Q&A

(2012) Question 53: What is the panel’s experience with addressing reforming unit stabilizer salting?

I actually have three examples that all apply to a reformer stabilizer. The first slide shows what we call our hot wash. By that, I mean we do not lower the temperatures. We will keep the bottoms re-boil temp in the 440°F to 480°F range. We then have two options on this hot wash. If we just see a high differential pressure on the overhead cooler, then we will put the water in front of that air cooler.

(2012) Question 54: Does the panel have experience chemically cleaning their reforming unit reactor circuit to minimize the lower explosive limit (LEL) when opening up equipment to the atmosphere in an effort to comply with environmental regulation? If so, is the chemical compatible with the catalyst?

HollyFrontier does not have experience using a chemical in this case. Our normal procedure involves coke burning prior to opening the reactor, and there has not been a problem with LEL in the system after that.

(2012) Question 29: How many refiners are using Layers of Protection Analysis (LOPA) in their Process Hazard Analysis (PHA) studies? How do they quantify the frequency and consequences of initiating events?

Phillips 66 has used LOPA since 2006 when we do our PHA studies. We apply it to the most severe events and use a scale of 1 to 5 for severity. So, if there is a Consequence 4 or 5, then we will apply LOPA to that event. Generally, those are the scenarios with a loss of containment component.

(2012) Question 30: How are water drains routed in alkylation units; for instance, in waterwash or propane drying services? What options exist for separation of the water and entrained light hydrocarbons? How can enclosed systems be monitored?

In many units, including both HF (hydrogen fluoride) and sulfuric acid alkylation units, there may be opportunity to drain water from vessels that contain hydrocarbon.

(2012) Question 31: What is the panel’s experience with temperature excursions (regeneration and otherwise) leading to the catalyst or equipment damage in reforming and isomerization units?

In a refinery where I used to work, our moving-bed reformer experienced a severe temperature excursion in the chlorination zone of the regenerator. After a prolonged outage on the regenerator, the unit was put back into white burns sooner than would have been recommended.

(2012) Question 32: What are the impacts of the presence of acetone in the alkylation unit feed? How is this formed in the FCC? Comment on both HF and sulfuric units.

In both HF and sulfuric acid units, acetone will consume acid, resulting in a reduced acid strength. Regarding sulfuric acid units, some documentation that I got from DuPont STRATCO indicated that one pound of acetone will consume about 10.5 pounds of acid.

(2012) Question 33: Increased feed sulfur increases acid consumption. How does it affect alkylate yield and/or alkylate properties?

In HF units, when sulfur is in the feed, it produces acid-soluble oil (ASO), organic fluorides, and polymers, which then have to be removed through the regeneration process. The light ends that are contained in this ASO can put more pressure on the regeneration system and lead to the higher acid losses. So that is the mechanism there.

(2012) Question 34: Fresh sulfuric acid fed to an alkylation unit can contain niter (nitrosylsulfuric acid) which may lead to excessive corrosion. What is niter; what does it do; can we test for it; and how can we reduce the levels in our fresh acid?

“Niter” is actually a common term referring to the amount of NOx (nitrogen oxide) or nitrates in the sulfuric acid. It is actually generated in the sulfuric acid regeneration process. One of the first steps you go through in acid regeneration is a combustion furnace. In that combustion furnace, you can generate NOx, which is really a function of your peak flame temperature and excess oxygen: the normal NOx contributors.

(2012) Question 35: Does the panel have any experience intentionally producing a ‘heavy’ alkylate stream? What are the disposition options for this stream?

Phillips 66 has one location that makes odorless mineral spirits (OMS), starting with the raw alkylate off of the deisobutanizer column. We take those bottoms through a rerun where we drive off to 340ºF, and then that stream goes right back into alkylation unit storage.

(2012) Question 36: What is the panel’s experience with the latest technologies used to control the bromine index (BI) in aromatic streams, other than clay treatment? How many units are operational, and how were these justified?

The most prevalent technologies for bromine index control are clay treating and selective hydrogenation of the olefins. At Axens, we recommend the selective hydrogenation route to control the olefins and trace diolefins that may appear in your aromatic streams. Last year at the NPRA Q&A, there was a similar question about the different reactive mechanisms between clay and selective hydrogenation.

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