Management of Spent Catalysts in Petroleum Refineries
Asian Petroleum Technology Symposium Program
On-going environmental concerns have had major impacts on the refinery industry ingeneral. First there was the response to phase out the lead in gasoline by most developedcountries, following the discovery of health hazard it poses on urban, young populationsthrough lead accumulation in their blood. Then there was the discussion in some countriesof a possible ban of an additive called MTBE (methyl tertiary butyl ether) which wasfound to contaminate groundwater through leaky underground storage tanks.Current regulations on the emission of sulfur oxides (SO
) from vehicles have pushed fuelsulfur contents to very low levels (~10 ppm in some jurisdictions). Refineries are nowfacing the formidable challenge of lowering the sulfur content in their products at a timewhen the good quality low-sulfur crude is becoming scarce. Technically, removing sulfurfrom the products during the refining stage is possible, however, the economic impactcould be substantial in terms of major process modifications needed. Another majorimpact on the refinery will be the expected increase in the need for catalyst replacementand disposal of the spent catalysts. This is because proportionally, more sulfur will reportto the catalysts that will hasten their service life through sulfur deposition.Safe disposal of these spent catalysts is a significant environmental problem as landfilldisposal is no longer generally accepted as the best practice. In many cases, the spentcatalysts have been classified as hazardous waste material and are subject to stringentdisposal guidelines. Most major refinery companies have set up special disposal practicesand only allow authorised waste collectors and processors to dispose the catalyst waste.
Metals in the Crude Oil and Catalysts
Crude oils are complex mixtures, ranging in consistency from water to tar-like solids, andin color from clear to black. An "average" crude oil contains about 84% carbon, 14%hydrogen, 1-3% sulfur, and less than 1% each of nitrogen, oxygen, metals, and salts. Crudeoils can generally be classified as paraffinic, naphthenic, or aromatic, based on thepredominant proportion of similar hydrocarbon molecules. Refinery crude base stocks mayconsist of mixtures of two or more different crude oils.Metals including nickel, iron, and vanadium are often found in crude oils in smallquantities and are removed during the refining process. Trace amounts of arsenic,vanadium, and nickel can accumulate in the pore structure of catalysts and poison theseprocessing catalysts.Fluid catalytic cracking (FCC) and hydrotreating are the major processes for convertingcrude oil into petroleum products in Singapore. FCC catalysts are ultimately contaminatedwith coke, vanadium and nickel in a manner and at a level that makes regenerationimpossible.Hydrotreating heavy oil also produces spent catalysts containing coke, nickel, andvanadium. In this instance, regeneration may be possible by selective removal of nickel,vanadium and iron, but irreversible deactivation ultimately occurs. Catalytic cracking