Introduction into Hydrochloric Acid Regeneration Technology

H. Weissenbaeck, SMS Demag Process Technologies GmbH, Vienna, Austria

Management Summary. Everyone operating a commercial carbon steel pickling facility has to provide fresh and to dispose spent acid. Total hydrochloric acid regeneration plants provide a means to virtually eliminating the cost and complex logistics associated with fresh and spent acid supply and disposal. SMS Demag is offering three different processes, each of which is capable of yielding a 99.5% acid return.

The Challenge During the final stages of hot deformation of carbon steel, as for example in a flat products hot rolling mill, the hot surface of the hot rolled product is oxidised by intensive contact with ambient air at high temperature. The higher the coiling temperature in the hot rolling mill, the higher the amount of iron oxides formed. The oxide layer covering both sides of hot rolled steel sheet is commonly called scale.

Before downstream processing in cold rolling mills and strip processing lines, hot rolled sheet has to undergo descaling, a process during which the surface scale layer is removed. To a certain extent more frequently applied to stainless steel and wire products, which are not in the focus of this article - this is possible by mechanical means, a bright and shiny finish can however only be obtained by applying chemical descaling agents that chemically dissolve the iron oxides. While a variety of acids and caustics may in principle be considered suitable to perform that task, the most widely adopted descaling agents are sulphuric acid (H2SO4, which in many integrated steel mills is available at low cost as a by product from coke oven batteries) and hydrochloric acid (HCl, which is a rather low cost chemical compound that can be procured from various sources). During chemical descaling, which is commonly referred to as pickling, sulphuric acid is transformed into ferrous sulphate while hydrochloric acid is transformed into ferrous and (to some extent depending on the composition of the scale layer) ferric chloride. Pickling of carbon steel thus is a process consuming fresh sulphuric or hydrochloric acid and delivering ferrous sulphate or ferrous chloride. Both, the procurement of fresh acid as well as the disposal of sulphates and chlorides, typically go along with high cost and complex logistics.

The Solution While as per today no feasible solution for the separation of iron from ferrous sulphate and the regeneration of spent sulphuric acid pickle liquors has been developed, SMS Demag is offering a range of processes for the total regeneration of spent hydrochloric pickle liquors, yielding recovery rates of up to 99.9% and virtually eliminating the need for fresh acid purchase and spent acid disposal. All these processes present significant improvements in feasibility over traditional, evaporative processes for the reclamation of only unbound HCl. Besides that, total acid regeneration is part of most pickling line operators environmental responsibility policy.

Spray Roaster Process The spray roaster process is a pyrohydrolytic process in which the spent acid is spray-atomized into a directly fired furnace and by contact with oxygen and steam splitted into Fe2O3 powder (solid phase) and HCl (gas phase). Reaction temperatures are in a range of 400 to 700 C. The gaseous HCl is further absorbed in water to form regenerated hydrochloric acid of about 18% strength that can be reused for pickling. It is common and attractive to use the slightly acidic rinse water from the pickling line as absorption liquid.
Spray Roaster Acid Regeneration Plant at Vega do Sul, Brazil

Commissioned by SMS Demag in 2003, Vega do Suls spray roaster acid regeneration plant (design capacity 4.300 liters per hour of processed waste acid) still represents our benchmark for excellent environmental

compliance and production results. The plant serves a pickling line with a production of roughly 1 million tons per year. It is equipped with latest state of the art automation and process control features implemented by SMS Demag.

The red iron oxide powder obtained from spray roasting is of significant commercial value and demanded by a variety of secondary industries, such as colours, pigments, concrete, catalysts and ferrites. A wide range of oxide post treatment technologies, enhancing particular characteristic features of the powder, such as bulk density, specific surface or chlorine content, to match individual customer requirements is available.

