Reactions in HYSYS

There are currently five different types of reaction that may be simulated in HYSYS and a number of
reactor types that they may be used with (and one special reactor that does not require any equations).
Reactions may also be used in Columns and Separators (though there are some limitations on the phases
that may be used by the reactions in those cases). The five reaction types are as follows:

Conversion

This reaction type does not require any thermodynamic knowledge. You must input the
stoichiometry and the conversion of the basis reactant. The specified conversion cannot
exceed 100%. The reaction will proceed until either the specified conversion has been
reached or a limiting reagent has been exhausted.

Conversion reactions may not be grouped with any other form of reaction in a reaction
set. However, they may be grouped with other conversion reactions and ranked to operate
either sequentially or simultaneously. Lowest ranking occurs first (may start with either 0 or
1). Just as with single reactions, simultaneous reactions cannot total over 100% conversion
of the same basis.

Conversion reactions cannot be used with Plug Flow Reactors or CSTRs. In general, they
should only be used in Conversion Reactors.

Equilibrium

Equilibrium reactions require that you know some sort of relation between the reaction's
equilibrium constant, Keq, and temperature. You may specify Keq in a number of ways:

As a constant. Enter either Keq or Ln(Keq).

As a function of Temperature. You specify A-D in the equation below

Ln(Keq) = A + B/T + C*Ln(T) + D*T

IMPORTANT: No matter what the units in your preferences, the T's used for this equation are in
Kelvin and thus your coefficients A-D must be adjusted accordingly if the T's for the information
you have are not also in Kelvin. If it becomes complicated to do so, you might choose to generate
a table of K vs. T and enter that as tabular data.

As tabular data of Keq vs. T (as suggested in the note above and from which HYSYS
fits the above equation).
Have HYSYS determine Keq from the Ideal Gas Gibbs Free Energy Coefficients.
This is similar to, but not exactly like what you get by attaching any equilibrium
reaction to a Gibbs Reactor (which just takes the stoichiometry). The difference
depends on the property package because the Gibbs reactor will take into account any
non-ideal behavior predicted by a thermo package such as Peng-Robinson. An
essentially ideal thermo package like Antoine would give almost exactly the same
 results for the two different methods.
You may also search for the reaction among the pre-
defined reactions in the HYSYS library (reached from the
Library Page of the Equilibrium Reaction window)

Supposedly, like Conversion reactions, equilibrium reactions may be calculated either

sequentially or simultaneously. I actually did not see any means by which reactions might be
designated sequential and suspect an error in the reference manuals in stating that it could be
so. Equilibrium reactions also cannot be used with Plug Flow Reactors or CSTRs. In general,
they should only be used in Equilibrium Reactors or General Reactors. They can, however,
also be used in the special Gibbs Reactor. When a reaction set is attached to a Gibbs reactor,
the stoichiometry involved in the reactions is used in its calculations.

Kinetic

All three of the remaining reaction types can be considered kinetic, in that they deal with an
expression for the rate of the reaction. Differentiating between the three becomes simply a
matter of formulation. In this first and simplest form, the rate equation is the one to the left
(this picture is taken from the Parameters Page of the Kinetics Reaction window). The first
term on the right hand side refers to the forward reaction, the second term to the optional
backward reaction. The k's are the reaction constants for which you must enter on the
Parameters Page the activation energies, E and E', and the pre-exponential factors, A and A'
(which are basically all of the constants lumped out front). The basis functions are not just
functions of the Base Component (which you set on the Basis Page -- see Chapter 11 of RV1
for an explanation of the Base Component or anything else having to do with reactions), but
are the products of the concentrations (or partial pressures, etc.) of any of the reactants or
products to whatever power (negative numbers and decimals are fine). For example, it just so
happens that for the reaction

CO + Cl2 --> COCl2

the rate law might be rCO = k[CO][Cl2]3/2

You actually enter the form of the basis functions on the first page, Stoichiometry, of the
reaction window. In the columns to the right of the one in which you enter the stoichiometric
coefficients, you must enter the forward and reverse order. The HYSYS default is to assume
an elementary reaction the stoichiometry parallels the order. Therefore for this reaction you
would leave the forward order of CO at 1 and enter 1.5 for the forward order of Cl2. Though
it is assumed there is no reverse reaction, you might, if you chose, leave a 1 for the reverse
order of the COCl2. As long as you did not enter a value for the reverse E and A, no reverse
reaction would take place.

The Chemicals Tutorial in the Tutorials Book will take you through an example of the use of
a Kinetics reaction in a CSTR.
Kinetic (Rev Eqm)

This form of the rate equation is fairly similar to the

standard kinetic form. The difference is that instead
of getting information about the reverse rate constant,
we use the relation:

Keq = kforward/kreverse

or, as is actually substituted into the standard form,

kreverse = kforward/Keq

Of course, in doing so we have implicitly assumed an elementary reaction as that is inherent

in the definition of Keq. Therefore there is no place to enter reaction orders. Keq is determined
by HYSYS in the same it was done for the equilibrium reaction above, except that this time
you are forced to enter the data in the Ln(K') format (again, if that's not what you have, don't
despair. Try creating an equilibrium reaction, defining it how you are able and then copy
over the constants that HYSYS generates).

