3/9/2017 Gibbs vs.

Reactor de Equilibrio

Gibbs vs. Reactor de Equilibrio

Con el fin de ahorrar tiempo y hacer posible que usted campare los resultados de los diferentes reactores,
este ejemplo comenzará usando los mismos componentes y reacciones que se emplearon en el Ejemplo de
Reactor de Flujo de Enchufes . Se recomienda, pero no es necesario, que trabaje primero con ese ejemplo (o
al menos eche un vistazo a la lista de componentes y reacciones). Si no tiene una versión propia de ese
ejemplo para iniciar este ejemplo, he puesto a disposición una versión completa de ese ejemplo titulado
PlugFlowEx.hsc ubicado en el directorio \\ Hartsook \ Hysys \ SAMP403directorio. También hay un
archivo que contiene este y todos los demás ejemplos completos del reactor llamados AllReactors.hsc en el
mismo directorio.

El Reactor de Gibbs
Comenzaremos con la instalación del Reactor Gibbs. Configure su diagrama de flujo de proceso (PFD)
como se ve a continuación (recuerde que el botón <Ctrl> es ideal para una conexión rápida, ya que cambia
entre el modo de conexión y el modo de conexión). El Reactor Gibbs está disponible en el menú de
Operaciones de la Unidad o desde la Paleta de Objetos pulsando el botón Reactores Generales

que abre este menú . Presione para el Reactor Gibbs.

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Note that it is not necessary to attach a liquid product stream to the reactor. All of the reactors may be run
with only one product stream (vapour or liquid). Should both phases be present in the product and only one
or the other product stream available, HYSYS will tell you it needs another product stream. At that point,
you must add another stream, but do not be dismayed. Remember, you can always mix them back together
again. Also note that you may add an energy stream to the reactor. That we have not indicates that we intend
the reactor to be adiabatic.

Since we desire the Gibbs Feed stream to be the same as the Plug Flow Feed stream, the easiest method is
to double-click on the Gibbs Feed, opening the property view, and switch to the Utilities Page. There, press
the button marked "Copy Stream Specs From ..." and choose the Plug Flow Feed stream.

You'll find that this is all that is required for the Gibbs reactor to work. If you so wished, you could now
open the reactor's property view and add a pressure drop on the Parameters Page. You can also switch to
the Reactions Page where you will see a couple more options. Currently selected should be Gibbs
Reactions Only. This is the choice that gives total equilibrium of all components (excluding those labeled
Inert, or otherwise specified, on the Composition Page). Below that is Specify Equilibrium Reactions,
the option that allows you to attach an equilibrium reaction set. We shall return to this option later in the
example. The last option is to have No Reaction occur at all. The reactor then would simply act as a
separator (provided both vapour and liquid product streams were connected).

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Changing nothing, however, we find our product stream looks like this

Note these are extremely different results than we obtained in the Plug Flow Example. The main difference
is that where in the PFR the reforming reaction was not occuring, here it is occuring in great quantity,
backwards. At this temperature, the equilibrium is to the left (something we did not even allow for in the
kinetic equations we defined for the reforming reaction), and methane is formed in what is called the
Sabatier reaction (same reaction, two names, go figure. We are ready to start putting in the Equilibrium
Reactor.

The Equilibrium Reactor

We cannot install a working equilibrium reactor without first creating the reactions it will use. Therefore
the first thing you must do is enter the basis environment. On the Simulation Basis Manager, switch to the
Reactions Page (close any other windows that might have been left open there). Before continuing any
further, if they are not already, I suggest that you change the names of the existing two reactions to
ReformingLH and WGSkin for consistency with my examples and to prevent confusion later (you will
begin to collect many very similar reactions). You should also probably change the name of the reaction set
containing those reactions to Kinetic. That completed, your window should look something like this

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Now, in the Reactions Sub-Group, press the Add Rxn ... button. Choose Equilibrium Reaction and
name the reaction that appears ReformormingEq. Since this is a very common reaction of interest, before
beginning to fill out coefficients we will check the Library Page to see if it is already stored in HYSYS.
Luckily for us, it is, as no one was kind enough to provide us with any equilibrium data on this reaction. As
you can see it is second on the list and the Water Gas Shift reaction that we will be adding next is first.

Highlight the reforming reaction and press the Add Library Reaction button. You will find the reaction
is now completely defined. HYSYS inputed for you a table of Keq vs. Temp values (from which it also
fitted the equation it uses to interpolate and extrapolate -- speaking of which, be aware of the temperature
range of the table from which HYSYS will draw its information). To learn more about ways of inputing
your own data into the form read the section on Equilibrium Reactions back on my Reactions page or
Section 11.3.3 of RV1.
Now that we are done with the reforming reaction, close this window and add a new equilibrium reaction
called WGSeq. Again, go to the Library Page and choose this time the first reaction on the list. Close the
window of the completed second equilibrium reaction.