Fluidised Bed Process Similar to the spray roaster process the fluidised bed process is of pyrohydrolytic nature and taking place in a directly heated furnace. However the conversion of waste acid into iron oxide and hydrogen chloride takes place in a fluidised bed at a temperature of about 850 C. Thus the iron oxide obtained from a fluidised bed hydrochloric acid regeneration plant is of granular, sintered consistency. Average pellet diameter is between 0.8 and 3mm depending on reactor setup. The pellets are suitable iron ore substitutes in steel making thus making the fluidised bed process the choice of many integrated steel works who do not consider the marketing and sale of iron oxide part of their core business. Absorption of HCl gas is performed in the same way as in spray roasting. However obtainable acid concentration (typically 17%) is slightly lower. One key advantage of fluidised bed acid regeneration plants over spray roasters is the lower NOx content of the stack emissions resulting from lower, less NOx-prone fuel combustion temperatures.
Fluidised Bed Acid Regeneration Plant for JFE Keihin, Japan

Due for commissioning in 2007, JFE Steels new acid regeneration plant, supplied by SMS Demag, will match the extraordinary strict emission limits of Kanagawa prefecture.

Hybrid Pyrohydrolysis Processes Some customers main purpose for operating a pyrohydrolysis plant is the production of high quality iron oxide powder. These customers commonly opt for a reactor design that combines the energy efficiency of a spray roaster with the homogenous and stable process conditions of a fluidised bed plant but require significant investments into dedusting and gas quenching technologies.

Hydrothermal Regeneration Process Hydrothermal Acid Regeneration is a relatively new field of technology, pioneered by SMS Demag and its Japanese research partners. It replaces the directly fired furnace and gas/liquid absorption by an alternative process route consisting of oxidation and hydrolysis. Formation of Fe2O3 takes place in the liquid phase thus dramatically reducing the caloric energy consumption. Using a preconcentrator, obtainable regenerated concentration acid concentration waste exceeds total 30%, HCl otherwise regenerated In acid

equals

acid

concentration.

comparison

pyrohydrolytic processes like spray roasting and fluidised bed pyrohydrolysis deliver only about 18%. Obtainable iron oxide quality is comparable to spray roasted iron oxide in terms of Cl-contamination; however specific surface of particles is adjustable to much higher figures by tuning of hydrolysis conditions. Besides its successful application for HCl regeneration, hydrothermal processes for the production of metal and rare earth oxides as well as for the recovery of HF and HNO3 from mixed acids bear a huge commercial potential and are currently undergoing intensive study in SMS Demags R&D facilities.

Market Trends The key to selecting the most suitable acid regeneration technology for a particular client is the marketability of iron oxide. If the client has access to unsaturated markets and runs all the required by-product marketing and logistics anyway, a spray roaster is the technology of choice. In case, oxide sales opportunities are uncertain and energy consumption is not a critical issue, he might consider a fluidised bed acid regeneration plant.

Process Comparison
Spray Roaster Pyrohydrolysis Recovery Yield Caloric Energy Consumption Electrical Energy Consumption Iron Oxide Consistency Iron Oxide Purity Equipment Size >99.5% 2700 kJ/l 100% (reference) powder Cl < 0.1% large Cl<3 mg/Nm Gaseous Emissions HCl<10 mg/Nm Fe2O3<20 mg/Nm Fluidised Bed Pyrohydrolysis >99.5% 4100 kJ/l 110% (typical) pellets Cl < 0.01% medium Cl<3 mg/Nm HCl<10 mg/Nm Fe2O3<20 mg/Nm NOx<20ppm Number of Commercial Installations Maturity of Process >200 >50 1 under development none Hydrothermal Regeneration >99.5% 1500 kJ/l 50% (typical) powder Cl < 0.1% small

mature (40 years)

mature (40 years)

Further Development Faced with increasing fuel cost and improving environmental regulations, the main development focus in total hydrochloric acid regeneration technologies is on energy consumption and environmental compliance. Besides this process automation and control as well as sophisticated process simulation and tuning are gaining more and more attention as they heavily influence process stability, product quality, plant lifetime and plant life cycle cost.

Related SMS Demag Range of Products and Services Our range of products and services covers the whole acid regeneration plant life cycle: feasibility studies, consulting, process simulation and optimisation,

engineering, equipment supply, construction and erection, commissioning, after sales service, revamping and modernisation, dismantling and disposal.
Herbert Weissenbaeck (herbert.weissenbaeck@sms-demag.at) is a managing director and member of the technology board at SMS Demag Process Technologies GmbH, Vienna, Austria