Q&A

(2010) Question 30: What process parameters can affect alkylate T90? What are the critical variables you monitor in both sulfuric and HF units? Discuss processing schemes, feed impacts and operating variables.

The type of feed is very significant for T90. Amylenes make alkylate with higher T90 in both sulfuric and HF units. Propylene generally makes lower T90 than butylene in HF units. However, with sulfuric-catalyzed technologies, propylene can increase T90 as discussed below.

(2010) Question 31: In your experience, when sampling the HF Alky iso-recycle stream, how and where is the sample neutralized prior to analysis? Can this approach be used for online GC analysis as well?

The isobutane recycle sample can be neutralized at the sample location using a chamber filled with alumina or KOH pellets. If using a KOH chamber, it is best to add a filter downstream to filter out any fines.

(2010) Question 32: In your experience, what contributes to Monel denickelification in the HF Acid Regenerator circuit? What are the potential problems associated with this?

Oxygen is a major cause of monel denickelfication. Oxygen can enter the circuit during loading operations. Care should be taken to avoid pressuring air contained within loading pipes/hoses into the unit.

(2010) Question 33: How do refiners avoid De-isobutanizer (DIB) column/reboiler fouling in sulfuric acid alkylation? What process conditions on the column do you use to detect this fouling? What process modifications do you take to minimize the impact of this fouling?

Fouling in the DIB column is almost always caused by salt deposits. These salts are typically sodium sulfate and sodium sulfite but can also contain calcium or magnesium if the effluent treating water is not demineralized. If these water-soluble salts are present in the DIB feed, the water will evaporate once inside the column leaving the solids behind.

(2010) Question 35: What experiences do the panelists have with naphtha hydrotreater combined feed exchanger fouling? How do you monitor fouling in this exchanger service?

Feed side fouling of the NHT feed/effluent exchanger can be attributable to polymerization of olefins or diolefins. Storage of unsaturated materials from the Coker/FCC/Visbreaker may exacerbate the problem with the introduction of oxygen as a free radical that can promote polymerization.

(2010) Question 36: What are the best practices for maximizing catalyst run length in NHT units that are limited by reactor pressure drop?

Marathon’s experience with NHT fouling has been primarily corrosion products from upstream units and oxygen related polymerization of the naphtha. The use of feed filters can help minimize the effects of corrosion products. Oxygen related polymerization has impacted our NHT units from air leakage across intermediate naphtha storage tank seals and in purchased naphtha.

(2010) Question 37: Silicon poisoning of NHT catalysts has been observed in refineries without coking units. In your experience, what are the potential sources of silicon and what are the best practices to manage risk of such poisoning?

Marathon has had to deal with issues of non-coker silicon in naphtha’s since at least 2001. For background purposes, it is Marathon’s experience that silicon blocks the pores on hydrotreating catalyst and can impact catalyst activity. In severe cases, silicon breaks through to the reforming catalyst can occur where it can form silicon dioxide during the regeneration process which can cover the platinum sites.

(2010) Question 70: How can you minimize the possibility of ignition and fire in the structured packing of main fractionators after they are opened for maintenance? Do you use chemicals to improve this procedure?

Zyme-flow products have been used in our past FCC turnarounds to mitigate pyrophoric compounds as well as decrease the amount of time to hydrocarbon free the main fractionator and associated pumparound circuits.

(2010) Question 71: For the main column, "tri lines" can be utilized to monitor bottoms level. When other level instruments are being verified or have failed, what are the best operating and safety practices being employed to verify the level? What do refiners use to monitor and control level in the bottom of the main column?

For the main column, "tri lines" can be utilized to monitor bottoms level. When other level instruments are being verified or have failed, what are the best operating and safety practices being employed to verify the level? What do refiners use to monitor and control level in the bottom of the main column?

(2010) Question 72: With advance controls on the FCCU and gas plants, what are refiners doing to train new operators and keep their experienced operators sharp and ready to handle FCCU upsets and emergencies? Are refiners using simulators to help with the training and retraining?

Sunoco employs Dynamic Matrix Control (DMC) on all the FCC gas plants and DMC on reactor and regenerator systems. One FCC has a complete process training simulator, and we are in the process of installing simulators on all of our FCC’s.

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