INSTRUCTOR: As I mentioned before, the evolution of catalytic cracking processes is really a good example of process engineering or reactor design to maximize the thermal efficiency of a process. The first cat cracking process was a batch process introduced in 1915, the McAfee process, from a Lewis acid. Aluminum chloride was used in the batch reactor system. But for commercial operation, you would need a floor reactor system. So Houdry cat cracking was the first commercial continuous process introduced in 1936.

The process used the natural aluminum silica solids particles as catalysts. And in the process, we're going to look at a configuration that has three reactors in parallel. These are fixed bed reactors essentially filled with the alumina silica pellets, packed with the alumina silica palettes as catalysts. So the gas oil feed is heated in a furnace, in a fired furnace to 800 degrees Fahrenheit, and the feed is fed from the bottom of this packed bed to go through cracking on catalyst surfaces, and the products are fed to a fractionater. In the fractionater, the products are separated into gas and gasoline and LCO, light cycle oil, as the major products from cat cracking.

As the cracking goes on, the catalysts are deactivated by coke buildup. And this happens pretty fast, within 10 minutes of the introduction of the feed into the reactor. Now, since this is an endothermic reaction, you would also imagine or could visualize that the temperature will go down as the feed moves from the bottom to the top of the reactor. So cracking isn't really very homogeneous because of this decreasing temperature.

Now, once the catalysts are deactivated within 10 minutes, all coked up, you bring in steam to strip the liquids, somewhat heavier liquids that are sticking onto the catalyst surfaces to remove them into the fractionater. And some of this will end up as heavy oil. Once this operation is finished, within about five minutes, then you bring in hot air to burn off the coke to reactivate the catalyst.

But to continue this cracking process in the meantime, while you are stripping the heavier products and reactivating the customers by burning the coke, you need to switch the feed to another reactor. So that is the second in the series. So you have a continuous feed and continuous production through the system using the swing reactor configuration, as we refer to.

The same thing happens in the second reactor. The catalyst is deactivated within 10 minutes, so you bring in the steam to strip the heavier products. And while you're doing that, obviously, and then later on, burning off the coke, you should switch the feed to another reactor. That would be the third reactor in these areas. And the products are all sent to a fractionater.

So by the time the third reactor is coked up, you can now switch the feed back to the first reactor. You will have enough time to steam strip and coke or decoke the first reactor, having these additional two reactors in the series. So that's essentially the cycle in the Houdry cat cracking reaction to enable a continuous flow system while the reactors are taken out of service for decoking operations.

You see the problem here. The endothermic reaction of cracking is decoupled, really, from the exothermic reaction of burning of the coke. So for that reason, the thermal efficiency of Houdry cat cracking is not very high, and it certainly needs to be improved.

Thermafor catalytic cracking process provided significant improvement over the Houdry cat cracking in terms of the thermal efficiency. Now, this improvement came with the change in the reactor configuration from a fixed bed in Houdry to a moving bed of catalyst now. So the catalysts are not fixed, but they are moving by gravity so that the reaction can be now conducted in just one reactor instead of having multiple reactors and switching between those reactors.

There was an improvement in the catalyst as well. Instead of using natural silica-alumina, now there are synthetic alumina-silica beads with more controlled activity, more homogeneous activity of the sites that the cracking goes on, which, of course, makes the control of the reactions better compared to the Houdry cat cracking.

So the integration of the reactor and the catalyst regenerators, as you will see, has increased the thermal efficiency very significantly over the fixed bed, the Houdry cat cracking.

Now, you can see that the feed is introduced along with the catalyst from the top of the reactors. So the particles move down with gravity at controlled flow rates along with the feed. So as the cracking goes on, on the catalyst surfaces, there is the activation. There's still coking going on, on the catalyst particles. So by the time they reach the bottom of the reactor flowing with gravity, the catalyst reactivity has been reduced to a significant extent. The catalysts are now ready to be reactivated or regenerated.

Steam, as you can see, is introduced from the bottom of the reactor to strip off all the volatile products during cracking, and the products are sent to a fractionator for separating into gas, gasoline, LCO, heavy oil, and so forth.

