Question 75: The butane stream from a catalytic polymerization (cat poly) unit, which contains 69% isobutene, 14% butylenes, and 17% normal butane, would appear to be an excellent alkylation unit feedstock, especially if isobutene is i
METKA (Sunoco, Inc.) We operate a cat poly and sulfuric alkylation unit within the same refinery. The configuration offers flexibility and synergies that allow various operating and business demands to be met. In our configuration, the cat poly debutanizer overhead feeds the alkylation unit to recover the isobutane and any remaining butylenes.
Similar to our other SPA experience, acid carryover from the effluent filtration system typically drops to the bottom of the downstream fractionators resulting in fouling and corrosion of the reboilers. Historically, we have not experienced any significant impact on the alkylation unit or sulfuric acid quality due to carryover from the cat poly unit. If carryover were to occur, we do expect that the phosphoric acid would be more of a corrosion and fouling concern than an acid consumption issue.
Below is a plot that basically shows the way in which the plants are configured. The BB is treated and split to the cat poly and alky units in parallel. Once we recover the C4s off the backend of the cat poly plant, the stream is fed back into the alkylation unit.
Gasoline ProcessesGasolineProcessesFCCDebutDepropBtmsCat GasolineC4,C4=PolyTreaterAlkyContactorsDepropDebutDepropBtmsLPGPolymer GasolinenC4,iC4ContactorEffluentDIBDebutnC4/AlkylatenC4AlkylateMake-up C4iC4PolyAlkyFCCGasolineMixed ButaneiC4nC4Rxr EffluentTreated C4, C4=EffluentTreatingPolyRxrs (FUNKY GRAPHIC)
ZMICH (UOP LLC) I have three points that I would like to make.
1) UOP does not have experience with traces of phosphorus in the alkylation unit feed.
2) UOP strongly recommends avoiding the possibility of phosphorus in the feed. The reason for this is that a combination of mineral acids will lead to a more aggressive corrosion than either of the two acids by themselves.
3) From a commercial perspective, UOP is aware of at least one refinery that feeds cat poly stream with feed from an FCC to an alkylation unit, and the process flow is shown in words as such: “Process flow is a stream goes through a water wash to remove phosphoric acid, the sand tower acting like a coalescer, and a UOP MeroxTM unit to remove sulfur before going to the alkylation unit.
Question 45: What are the procedures/rules governing the transportation and disposal of catalyst contaminated with arsenic, mercury, barium, or other heavy metals? Are there maximum limits for any of these?
SHARPE (Flint Hills Resources, LP)
The spent catalyst needs to be shipped offsite and sent for metals reclamation or disposal. If it is going for disposal, it will have to be characterized to determine if 1) it is a hazardous waste, which it is most of the time, and 2) it meets the applicable Land Disposal Restrictions (LDRs). It would have to be treated, as part of disposal, to meet the LDRs.
Regarding transportation, if the catalyst needs to be shipped offsite for reclamation, it will have to be determined if it is hazardous material or contains hazardous substance. So by default, spent catalysts generally fit into that category. Take a look at the Hazardous Materials’ Table listed on the slide.
Overall, there are no maximum limits for disposal or transportation, but the catalyst does have to be transported and disposed of properly. It ends up being classified as a hazardous waste and subject to all the laws regarding that classification.
CHRIS STEVES (Norton Engineering)
The transportation and disposal of spent catalysts are governed by DOT (Department of Transportation) and RCRA (Resource Conservation and Recovery Act) regulations. A spent catalyst with leachable levels of arsenic, mercury, or barium (or five other regulated heavy metals) above their TCLP limit, will be regulated by the U.S. EPA (Environmental Protection Agency) as RCRA hazardous waste. If the material is spent hydrotreating catalyst from the petroleum refining industry, it will automatically be regulated as RCRA hazardous waste regardless of the metals content. Regulated RCRA hazardous waste must be properly disposed of at an approved treatment, storage, and disposal facility (TSDF). The actual levels of contamination will affect the options and cost for disposal. All RCRA hazardous wastes are regulated as DOT hazardous materials when shipped offsite, and all the basic rules for hazardous materials shipment must be followed.