Hydrochloric Acid: Corrosion under Control

URSULA LIECHTI URS HALLER SULZER CHEMTECH The distillation, concentration and purification of hydrochloric acid (HCl) places stringent requirements on engineering and process engineering: As an aqueous solution, HCl is highly corrosive; accidents or damage in plants can have tremendous economic and ecological consequences. The employment of suitable corrosion-resistant materials is therefore vitally important. With the experience that it has acquired over many years, Sulzer Chemtech is now a competent supplier of HCl distillation plants.
Hydrochloric acid results as a by-product or waste product in a gaseous or liquid form in various processes of the chemical industry and environmental engineering (Fig. 1s). But seldom in a pure form it is usually aqueous solutions with hydrochloric acid concentrations of between 18 and 24%. In addition, there are contaminations caused through various by-products, in particular salts and organic compounds. In general, this hydrochloric acid cannot be

1s Typical fields of application for the concentration of hydrochloric acid are chemical reactions with chlorine, where hydrochloric acid is produced as a by-product, the chlorination of alcanes and the purification of waste gases in environmental engineering.

Pure H2O Parent material Reaction HCl aqueous (waste product) Product Pure HCl gas Distillation

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recycled as such any more and therefore has no market value. Furthermore, it cannot be disposed by way of the waste-treatment plant, because the concentration is too high; the neutralization and clarification of the hydrochloric acid results in a high salt load and also additional costs. Nevertheless, it can be used again if the acid is concentrated and purified. Various techniques are applied for this, depending on the desired yield of hydrochloric acid or the required degree of purity. Sulzer Chemtech has experience with both the calcium chloride (CaCl2) and the double-pressure process. The following describes the demanding double-pressure process in detail.

TWO STAGES TO SUCCESS

With the double-pressure process, one each pressure and vacuum columns are connected in series (Figs. 2s and 3s). The 1525% hydrochloric acid is separated at a pressure of 46 bar and a temperature of up to 160 C in the pressure column. The head product, HCl gas, can be used further, namely directly or dried and compressed for reactions, or with the aid of an absorber, processed to a commercial aqueous solution with water. The bottom product, an azeotropic hydrochloric acid mixture, cannot be separated any further through normal distillation (see box, p. 36). This bottom product is now routed to the vacuum column. As a result of the underpressure, the azeotropic point is displaced to such an extent that highly concentrated hydrochloric acid (about 22%) is

obtained as bottom product. Water with a low content of hydrochloric acid in the ppm range is produced as head product. The 22% hydrochloric acid is returned to the pressure column again via the circuit. This technology places enormous demands on the process-engineering system and also the employed materials. In the last few years, Sulzer Chemtech has concerned itself intensively with the process of hydrochloric acid distillation by means of the double-pressure system, and therefore possesses the know-how needed for the design and construction of these plants. Different materials are employed depending on the field of application. The corrosion-resistant reaction of the materials differs with the various pressures and temperatures. Since the stability of the material cannot be calculated, a wealth of practical experience is needed to select the correct materials for the construction of such a plant (Fig. 4s). This applies not only to the column jacket and the pipework, but also to the packings (Fig. 5s) and the column internals. Sulzer Chemtech has developed a broad spectrum of diverse materials over the years, which can be employed in a goal-oriented manner. Depending on the contaminations, temperature and required throughput, the appropriate version can be selected in graphite, various plastics, ceramic, etc. The requirements for the elements of the measuring section, e.g. thermocouples, pressure pick-ups and

2s A plant designed according to the double-pressure system with vacuum and distillation columns.

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3s The double-pressure distillation system for hydrochloric acid produces pure HCl gas without any contamination through by-products.

Vacuum column HCl >22%

Pure H2O

Pure HCl gas 56 bar, 160 C

HCl ~28%

valves, are complex. Questions concerning the thermal conductivity, permeation, sealing and safety of operation have to be considered during the selection of the appropriate components.

