Converting Hydrogen Sulfide by the Claus Process

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Hydrogen sulfide (H2S) is a smelly, corrosive, highly toxic gas. Besides its other bad habits, it also deactivates industrial catalysts. H2S is commonly found in natural gas and is also made at oil refineries, especially if the crude oil contains a lot of sulfur compounds. Because H2S is such an obnoxious substance, it is converted to non-toxic and useful elemental sulfur at most locations that produce it. The process of choice is the Claus Sulfur Recovery process.

Description of the Claus Process

First the H2S is separated from the host gas stream using amine extraction. Then it is fed to the Claus unit, where it is converted in two steps: 1. Thermal Step. The H2S is partially oxidized with air. This is done in a reaction furnace at high temperatures (1000-1400 deg C). Sulfur is formed, but some H2S remains unreacted, and some SO2 is made. 2. Catalytic Step. The remaining H2S is reacted with the SO2 at lower temperatures (about 200-350 deg C) over a catalyst to make more sulfur. A catalyst is needed in the second step to help the components react with reasonable speed. Unfortunately the reaction does not go to completion even with the best catalyst. For this reason two or three stages are used, with sulfur being removed between the stages. Engineers know how different factors like concentration, contact time and reaction temperature influence the reaction, and these are set to give the best conversions. The reaction is as follows: 2H2S + SO2 ==> 3S + 2H2O Inevitably a small amount of H2S remains in the tail gas. This residual quantity, together with other trace sulfur compounds, is usually dealt with in a tail gas unit. The latter can give overall sulfur recoveries of about 99.8%, which is very impressive indeed.

Sulfur Production by the Claus Process

Process Improvements
Over the years many improvements have been made to the Claus process. Recent developments include:
SUPERCLAUS (TM).

A special catalyst in the last reactor oxidizes the H2S selectively to sulfur, avoiding formation of SO2. Significantly higher conversions are obtained at modest cost. Oxygen Claus. The combustion air is mixed with pure oxygen. This reduces the amount of nitrogen passing through the unit, making it possible to increase throughput. Better Catalysts. Higher activities have been achieved with catalysts that provide higher surface areas and macroporosity.

More improvements can be expected. Here are some possibilities. CS2 destruction. Carbon disulfide (CS2) is a side product made in the furnace. Laboratory work has shown that special catalysts operating in the furnace can destroy the CS2 before it gets into the catalytic section. A commercially available catalyst like this might be developed for use in a Claus plant. Catalyst Temperature Policy. The conversion of H2S goes faster at higher temperatures, but a more favorable equilibrium is obtained at lower temperatures. It isn't obvious whether higher or lower temperatures are needed in the third converter. Kinetic modelling may supply the answer, thereby improving conversion or reducing catalyst replacement cost.

Other Ways to Process Sour Gas

Some H2S-containing gas is unsuitable for treatment by amine extraction because of high CO2 levels. These streams often lend themselves to processing by so-called

liquid redox processes such as SulFerox or ARI-LO-CAT. Instead of air, these processes use a liquid solution containing oxidized iron. Several novel processes are being developed to make hydrogen as well as sulfur from H2S. These are sometimes called H2S splitting processes. Hydrogen is a valuable gas that is needed in oil processing and for the manufacture of ammonia and methanol

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Sulfur Recovery Unit (SRU)

H2S removed in the AGR process is sent to the sulfur recovery unit (SRU) as acid gas. SRU recovers H2S as elemental sulfur through the Claus reaction (see the attached figure). Reactions occur in two stages: the flame reaction stage and the catalytic reaction stage. The former consists of a high-performance burner, mixing chamber, and heat removing boiler, while the latter has two to three reactor stages. The sulfur recovery rate of the Claus process is about 95 to 97%. The tail gas that contains unrecovered sulfur is fed to the tail gas treating unit (TGT). The recovered sulfur is stored in the sulfur pit and shipped as product after undergoing a degassing process to remove H2S. The Claus process is an equilibrium process, and a modified version of it with direct oxidation catalysts stored in the final stage is called SUPERCLAUS. Since this improved process does not depend on Claus equilibrium, it can attain a 99% recovery ratio without TGT (Licensor: Jacobs Comprimo).

It is important for the Claus process that appropriate burners be selected and use the right catalysts to ensure high recovery rate and long service life. For a licensed process, the licensor does such selection and design, but in other cases, Chiyoda Corporation can do the design work by ourselves as we have sufficient knowledge and experience to design the unit such as to select burners and catalysts and design mixing chambers, etc. The SUPERCLAUS process that features 99% recovery without TGT is a unique process and Chiyoda Corporation has plenty of experience in and out of Japan.