For an example of the use of this type of reaction, see my Plug Flow Example.

Langmuir-Hinshelwood

This is the most complicated of all the reaction forms and is therefore the one that is not even
mentioned in any of the manuals (either on-line or off). Therefore it falls to me to explain it.
I go through all of this in detail in the Plug Flow Example, so if you decide you do need to
use this form, I recommend you work through that.Langmuir-Hinshelwood is mainly used to
model heterogeneous catalysis. The rate of reaction is slowed when you have a finite number
of active sites on the catalyst, some of which may become blocked to reaction by the
products being formed. Hence, to the standard rate equation is added a denominator (this is
almost exactly like the form for enzyme catalysis for those of you who have had
Biochemistry).
General Information on Reactions

If you are looking for a step by step instruction on every stage of the creation of a reaction and the use of
reaction sets, you won't find it here. You will find explanations of that stuff in any of my reactor examples
(Plug Flow Example, Gibbs and Equilibrium Reactors, Conversion Reactor), or you may look in Chapter 11
of Reference Volume 1 (does an excellent job with this kind of stuff), or work through the Chemicals
Tutorial in the Tutorials Book. What I am going to list here are the little pearls of wisdom I picked up while
working through the reactions myself and that may or may not be mentioned in the manuals.

1. You do not need to go back to the basis environment every time you want to edit reactions. You can
create or change reactions in the simulation environment using the Reactions Package under the
Flowsheet menu. You cannot, however, import or export reactions except from the basis
environment.
2. Modifications can be made to reactions on a specific reactor's property view pages that are local
only and do not apply globally. Local changes always take precedence over the global settings. (Not
an option in PFR). See Section 13.13 of RV2.
3. The components you have in a reaction need not have been previously included in the fluid
packages' component list. When you finally associate a reaction set with the fluid package,
whichever of its reaction's components are not already there will be added then to the fluid package.
4. There are places (such as when entering the kinetics parameters) where you shall find that no matter
how many significant digits you enter in, only 2 sig. figs will be displayed. This is a short coming of
HYSYS and will be fixed in future versions. The extra unseen digits are used in the calculations, but
the only way to see them is to export them to a Spreadsheet (using the secondary mouse button,
simply drag the number from the reaction window to a cell of the Spreadsheet Page of the
Spreadsheet).
5. Under the Stoichiometric Page of a reaction window, the item called "Reaction Heat" is not the
Heat of Reaction as we know it. In fact, they have opposite signs (an exothermic reaction has a
positive Reaction Heat).
6. Remember whenever defining an Equilibrium constant using Ln(Keq) = A + B/T + C*Ln(T) + D*T,
that T is in Kelvin.
7. HYSYS does not show you the units of the Activation Energy it displays. If you would like to
display it in the same units you entered, you must go into your preferences set and set the units of
Molar Enthalpy to the units you would like Activation Energy displayed in, as Activation Energy
does not have its own category. Reaction rate does have its own category. The Pre-exponential
factor has the same units as Reaction rate (the units set on the basis page, NOT necessarily the units
set in the preferences which seem to only be for reporting purposes) divided by the Basis Units.

Reactors
Though I plan to tell you about all of the reactors, pay special attention to the info on the Plug Flow and
Gibbs Reactors, as they are the ones you will likely use the most. With the exception of the Plug Flow
Reactor, the property views of the various reactors are essentially the same. You must specify a liquid
and/or vapour product stream for all reactors (again, except for plug flow which has one and only one
product stream). All reactors are assumed adiabatic until an energy stream is attached (at which point some
further specification such as outlet temp or energy input is required).With the exception of the Plug Flow
Reactor and the Gibbs Reactor, all of the reactors also have a number of pages in their property views
related to the reactions in them. There you may make changes to the reactions that only take effect in that
particular reactor. Local changes always take priority over global changes (so make sure you are aware of
whether the change you are making is local or global).

Appearance in PFD / Object Palette Description

Button
The Plug Flow Reactor can be used with Kinetics,
Kinetics (Rev. Eqm.), or Langmuir-Hinshelwood reactions
(any number and combination of the three types can be used
in the reaction set). An excellent description of each of the
PFR's inputs can be found in Section 13.10 of RV 2. You can
also get a good idea of the way to go about setting up a PFR
in your simulation by working through my Plug Flow
Example.

