DEVELOPMENT AND MODELING OF MEMBRANE PROCESSES FOR THE REGENERATION OF ACID PICKLING SOLUTIONS

The doctoral thesis focuses on a novel integrated process for the recovery and valorisation of acid and metal salts present in the waste solutions of the pickling process. The proposed process is based on the integration of two innovative membrane technologies, the Diffusion Dialysis and the Membrane Distillation, coupled with a reactive precipitation section. This hybrid process allows the recovery and the enhancement of waste solutions, as well as optimal operating conditions for the continuous pickling process, thus improving its efficiency. Hydrochloric acid recovery was assessed through a detailed study on the Diffusion Dialysis process by implementing a wide experimental campaign using artificial solutions produced in laboratory, in order to understand and characterize the system. A mathematical model was developed with time and space distributed-parameters structure for the effective simulation of steady state and transient batch operations, thus providing an operative tool for the design and optimization of DD units. Selective separation of metal salts was reached by precipitating ferric hydroxide and maintaining ammonium and zinc chlorides in solution, which can be used as fluxing solution in the galvanizing process itself, thus implementing the typical Circular Economy concept. The feasibility of the proposed process is demonstrated through the use of a purposely developed process simulator able to predict steady state operation of the integrated process and to perform sensitivity analysis for the identification of the best operating conditions of the system. An experimental campaign was carried out with a demonstrator unit, jointly designed and constructed by Fraunhofer ISE (Freiburg, Germany), eventually installed in the real industrial environment of Tecnozinco s.r.l hot-dip galvanizing plant in Carini, Sicily. The campaign assessed the integration performance of the different units and the process reliability, resulting in a minimization of spent pickling solution disposal and in high quality recovered compounds. An engineering economic analysis was carried out in order to assess the economic feasibility of the proposed process. The economic model was implemented in the gPROMS simulation platform and was used to conduct an optimization analysis, defining the optimal operational and design conditions for which the process is more profitable and performing. The process simulator was also used to provide a scale-up of the demonstrator plant. The results have shown that the process has a good potential for industrial implementation, thanks to the economic and environmental benefits

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, a single-cell diffusion dialysis module equipped with a FumaTech Anion Exchange Membrane (AEM), operated in a batch mode, has been employed in order to study the effect of some parameters on the efficiency of HCl recovery from waste pickling acidic solutions. In addition, a mathematical model, capable of simulate and predict this process, has been also developed and validated with experimental information. The laboratory test-rig and procedures have been first evaluated and optimised by measuring salt and water fluxes with artificial NaCl solutions with different types of AEMs. Then, experiments with HCl solutions were carried out, at different compositions of diffusate and retentate streams, varying HCl concentration values in the range of 0.1-3 M. HCl and water osmotic fluxes were measured and their dependence on operating conditions was identified. Also the effect of the presence of selected iron salts were investigated in order to simulate the operation of the system when treating actual pickling solutions. In particular, the acid diffusion permeability as well as the water osmotic permeability tend to increase when increasing the solution concentration. In addition, an increasing HCl recovery is detected in the presence of iron chloride. References [1] Luo et al., Diffusion dialysis processes of inorganic acids and their salts: the permeability of different acidic anions, Separation and Purification Technology 78 (2011), 97-102 [2] Xu et al., Recovery of hydrochloric acid from the waste acid solution by diffusion dialysis, Journal of Hazardous Materials 165 (2009), 832-83

Combining Membrane and Zero Brine Technologies in Waste Acid Treatment for a Circular Economy in the Hot‑Dip Galvanizing Industry: A Life Cycle Perspective

