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(2012) Question 43: In reforming units, what equipment could be susceptible to high temperature hydrogen attack (HTHA)? How are panelists approaching evaluation and replacement of equipment that could be susceptible to HTHA?

First, a little background: API 941 discusses high temperature hydrogen attack. At low temperatures, less than about 430°F, carbon steel has been used successfully up to 10,000 psi. But with elevated temperatures, the molecular hydrogen will dissociate into atomic hydrogen, which can readily enter and diffuse into the steel.
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Question 44: How is coke on catalyst in fixed-bed and moving-bed reforming units tracked? How is this data used to adjust the reactor inlet temperatures in order to maintain constant product octane?

In our cyclic units, just based on the air consumption, we can measure the coke each time a reactor comes out for a regen. We are not grabbing samples. Our experience with the cyclics is that if you get up around 8% coke on catalyst, the unit will be pushed a little too hard. You will then need to think about backing it down on feed rate octane, finding a better-quality feed, or possibly increasing the hydrogen/oil ratio.
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(2012) Question 45: What is the maximum allowable limit for the iron content of a reforming catalyst? Is this limit the same for semi-regenerative and continuously-regenerative catalysts?

We have seen that the maximum allowable iron on catalyst cannot be reduced to a simple number. Historically, about 3,000 wppm is the level at which we see yield start to suffer, but not every wppm of iron has the same impact on the unit. Iron deposited on the surface of the catalyst, usually from corrosion-related byproducts, tends to have less of an impact on the overall performance.
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(2012) Question 46: Are refiners modifying the operating conditions in reforming units, for example, chloride on catalyst, in order to capture margin differences between natural gas, used as fuel, and liquid products?

I will start with a bit of review of some reactions, and then I will get into a couple of examples of what we have done at HollyFrontier. Of course, the downside to reforming is that the liquid product has less volume than the feed to the unit due to physical laws inherent to the chemical reactions. First, the high-octane product will have a higher density than the feed; and second, some portion of the feed will be cracked to LPGs and fuel gas in the process.
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(2012) Question 47: How often do you replace your reformer catalyst? What is monitored, and what triggers the replacement? How has the increased spread between natural gas prices and liquid product prices impacted these decisions?

HollyFrontier operates five semi-regen reformers and two CCRs. There has not been a specific effort to replace catalyst in order to take advantage of the higher liquid product yield that is possible with newer catalyst. However, the spread between natural gas and liquids certainly impacts the decision when looking to upgrade. For two of the semi-regen units, the most recent catalyst replacements were installed after approximately 20 regen cycles, which included multiple dumping and screening events.
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(2012) Question 48: Discuss recent advances in reforming catalyst technology. What performance improvements are being researched?

The most current catalysts on the market are multi-promoted using a number of different promoters beyond the base platinum-rhenium or platinum-tin. It is not a one-size-fits-all market, so there are tailored designs for different needs. For CCRs, the current drive is for improved yields. Units are often octane-long. The goal is now to maximize barrels as best as we can.
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