from heavy metals. In this work, two single-cell DD modules equipped with Fumasep FAD membranes were used for the first time for the separation of sulfuric acid from copper. The first module consisted of a laboratory-scale DD unit operated in a batch configuration to study the effect of process parameters on the efficiency of sulfuric acid recovery. The latter one was a large-scale DD unit operated in a continuous configuration to simulate the process operation at the industrial scale. Results showed that F…