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Nov-2015

Catalyst selection – a refiner’s perspective

The refining industry is fortunate to have the catalyst suppliers as our partners. They have been leaders in developing new technology for refining.

George Hoekstra
Hoekstra Trading

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Article Summary

Some of their innovations have been worth billions. Let’s look at one story of a billion dollar innovation. This story begins in 1998. It was a time of oil industry layoffs, mergers, and restructurings. The refining business was starving for profits. This was the environment in 1998, when Akzo Nobel introduced their STARS hydroprocessing catalysts.

STARS catalysts

Figure 1 is an excerpt from a 1999 Akzo NPRA paper published shortly after the rollout of their STARS catalyst KF 757.

The chart shows reactor temperature versus time for a commercial diesel hydrotreater. The blue data show an unmistakable improvement for the new KF 757 STARS catalyst, compared to the previous catalyst. It’s rare to see such clear separation in commercial data. This unit was on its way to doubling cycle life.

When Akzo rolled out STARS in 1998, they released a lot of pilot plant and commercial data that made it very clear this was a breakthrough innovation.  Four years later, in 2002, STARS catalysts were in 60 commercial units.

Then in 2004, when ultra-low sulphur diesel came in the USA, STARS catalysts and similar competitive products swept through the industry by stampede, in what was to be a billion dollar innovation.

Type II catalysts

The name STARS is an acronym, it stands for Super Type II Active Reaction Sites. The science behind STARS involves forming a stable cobalt moly disulphide nanostructure called a Type II reaction site. Type II technology is what made STARS a breakthrough; and to really understand the story of this billion dollar innovation, we have to turn the clock back further, to research done by Haldor Topsoe in the 1980’s.

Figure 2 is an excerpt from a 1984 Haldor Topsoe paper presented at the 9th Iberoamerican Symposium on Catalysis, Lisbon, Portugal, July 16, 1984. There are 2 lines on the chart; the lower line is labelled Type I, and the upper line Type II.

I will read the text below the chart, it says, quote “It is observed that all the data group along two lines, suggesting the existence of two types of Co-Mo-S, which in the following will be termed Type I and Type II. It is interesting that the high temperature form (Type II), has a higher specific activity per Co atom, than the Type I.” End quote.

I believe this is the first time the term “Type II” ever appeared in print with reference to the high activity of Type II active sites. The steep slope of the “Type II” line showed the connection between the “Type II” nanostructure and its high activity. That discovery by Haldor Topsoe in 1984 laid the foundation for a billion dollar innovation.

So in fact the stampede that occurred in 2004 should be called the Type II catalyst stampede. It was a billion dollar innovation that eventually involved all the catalyst suppliers and all refiners, and swept the entire market.

Still today our industry is benefiting from Haldor Topsoe’s discovery of Type II activity in 1984, from Akzo and Albemarle’s great commercial innovation of STARS catalysts in 1998, and from the work of all the catalyst suppliers who continue to develop and deliver improved catalyst technology to the industry.

I will come back to this story of Type II catalysts shortly. But first, let’s fast forward to 2014, and look at today’s catalyst market from the refiner’s perspective.

21st century catalysts - A refiner’s perspective
Today there is an abundance of catalyst brands. Figure 3 shows a partial list of names you’ll hear if you start shopping for hydroprocessing catalysts. Within most brands, there are several different flavours of products. By flavours I mean, for example, CoMo or NiMo, high density or low density, high metals or low metals, trilobes or quadrilobes, and stacked beds.

When you take all the brands and multiply by all the flavours, you have 200 options.
If you were a busy process engineer needing to select catalyst, how would you deal with 200 options that are presented to you with conflicting claims? From your perspective, it looks bewildering. You would be forced to simplify things.

You could stick with the incumbent. That is simple, safe, sure, the path of least resistance.
You could try something new, but that seems like “rolling the dice” when you have so many options and no basis to judge the conflicting claims.
Or you could do some independent testing. That option is being used increasingly today, and it is more accessible than ever before.
 
Independent testing
These pilot plants are used for independent catalyst testing at the company called C Solutions LTD. in Thessaloniki, Greece. They are designed specifically for side by side independent testing of competitive hydroprocessing catalysts, and they run around the clock for only that purpose.
 
Site-specific proprietary projects
C Solutions does lots of site-specific proprietary projects for refiners. Each site-specific project is sponsored by a single client, usually for a specific VGO or hydrocracking unit that requires a tailored test program.

With a site specific proprietary project, you send two drums of your unit’s feed and four candidate catalysts to C Solutions, one of your people will work with C Solutions to plan and oversee the tests, C Solutions will run the program on your feed and you will draw your conclusions.


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