So the used catalysts, then, leaving the reactor is sent to a furnace where hot air is introduced to burn off the coke on the surface of the catalyst to regenerate the active sites. And the regenerated catalysts, the hot particles now, are put on bucket elevators to be sent up to the top of the reactor to close the catalyst cycles.

So the thermal integration here is such that the heat that is generated by burning the coke heats the catalyst particles. And these are hot enough to actually have the cracking take place on the surface. You can see that there is no external heater in this reactor scheme in Thermafor Cat Cracking.

But there is still more heat losses, especially in this bucket elevator system, transporting the hot catalyst particles to the top of the reactor. Thermal efficiency, although much improved over the Houdry fixed bed process, there is still a lot of room for improvement in thermal efficiency through the integration of endothermic and exothermic reactions.

SPEAKER: The Torrance refinery is a 750-acre facility located just outside of Los Angeles, California. At the time of the explosion, the refinery was owned by ExxonMobil. An important part of the refining process takes place in the facility's fluid catalytic cracker or FCC unit. In the FCC unit, heavy hydrocarbons from crude oil are broken or cracked into smaller hydrocarbons, which can then be processed into gasoline and other fuel products.

The heavy hydrocarbons are first fed into a reactor where they mix with a catalyst. The heavy liquid hydrocarbons are converted into lighter hydrocarbon vapors as they travel up the reactor. At the top of the reactor, the lighter hydrocarbon vapors are separated from the catalyst. The hydrocarbon vapors then flow to the main distillation column.

The catalyst falls down the side of the reactor, where it moves through a slide valve to a piece of equipment called the regenerator. During the reaction, a layer of carbon called coke forms on the catalyst that must be removed. Inside the regenerator, air is added, and the coke on the catalyst is burned off. The catalyst is then fed back to the reactor through a slide valve, and the cycle is repeated.

When the coke is burned off the catalyst, this creates products of combustion called flue gas. The flue gas flows out the regenerator and enters a system comprised of multiple pieces of equipment which remove any remaining catalyst particles present. The regenerator and flue gas system comprise the air side of the FCC unit.

The last piece of equipment in the flue gas system is called the electrostatic precipitator or ESP. The ESP removes small catalyst particles using static electricity. While the ESP is energized, it creates sparks, which are sources of ignition.

It is critical that the flammable hydrocarbons in the reactor do not flow into the air side of the FCC unit as this could create an explosive atmosphere. To avoid this hazard, the two slide valves connecting the reactor and regenerator are used to maintain a catalyst barrier between the pieces of equipment.

The sequence of events that eventually lead to the explosion at the refinery began on Monday, February 16, 2015, when a piece of equipment in the air side of the FCC unit called the expander vibrated forcefully enough that the refinery's control system automatically transitioned the FCC unit to a standby mode known as safe park.

During safe park mode, the flow of hydrocarbons into the reactor is turned off. The flow of air into the regenerator is also stopped. The two slide valves connecting the reactor and regenerator are closed to ensure a catalyst barrier is maintained. Steam is then forced into the reactor to prevent hydrocarbons in the main distillation column from flowing back inside.

The ESP remains energized during safe park. One slide valve however had eroded over six years of operation. And even though it closed, it could not maintain a catalyst barrier in the reactor. Within seven minutes of the unit going into safe park, all of the catalyst in the reactor fell through the slide valve into the regenerator.

A direct pathway was created for hydrocarbons to flow between the reactor and the regenerator. But the pressure of the steam flowing into the reactor as part of safe park mode was high enough to prevent hydrocarbons in the main column from flowing back inside.

With the unit in safe park mode, operators attempted to restart the expander several times but were unable to do so. Refinery personnel met to identify a strategy to repair the expander and bring the FCC unit back on line. Operations personnel predicted the expander could not restart because catalyst had likely accumulated inside.

On Tuesday, February 17, a meeting took place involving a group of refinery personnel. The group discussed a similar expander outage that occurred in 2012 for which the refinery had developed what is called a variance.

A variance is a management-approved deviation from procedure. The group decided to use the 2012 variance, which allowed a departure from the typical requirements for isolating the expander. Part of that process involved installing a blind in one of the expander's outlet flanges.

