Sulfur deactivation of nickel methanation catalysts

Journal Article · Sun Aug 01 04:00:00 EDT 1982 · J. Catal.; (United States)

DOI:https://doi.org/10.1016/0021-9517(82)90267-6· OSTI ID:6568524

Fitzharris, W D; Katzer, J R; Manogue, W H

Sulfur deactivation of supported Ni in CO hydrogenation was studied in an all-quartz internal-recycle reactor with a feed containing 4% CO in H/sub 2/. Thirteen ppB H/sub 2/S reduced the steady-state methanation activity of Ni/..gamma..-Al/sub 2/O/sub 3/ about 200-fold at 661 K; 100 ppB H/sub 2/S reduced the activity 5000-fold. A dual site Langmuir-Hinshelwood rate expression predicts both the CO partial pressure dependence and the S poisoning. Poisoning and chemisorption data indicate formation of a stable two-dimensional surface sulfide with a S:Ni surface atom ratio of 1:2 for 13 ppB H/sub 2/S in H/sub 2/ at 661 K. The surface sulfide has a free energy of formation of at least -26 kcal/mole which is 15 kcal/mole more stable than bulk Ni/sub 2/S/sub 3/. Sulfur poisoning is due to geometric effects, i.e., site blockage, rather than electronic effects since the activation energy for methanation over S-poisoned Ni was the same as that over unpoisoned Ni, 24 kcal/mole.

• Research Organization: Univ. of Delaware, Newark
• OSTI ID: 6568524
• Journal Information: J. Catal.; (United States), Journal Name: J. Catal.; (United States) Vol. 76:2; ISSN JCTLA
• Country of Publication: United States
• Language: English

Related Subjects

090121* -- Hydrocarbon Fuels-- Chemical Synthesis-- (1976-1989)
10 SYNTHETIC FUELS
ALUMINIUM COMPOUNDS
ALUMINIUM OXIDES
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CATALYSIS
CATALYST SUPPORTS
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTIONS
DATA
DEACTIVATION
ELEMENTS
EXPERIMENTAL DATA
HYDROGEN COMPOUNDS
HYDROGEN SULFIDES
INFORMATION
METALS
METHANATION
NICKEL
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
SULFIDES
SULFUR COMPOUNDS
TRANSITION ELEMENTS