Corrosion of 310 stainless steel in H2-H2O-H2S gas mixtures Studies at constant temperature and fixed oxygen potential
(Previously announced in STAR as N81-19276)
Engineering topics
Publications and source records attributed to Jacob, K. T..
(Previously announced in STAR as N81-19276)
Corrosion of SAE 310 stainless steel in H2-H2O-H2S gas mixtures was studied at a constant temperature of 1150 K. Reactive gas mixtures were chosen to yield a constant oxygen potential of approximately 6 x 10 to the minus 13th power/cu Nm and sulfur potentials ranging from 0.19 x 10 to the minus 2nd power/cu Nm to 33 x 10 to the minus 2nd power/cu Nm. The kinetics of corrosion were determined using a thermobalance, and the scales were analyzed using metallography, scanning electron microscopy, and energy dispersive X-ray analysis. Two corrosion regimes, which were dependent on sulfur potential, were identified. At high sulfur potentials (p sub S sub 2 less than or equal to 2.7 x 10 to the minus 2nd power/cu Nm) the corrosion rates were high, the kinetics obeyed a linear rate equation, and the scales consisted mainly of sulfide phases similar to those observed from pure sulfication. At low sulfur potentials (P sub S sub 2 less than or equal to 0.19 x 10 to the minus 2nd power/cu Nm) the corrosion rates were low, the kinetics obeyed a parabolic rate equation, and scales consisted mainly of oxide phases.
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The stability of chromium sulfate in the temperature range from 880 K to 1040 K was determined by employing a dynamic gas-solid equilibration technique. The solid chromium sulfate was equilibrated in a gas stream of controlled SO3 potential. Thermogravimetric and differential thermal analyses were used to follow the decomposition of chromium sulfate. X-ray diffraction analysis indicated that the decomposition product was crystalline Cr2O3 and that the mutual solubility between Cr2(SO4)3 and Cr2O3 was negligible. Over the temperature range investigated, the decomposition pressure were significantly high so that chromium sulfate is not expected to form on commercial alloys containing chromium when exposed to gaseous environments containing oxygen and sulfur (such as those encountered in coal gasification).
As a part of a program for the development of a sulfur probe for monitoring the sulfur potential in coal gasification reactors, an investigation was conducted regarding the efficiency of the solid electrolyte cell Ar+H2+H2S/CaS+CaF2+(Pt)//CaF2//Pt)+CaF2+CaS/H2S+H2+Ar. A demonstration is provided of the theory, design, and operation of a solid-state sulfur probe based on CaF2 electrolyte. It was found that the cell responds to changes in sulfur potential in a manner predicted by the Nernst equation. The response time of the cell at 1225 K, after a small change in temperature or gas composition, was 2.5 Hr, while at a lower temperature of 990 K the response time was approximately 9 hr. The cell emf was insensitive to a moderate increase in the flow rate of the test gas and/or the reference gas. The exact factors affecting the slow response time of galvanic cells based on a CaF2 electrolyte have not yet been determined. The rate-limiting steps may be either the kinetics of electrode reactions or the rate of transport through the electrolyte.
The stability fields of various sulfide phases that form on Fe-Cr, Fe-Ni, Ni-Cr and Fe-Cr-Ni alloys were developed as a function of temperature and the partial pressure of sulfur. The calculated stability fields in the ternary system were displayed on plots of log P sub S sub 2 versus the conjugate extensive variable which provides a better framework for following the sulfidation of Fe-Cr-Ni alloys at high temperatures. Experimental and estimated thermodynamic data were used in developing the sulfur potential diagrams. Current models and correlations were employed to estimate the unknown thermodynamic behavior of solid solutions of sulfides and to supplement the incomplete phase diagram data of geophysical literature. These constructed stability field diagrams were in excellent agreement with the sulfide phases and compositions determined during a sulfidation experiment.
Measurements on the solid electrolyte cell (Ar + H(2) + H(2)S/CaS + CaF(2) + (Pt)//CaF(2)//(Pt) + CaF(2) + CaS/H(2) + H(2)+Ar) show that the emf of the cell is directly related to the difference in sulfur potentials established at the Ar + H(2) + H(2)S/electrode interfaces. The electrodes convert the sulfur potential gradient across the calcium fluoride electrolyte into an equivalent fluorine potential gradient. Response time of the probe varies from approximately 9 hr at 990 K to 2.5 hr at 1225 K. The conversion of calcium sulfide and/or calcium fluoride into calcium oxide is not a problem anticipated in commercial coal gasification systems. Suggestions are presented for improving the cell for such commercial applications.