On the morning of Wednesday, February 18, Exxon Mobil maintenance attempted to install that blind but were unable to do so because steam was escaping through the open flange. Steam from the reactor had traveled through the leaking slide valve into the air side of the FCC unit.

Using the variance as a guide, the flow of steam into the reactor was decreased in an attempt to reduce the amount escaping from the expander. But the variance did not evaluate whether this flow rate was sufficient to prevent hydrocarbons from flowing into the reactor from the main distillation column.

And unknown to the operators, light hydrocarbons from a separate unit had flowed through a leaking heat exchanger into the main column, increasing pressure inside. With the flow of steam reduced and less pressure in the reactor, nothing could prevent the hydrocarbons from flowing back from the main distillation column. The hydrocarbons flowed into the reactor, where they escaped through the leaking slide valve into the air side of the FCC unit.

At 8:07 AM, a maintenance supervisor working in the FCC unit received an alarm on his personal hydrogen sulfide monitor warning him that hydrocarbons were leaking nearby. By 8:40 AM, multiple workers around the expander received the same alarm, and the FCC was evacuated.

In an attempt to mitigate the problem, a supervisor ordered the flow of steam to the reactor to be increased, but it was too late. A flammable hydrocarbon mixture was flowing through the air side of the FCC unit and moving toward the ESP with its multiple ignition sources. There the flammable hydrocarbon mixture violently exploded.

 Fluid catalytic cracking, or FCC, is the last step in the evolution of cat cracking processes-- also introduced in 1942, just like TCC or Thermafor Cat Cracking, during the Second World War in an effort to make high-octane number gasoline. Remember that high-octane number relates to high power as you can have higher compression ratios in the combustion engines.

FCC really shows an excellent integration of the cracking reactor, an endothermic reactor, with the catalyst regenerator and exothermic reactor for very high thermal efficiency. FCC is now used universally in oil refineries throughout the world-- has replaced all the previous cat cracking processes.

Now, in FCC, in the feed, that is gas oil preheated to about 300 degrees Fahrenheit-- is introduced into the reactor with steam. The riser part of the reactor where the hot catalyst particles-- as you see, the green line coming from the catalyst regenerator-- are full of dyes. The particles are full of dyes because they're smaller particles. They are full of dyes and flowing gases and vapors. So they have a huge surface area to meet the incoming feed at temperatures that are close to 1,000 degrees Fahrenheit.

So cracking reactions on these very fine particles that are full of dyes and flowing with the reactants takes place in a very short space of time, something that could be measured with seconds. And the products are sent to a fractionator after going through a series of cyclones, obviously, to separate the small fluid dyes, the particles of the catalyst.

In the fractionators, the products, as usual, are separated into gas, gasoline, light cycle oil, heavy cycle oil, and, finally, the heaviest fractions, decant oil.

Remember that LCO is used in the US for making diesel fuel through hydrocracking and hydrogenation. And decant oil could be used as fuel oil or as feedstock for making carbon black or white coking to make needle coke for graphites, electrodes.

Coming back to the reactors, the cat cracking reactor, the coked catalyst now, the end of the riser where this cracking reaction takes place, are sent through the regenerator. It's not fully coked on the surface, lost its activity. Through the red line, it's sent to the regenerator where air is introduced to burn off the coke.

The temperatures in the regenerator could reach to 1,300 to 1,400 degrees Fahrenheit. You should remember that the catalysts now are much improved, as well. It may include zeolites that would take high temperatures and very controlled reactivities through pore size distribution and so forth.

So the combustion products or flue gases from this catalyst regenerator could be sent to a CO boiler because the gas may contain significant amount of carbon monoxide, which could be burned to CO2 to provide additional heat or to generate additional heat.

So the catalysts that are now regenerated are sent to the reactor to close the catalyst cycle through that green line, as you see, to meet the incoming feed. So our catalyst cycle is pretty much complete at this point.

But note this excellent integration, thermal integration, of the catalyst regeneration, the exothermic process, with the cracking reactions where the catalysts that are heated in the regenerator are sent in a very effective manner to the reactor without much heat loss. So that is the ultimate, if you will, thermal efficiency of a process. And that's why FCC is now the universally accepted catalytic cracking process.