An innovative approach of combining membrane and zero brine technologies for a joint treatment of industrial liquid waste is investigated regarding its environmental impacts compared to the existing liquid waste treatment. The object of investigation is the generation of waste acid solution by a hot dip galvanizing plant in Sicily, Italy. The waste acid solution contains hydrochloric acid, iron and zinc, which makes it a hazardous waste according to EU classifcations. Environmental impacts are studied for two scenarios in the Tecnozinco hot-dip galvanizing plant in Sicily, Italy: (i) the current process of pickling with linear disposal of waste acid and (ii) the pickling combined with in-situ treatment of the waste acid using a combination of difusion dialysis (DD), membrane distillation (MD) and a precipitation reactor. Results are obtained via an attributional life cycle assessment (LCA) approach focusing on the water footprint profle of the process. The linear disposal path creates signifcant costs, environmental burdens and risks during the 1500 km transport of hazardous liquid waste. The combination of DD and MD, complemented with a zero-brine precipitation reactor, closes internal material loops, could save local water resources and reduces costs as well as environmental impacts. Reduction potentials of 70–80% regarding most LCA impact categories can be expected for the application of the novel technology combination supporting the galvanizing pre-treatment process under study. Therefore, the application of such technology on the way forward to a more circular economy is recommended from an environmental viewpoint, especially in process plants similar to the investigated one

Economic Benefits of Waste Pickling Solution Valorization

An integrated hybrid membrane process, composed of a diffusion dialysis (DD), a membrane distillation (MD) and a reactive precipitation unit (CSTR), is proposed as a promising solution for the valorization and onsite recycling of pickling waste streams. An economic analysis was performed aiming to demonstrate the feasibility of the developed process with a NPV of about EUR 40,000 and a DPBP of 4 years. The investment and operating costs, as well as the avoided costs and the benefits for the company operating the plant, were analyzed with an extensive cost tracking exercise and through face-to-face contact with manufacturers and sector leaders. A mathematical model was implemented using the gPROMS modelling platform. It is able to simulate steady state operations and run optimization analysis of the process performance. The impact of key operating and design parameters, such as the set-point bath concentration and the DD and MD membrane areas, respectively, was investigated and the optimal arrangement was identified. Finally, operating variables and design parameters were optimized simultaneously in a nonlinear framework as a tradeoff between profitability and environmental impact. We show how the integration of new technologies into the traditional pickling industry could provide a significant benefit for the issues of process sustainability, which are currently pressing

Economic Benefits of Waste Pickling Solution Valorization

An integrated hybrid membrane process, composed of a diffusion dialysis (DD), a membrane distillation (MD) and a reactive precipitation unit (CSTR), is proposed as a promising solution for the valorization and onsite recycling of pickling waste streams. An economic analysis was performed aiming to demonstrate the feasibility of the developed process with a NPV of about EUR 40,000 and a DPBP of 4 years. The investment and operating costs, as well as the avoided costs and the benefits for the company operating the plant, were analyzed with an extensive cost tracking exercise and through face-to-face contact with manufacturers and sector leaders. A mathematical model was implemented using the gPROMS modelling platform. It is able to simulate steady state operations and run optimization analysis of the process performance. The impact of key operating and design parameters, such as the set-point bath concentration and the DD and MD membrane areas, respectively, was investigated and the optimal arrangement was identified. Finally, operating variables and design parameters were optimized simultaneously in a nonlinear framework as a tradeoff between profitability and environmental impact. We show how the integration of new technologies into the traditional pickling industry could provide a significant benefit for the issues of process sustainability, which are currently pressing

Diffusion Dialysis for Separation of Hydrochloric Acid, Iron and Zinc Ions from Highly Concentrated Pickling Solutions

Acid recovery from pickling waste solutions is an important step to enhance hot-dip-galvanizing industry 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 study, a laboratory scale unit operating in batch and a continuous large scale unit, both equipped with Fumasep anionic exchange membranes, were tested. Results obtained show that zinc and iron concentration affect the HCl recovery in opposite ways. Iron chlorides enhance acid recovery, while zinc chlorides considerably tend to diffuse through the membrane because of negatively charged chloro-complexes formation and slightly reduce the acid diffusion. A multi-components mathematical model, with a time-dependent and distributed-parameters architecture, was adopted enabling the prediction of operations with hydrochloric acid, zinc, and iron metals both in batch and in continuous dialyzers. As a result, a good comparison between model simulations and experiments was achieved in both configurations