Our next job is to create a reaction set for our two new reactions. Though, HYSYS will allow you to put
kinetic and equilibrium equations in the same reaction set (see the General Reactor), you could not put these
in the same reaction set with the others because they refer to the same two reactions (evaluated in different

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ways). Create a new reaction set from the reactions page of the Simulation Basis Manager and call it
Equilibrium. Add the two reactions you just created to the active list. It should now look like this:

Close the window. Back again on the Simulation Basis Manager, highlight the reaction set you just created
and push the Add to FP button as we must associate the reaction with our fluid package before it can be
used in the flowsheet. There should be only on fluid package listed (if there is more than one, pick the one
that is used on your main flowsheet). Select it, then push Add Set to Fluid Package. The completed
Reactions Page of the Simulation Basis Manager should look like this:

Note the Assoc. Fluid Package box only shows those Fluid Packages associated with the highlighted
reaction set.

You may now return to the simulation environment as we are ready to install the equilibrium reactor.

The Process "Switch"

Rather than simply create another feed stream for the Equilibrium Reactor copied from the PFR or
Gibbs Reactor, let us assume that you wish to compare the results of the two different reactors on the rest of
an involved process. You could simply use Save As to make a copy of the file and substitute one reactor for
the other, but that makes comparison of results difficult and cumbersome. You could also use the Logical
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Operation Balance to dynamically copy the feed to one reactor to another stream which would then become
the feed to the other reactor. That way you can have the upstream of the plant duplicated to both reactors on
the same flowsheet. Unfortunately, to get the downstream part of the plant, you would have to copy every
stream and unit, a difficult prospect in itself, which would clutter your PFD, and then you would have to
make every future adjustment to the downstream section twice, a tedious business at best and heaven help
you if you have a downstream stream affecting an upstream stream. Basically, this option is out for any but
the simplest of flowsheets or unless you only care about the immediate output after the divergence.

Your last, and I think best option (though there are times when a Save As might well be the most
expedient solution), is a technique which I find HYSYS well suited to take advantage of, but which I found
curiously missing from the manuals. I call it the Process "Switch". It takes advantage of a lesser used option
in the preferences allowing you to make multiple connections to the same stream and the ability of HYSYS
to "ignore" unit operations without you deleting them.

Therefore to start, open the Preferences from under the Tools menu. On the first page, marked
Simulation, check the box marked Multiple Stream Connections. You may then close the Preferences
window.

Since there is no point tempting fate by upsetting HYSYS and to make things clearer to you, we will go
ahead and make HYSYS ignore the Gibbs Reactor. Open that reactor's property view and switch to the
Parameters Page. Check the box that says Ignore This Unit Op During Calculations. The reactor should
now turn yellow and the product stream to a pale blue, indicating it is not solved.

It is time to place the Equilibrium Reactor on the PFD. Either do so from the Unit Ops Menu or as
follows from the Object Palette.

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Push which opens this menu . Press for the Equilibrium Reactor.

Your PFD should look something like this:

Now from the Equilibrium Reactor's Property View, go to the Connections Page and for the Feed stream,
go to the drop down menu and choose FeedG or whatever you called the feed to the Gibbs Reactor (if you
had not already changed the multiple streams option in the preferences, that feed stream would not be a
listed option). Now if you were to go right to the Vapour Outlet and attempt to connect ProductG, you
would get this error:

I believe this is due to the similarity of the two units you are trying to "switch" out. When I tried this first
with a Gibbs Reactor and a PFR, I did not get the error. There is an easy way around it, however. Simply

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attach a valve with zero pressure drop (don't forget this) to the Equilibrium's Vapour Outlet, then
in the valve's property view, set the outlet to be ProductG or whatever you called the Gibbs Outlet.

Note: When I was experimenting with the "switch" and the PFR, the PFR began having trouble
doing its integration and I was forced to set the segment initialization to Re-initialize for it to
work.

When you are finished connecting, your reactors should look like this:

Now all that remains is to specify the Equilibrium Reactor. All you need to do is open the Equilibrium
Reactor Property View, move to the Reactions page and attach the Equilibrium Reaction Set. HYSYS will
do the rest.

You may now switch back and forth between the two reactors. I recommend that you try to have one of
the two "ignored" at all times (though in this simple case nothing crazy happens and you should observe
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what happens if you break this "rule"), thus you would start a "switch" by going to the Parameters Page of
the Equilibrium Reactorand setting it to be ignored. Then go to the Gibbs Reactor and remove the command
to ignore.