DIFFERENT MATERIALS, DIFFERENT PROBLEMS

The processing of hydrochloric acid is always associated with the same problems. The acid is very corrosive even in the diluted form and leads to severe corrosion of the majority of materials employed in chemical plants within a short space of time. In general, the problems of corrosion become more

serious with higher temperatures and pressures. With normal highquality steel and a temperature of 160 C, for example, up to one centimetre is etched away every 10 minutes. Acid-resistant materials also react to contaminants frequently in an unforeseen manner. The chlorine content of hydrochloric acid has a devastating effect on graphite heat exchangers, and even traces of organic solvents can attack plastics. A high proportion of water in the pressure stage (at 46 bar) of a hydrochloric acid distillation plant can destroy stoneware and porcelain, and even glass and enamel.

THE AZEOTROPIC POINT OF HYDROCHLORIC ACID

A mixture is azeotropic when the composition of the vapour is the same as that of the liquid. This mixture behaves like a pure substance and cannot be separated into its constituents by means of conventional distillation. With hydrochloric acid in aqueous solution, the azeotropic point is approximately 20%. It can be reduced to a lower value through overpressure and brought to a higher value with underpressure. There is hardly any indication of the existence of the azeotropic point at higher pressure in the literature open to the public. Marked deviations can occur through contamination of the aqueous hydrochloric acid. The exact values can only be determined in each case by means of experiment. Sulzer Chemtech has acquired the respective experience through its work with hydrochloric acid processes over many years.

4s Simulation of a typical case of damage during the processing of hydrochloric acid: structured packing made of apparently corrosion-resistant steel, destroyed by corrosion.

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5s The packing (photo: a Mellacarbon packing from Sulzer Chemtech) is a key component in the HCl distillation column.

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On the other hand, the same materials have stood the test at a lower temperature in the absorption stage. The high temperatures lead to clearly faster corrosion rates, and the resultant leakages can result in the most severe damage, with the respective consequences for human beings and the environment, as well as additional costs for the loss of production. Operational safety and the reliability of the distillation columns are therefore matters of great concern for the operator. But the safety of the plants can be guaranteed if the materials are selected correctly.

SELECTION OF THE MATERIALS DECISIVE

The material can only be chosen in intensive co-operation with customers, suppliers and the plant constructor. At the same time, all the relevant aspects have to be considered it is here that reliability, safety and the life cycle of the plant are decided. It is true that various special materials which have been employed hitherto have a high corrosion resistance, but they are also very expensive and difficult to work. For example, metals such as tantalum, niobium and zirconium are just as expensive as gold; but they are very difficult to process, and there are only a few specialists in the world who can master this. Tantalum of a thickness of only a

few millimetres, for instance, is used quite frequently as a lining in the columns. In view of its high melting point, it is very difficult to weld together. Teflon is also difficult to process. When Teflon with its low melting temperature is welded together, it has to be made with a fully protective mask, because highly toxic vapours are released during the welding operation. In the last few years, Sulzer Chemtech has made great efforts to find materials that can withstand the chemical exposure and physical stress, and are also more economic than those employed hitherto with success; and the developments continue. To ensure that customers can concentrate hydrochloric acid economically in plants with high operational safety.

FOR MORE DETAILS

Sulzer Chemtech AG Urs Haller, 0600 Postfach 65 CH-8404 Winterthur Switzerland Telephone +41 (0)52-262 37 98 Fax +41 (0)52-262 00 76 E-mail urs.haller@sulzer.com

METAL, PLASTIC OR CERAMIC?

The material to be used depends on various factors and is decided from case to case. The selection can be made from three principal groups: plastics, metals and ceramic. Plastics For low temperature: Polypropylene Glass-fibre reinforced plastics (GRP): new materials for this field of application For higher temperatures: Various representatives of the Teflon family, e.g. PFA, PTFE, ICTFE, which differ, above all, through their thermal stability Metals Corrosion-resistant steel (possibly with PTFE liner) Tantalum Zirconium Niobium Graphite Ceramic materials Very suitable for high gas temperatures; with liquids, however, only in relatively low temperatures.

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