Economic Benefits of Waste Pickling Solution Valorization

An integrated hybrid membrane process, composed of a diffusion dialysis (DD), a membrane distillation (MD) and a reactive precipitation unit (CSTR), is proposed as a promising solution for the valorization and onsite recycling of pickling waste streams. An economic analysis was performed aiming to demonstrate the feasibility of the developed process with a NPV of about EUR 40,000 and a DPBP of 4 years. The investment and operating costs, as well as the avoided costs and the benefits for the company operating the plant, were analyzed with an extensive cost tracking exercise and through face-to-face contact with manufacturers and sector leaders. A mathematical model was implemented using the gPROMS modelling platform. It is able to simulate steady state operations and run optimization analysis of the process performance. The impact of key operating and design parameters, such as the set-point bath concentration and the DD and MD membrane areas, respectively, was investigated and the optimal arrangement was identified. Finally, operating variables and design parameters were optimized simultaneously in a nonlinear framework as a tradeoff between profitability and environmental impact. We show how the integration of new technologies into the traditional pickling industry could provide a significant benefit for the issues of process sustainability, which are currently pressing

Design of a novel membrane-integrated waste acid recovery process from pickling solution

Hydrochloric acid pickling is a common practice in steel manufacturing industry. During the process, acid is consumed to dissolve surface oxides and metals ions are accumulated in the solution, which becomes less effective with time. In addition, the costly and risky waste acid disposal is another issue affecting the hot-dip galvanizing industry. In this work, a novel sustainable waste acid recovery process from pickling solutions based on circular approach is proposed to tackle these issues. The innovative system allows (i) the continuous regeneration of pickling solutions to enhance process rate and performance and (ii) minimise the highly expensive and environmentally risky wastewater disposal. In this way, refilling pickling baths with fresh acid, as done in conventional operation, can be avoided and can be carried out continuously under optimal working conditions. Moreover, the recovery of valuable substances (e.g. metal hydroxide or salts solution) can be obtained as an additional benefit. Continuous treatment and regeneration of pickling solution can be accomplished by coupling diffusion dialysis (DD) and membrane distillation (MD) technologies with a reactive precipitation unit where iron ions can be separated from the zinc-rich solution, in order to recover valuable products. To this purpose, a steady state process simulator was developed to predict the operation of the proposed integrated process

Experimental investigation and modeling of diffusion dialysis for HCl recovery from waste pickling solution

Hydrochloric acid recovery from pickling solutions was studied by employing a batch diffusion dialysis (DD) laboratory test-rig equipped with Fumasep membranes. The effect of main operating parameters such as HCl concentration (0.1–3 M) and the presence of Fe2+ (up to 150 g/l) was investigated to simulate the system operation with real industrial streams. The variation of HCl, Fe2+ and water flux was identified. When only HCl is present, a recovery efficiency of 100% was reached. In the presence of FeCl2, higher acid recovery efficiencies, up to 150%, were observed due to the so-called “salt effect”, which promotes the passage of acid even against its concentration gradient. A 7% leakage of FeCl2 was detected in the most severe conditions. An original analysis on water flux in DD operation has indicated that osmotic flux prevails at low HCl concentrations, while a dominant “drag flux” in the opposite direction is observed for higher HCl concentrations. A comprehensive mathematical model was developed and validated with experimental data. The model has a time and space distributed-parameters structure allowing to effectively simulate steady-state and transient batch operations, thus providing an operative tool for the design and optimisation of DD units

Diffusion Dialysis for Separation of Hydrochloric Acid, Iron and Zinc Ions from Highly Concentrated Pickling Solutions

Acid recovery from pickling waste solutions is an important step to enhance hot-dip-galvanizing industry 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 study, a laboratory scale unit operating in batch and a continuous large scale unit, both equipped with Fumasep anionic exchange membranes, were tested. Results obtained show that zinc and iron concentration affect the HCl recovery in opposite ways. Iron chlorides enhance acid recovery, while zinc chlorides considerably tend to diffuse through the membrane because of negatively charged chloro-complexes formation and slightly reduce the acid diffusion. A multi-components mathematical model, with a time-dependent and distributed-parameters architecture, was adopted enabling the prediction of operations with hydrochloric acid, zinc, and iron metals both in batch and in continuous dialyzers. As a result, a good comparison between model simulations and experiments was achieved in both configurations