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Management of Spent Catalysts in Petroleum Refineries
Asian Petroleum Technology Symposium Program
David T. LiangDeputy DirectorInstitute of Environmental Science and EngineeringSingapore
Catalysts are indispensable in the petroleum refining and petrochemical industry forroutine production of gasoline, diesel fuels, jet fuels, heavy oil hydrocarbons,petrochemicals and plastics. Hydrocarbons (HT and HDS) and residue hydro-desulfurization (RDS) are the major processes for converting crude oil into these petroleumproducts. During processing, catalysts will become contaminated with impurities in thecrude oil feed and become deactivated. When that happens, they are usually sent forregeneration where contaminates are removed. Ultimately, they will be contaminated withcoke, sulfur, vanadium and nickel in a manner and at a level that makes regenerationimpractical. At this stage, catalysts are considered
and they may pose significantenvironmental problems, as landfill disposal is no longer accepted as best practice.Hydro-desulfurization (HDS/RDS) of heavy oil produces spent catalysts that containmolybdenum (Mo), vanadium (V), nickel (Ni) or cobalt (Co) at concentration levels thathas been found to be economical for recovery. Due to its complex nature, metal recoveryfrom HDS/RDS spent catalysts involves a combination of pyro- and hydro- metallurgicalprocesses. At present, only a handful of companies are capable to do so on a commercialscale and in an environmentally acceptable manner. The energy savings and environmentbenefits associated with these recycling activities are also quite significant. It has beenestimated that recycling of various metal scraps consumes approximately 33% less energyand generates 60% less pollutants than the production of virgin material from ore.However with increasing demand of ever more complex metallic composite and alloymaterials in modern manufacturing processes, it becomes imperative to developappropriate methods for the recovery of these valuable metals.The present paper will provide a brief overview of the management practices and recoveryof metals from spent catalysts, with the focus on the technologies, issues and opportunitiesassociated with the recycling of valuable metals. Potential impacts of issues such as theBasel Convention and environmental legislation are also highlighted.
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
Management of Spent Catalysts in Petroleum Refineries
Asian Petroleum Technology Symposium Program
 3/11breaks complex hydrocarbons into simpler molecules in order to increase the quality andquantity of lighter, more desirable products and decrease the amount of residuals.Catalytic cracking is similar to thermal cracking except that catalysts facilitate theconversion of the heavier molecules into lighter products. Use of a catalyst in the crackingreaction increases the yield of improved-quality products under much less severe operatingconditions than in thermal cracking. Typical temperatures are from 850-950 degrees F atmuch lower pressures of 10-20 psi. The catalysts used in refinery cracking units aretypically solid materials (zeolite, aluminum hydrosilicate, treated bentonite clay, fuller'searth, bauxite, and silica-alumina) that come in the form of powders, beads, pellets orshaped materials called extrudites.
Fluid Catalytic Cracking
The most common process is FCC, in which the oil is cracked in the presence of a finelydivided catalyst which is maintained in an aerated or fluidized state by the oil vapors. Thefluid cracker consists of a catalyst section and a fractionating section that operate togetheras an integrated processing unit. The catalyst section contains the reactor and regenerator,which with the standpipe and riser forms the catalyst circulation unit. The fluid catalyst iscontinuously circulated between the reactor and the regenerator using air, oil vapors, andsteam as the conveying media.A typical FCC process involves mixing a preheated hydrocarbon charge with hot,regenerated catalyst as it enters the riser leading to the reactor. The charge is combinedwith a recycle stream within the riser, vaporized, and raised to reactor temperature (900-1,000 degrees F) by the hot catalyst. As the mixture travels up the riser, the charge iscracked at 10-30 psi.Spent catalyst is regenerated to get rid of coke that collects on the catalyst during theprocess. Spent catalyst flows through the catalyst stripper to the regenerator, where most of the coke deposits burn off at the bottom where preheated air and spent catalyst are mixed.Fresh catalyst is added and worn-out catalyst removed to optimize the cracking process.
Treatment Processes
Throughout the history of refining, various treatment methods have been used to removenon-hydrocarbons, impurities, and other constituents that adversely affect the properties of finished products or reduce the efficiency of the conversion processes. Treating caninvolve chemical reaction and/or physical separation. Typical examples of treating arechemical sweetening, acid treating, clay contacting, caustic washing, hydrotreating, drying,solvent extraction, and solvent dewaxing. Sweetening compounds and acids desulfurizecrude oil before processing and treat products during and after processing. Following theSecond World War, various reforming processes improved gasoline quality and yield andproduced higher-quality products. Most of these involved the use of catalysts and/orhydrogen to change molecules and remove sulfur. A number of the more commonly usedtreating and reforming processes are described in this chapter of the manual.

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