If you examine the product stream as you are switching back and forth, you will see that the results of
the two reactors, as they are currently configured, are almost identical. This kind of confirmation is good to
see as the reactors go about this calculation in completely different ways. You can see this for yourself by
going into the reaction manager and changing one of the equilibrium reactions (or a copy) to have a fixed K
of, say, 1. (I leave it to you to remember how to do it). You will then find that while the results for the
Equilibrium Reactor change drastically, the Gibbs Reactor continues to give the same "correct" values. This
same technique can be used later to show that when an equilibrium reaction set is attached to the Gibbs
Reactor, that it is truly only taking the stoichiometry info.
Another important thing to note about the similar results is that the thermodynamic property set we are
using is Antoine. This is one of the thermodynamic packages that has essentially ideal vapour and liquid
phases. You'll find that if you change your thermo package to one of the non-ideal ones, like Peng-
Robinson, that the results of the Gibbs Reactor begin to diverge from those of the Equilibrium Reactor
(remember the equalibrium reactions set Keq as a function of T only). More so in other examples than this
one. (You may also have noticed that for whatever reason, the PFR takes a lot longer to re-calculate in
Antoine than in PR). To see a case where the difference caused by the thermo package is more severe see
the file called methpuz.hsc in \\Hartsook\Hysys\SAMP403.

Now we are ready to experiment with attaching reactions to the Gibbs Reactor. Open its property view
and go to the Reactions Page. Switch the Reactor Type to Specify Equilibrium Reactions. Try attaching
one of the reaction sets to the reactor. You probably were not suprised to see that you could not select the
Kinetic set, but you might have been suprised to discover that you also could not attach the Equilibrium
set! Located down at the bottom, in the Trace Window, is this explanation:

"There is no need to specify reactions if all of them are equilibrium type. Gibbs Reactor will
take care of attaining equilibrium by itself"

Remember that in the standard setting on the Gibbs Reactor, the reactor will solve for the equilibrium of all
possible reactions (element balance is maintained). As it turns out, with the limited number of components
in this example, the two reactions we are exploring compose the entirety of possible independent reactions.
HYSYS will not allow you to attach a set containing both reactions as it could accomplish the same thing
better by simply forcing you to choose Gibbs Reactions Only.

Frequently, however, you do not want all possible reactions to go to equilibrium. Suppose instead you
wish to model a system that normally does not go to equilibrium quickly (there is a large activation energy).
You, however, know that there is a catalyst which will lower the activation energy for the reaction you want
and only the reaction that you want. You know that eventually a PFR will be used, but for whatever reason,
you do not wish to model one yet. It is sufficient to assume that the Plug Flow would sufficiently near
equilibrium that you may model the reactor as if it went all the way to equilibrium. In a case such as this,
you would want to use an Equilibrium or Gibbs Reactor with only the one reaction attached. This is the
time to use the Specify Equilibrium Reactions option in the Gibbs Reactor.

For this example, we must first de-activate one of the reactions in the Equilibrium Set before we may
use it. Let us assume that we wish to focus on the Water Gas Shift reaction and expect to see little or no
Reforming (at the temperatures we are operating at, a not unreasonable assumption). Under the Flowsheet
menu, select Reaction Package. This will open a window showing the available reactions and reaction sets.
Double-click on Equilibrium and its window will open. Highlight ReformingEq and push the Make
Inactive -> button.

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Note that in my file AllReactors.hsc, instead of de-activating the reaction from Equilibrium,
I made a new reaction set called GibbsEquil, which I set up with the one equation active and
the other equation inactive.

Now, attach the modified reaction set to the Gibbs Reactor. It should work without a hitch. (Note that if
you attempt to use the Composition Page now, the reactor will automatically revert back to Gibbs
Reactions Only). Compare the results you get now with the results from the Equilibrium Reactor using the
same reaction set. Yet again they are almost exactly the same.

Two final notes:

1. A menos que se le proporcionen datos específicos de Equilibrium para usar, sus resultados tienen más
probabilidades de ser precisos usando el Reactor de Gibbs que con el Reactor de Equilibrio.
2. Al definir Reacciones de Equilibrio, comprenda que puede elegir que HYSYS determine Keq a partir
de los Coeficientes de Energía Libre de Gibbs de Gas Ideal. Esto es casi lo mismo que lo que hace
con las reacciones de equilibrio en el Reactor de Gibbs. La diferencia es que Gibbs tendrá efectos no
ideales del paquete termodinámico, mientras que la reacción de equilibrio así definida permanecerá
en el caso ideal.

Volver a la Página de Reacciones | Volver a la página de HYSYS | Volver a la página principal del CENG
403

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