Quirks of the PFR: HYSYS "integrates" over the length of

the reactor by dividing it into a number of sub-volumes (like a
series of CSTRS). The default is 20 sub-volumes. The most
noticeble effect of this to the user is in the reactor profiles.
The various characteristics are given as values vs reactor
length. The lengths listed are the midpoimts of the
subvolumes. For example, a 10 m length reactor with 20
subdivisions would give profiles starting at .25 m and
incrementing by .5 m (the size of a subdivision), finishing
with 9.75 m. Not realizing this at first I was irritated that the
profiles were not showing me the entering and exiting values
(0 and 10 m). Not to worry, the .25 and 9.75 m values are, in
fact, the same as 0 and 10 m. Everything within a subvolume
is the same (like a CSTR)

Another quirk of PFR is that on very rare occasions (see the

note in the gibbs reactor example). The integration
mechanism gets confused. To fix the problem, try looking at
the Reactions page of the reactor property view. Under
"Initialize segment reactions from:" make sure the re-init
radio button is chosen. Normally, you would not pick this
option as it takes the longest time to run. For details on how
HYSYS handles the three options see Section 13.10 of RV2
(p. 464).
 The CSTR can be used with Kinetics, Kinetics (Rev. Eqm.),
or Langmuir-Hinshelwood reactions (any number and
combination of the three types can be used in the reaction set).
An excellent description of each of the CSTR's inputs can be
found in Section 13.13.3 of RV 2. You can also get a good
idea of the way to go about setting up a CSTR in your
simulation by working through the Chemicals Tutorial in the
Tutorials Book. In addition you might want to take a look at
my Case Studies Example, where I build on the tutorial by
adding a case study. I use the Spreadsheet feature to access
the actual conversion % of the CSTR in the tutorial.

Quirks of the CSTR: CSTR is primarily for liquid reactions,

of course, but HYSYS will conduct the gaseous reactions as
well. The less the "liquid" volume, the more of the total
volume available for the vapour phase reactions (i.e. HYSYS
uses the total volume minus the volume you set for the liquid
to calculate the volume of the gas, whether or not any liquid is
actually present in the stream).
The Gibbs Reactor (like the one in Aspen) is unique among
the reactors in that you are not required to enter a reaction set
for it to work. The Gibbs reactor works by finding the
equilibrium state with the lowest Gibbs Free Energy. It
appears to be akin to finding all the possible equilibrium
reactions and allowing them all to equilibrate. It's nice
because you do not need to know anything about the
individual equilibrium constants. On the Composition page
you can set the production of components or set any of them
to be inert.

You may also set, on the Reactions page, the Gibbs reactor to
behave like an equilibrium reactor (you must then attach an
equilibrium reaction set, also see quirks below), or like a
separator (no reaction). See the example which will teach you
about the Gibbs reactor, the Equilibrium Reactor, and my
"switch" technique. The "switch" is also mentioned on my
opens tools and tricks page.

Quirks of the Gibbs Reactor: There is something very

important to note when attaching equilibrium reactions to the
Gibbs reactor. The Gibbs reactor takes only the stoichiometry
then, of the attached reactions and applies its own free energy
minimization technique to it. Only components listed as
reacting in the reaction set undergo any reaction. Note that
HYSYS will not allow you to attach a reaction set which
would include all of the possible independent reactions as that
would simply duplicate the effect of setting the reactor to full
Gibbs reactions. The part of this that is important to you in the
design classes is that the results of the Gibbs calculations
come extremely close to the values obtained in the
equilibrium reactor using correct data, while not making use
of any data on Keq. Thus if you need to simulate a reactor in
which you want certain reactions equilibrated, but not others
(for instance, because a certain catalyst is employed allowing
those particular reactions to equilibrate quickly, but not aiding
any other reaction) and yet have no or untrustworthy data on
the equilibrium constants, you are better off using the Gibbs
reactor set on "Specify Equilibrium Reaction" than using
the Equilibrium Reactor.

Two postscripts on this: 1) If you use the above technique, it

doesn't matter what you set the equilibrium constant, a fixed
constant of 1 is fine, because you only need the stoichiometry.
2) Before using the above technique, check the equilibrium
reaction library. The one you need may already be there, in
the temperature range you desire (even then, however, the
Gibbs way may still be better).

One last note, there appears to be a minor bug in HYSYS, in

that, when operating the Gibbs Reactor in Equilibrium
Reactor mode, a button appears that would show you the %
conversion, reaction extent, etc. Unfortunately, even when the
Gibbs Reactor had completed its calculations, the matrix
remained blank.

If you would like to experiment with the similarities and

differences between the Gibbs reactor and the Equilibrium
Reactor yourself, see the example for a good way to go about
it.

The Equilibrium Reactor uses reaction sets with only,

surprise, equilibrium reactions in it. You can read more about
it in Section 13.13.4 of RV 2. You can also see the example in
which I compare it to a Gibbs Reactor. In general, I
recommend making use of the Gibbs Reactor over the
Equilibrium Reactor.
 opens

then,
The Conversion Reactor deals with, yep, you guessed it,
conversion reactions. You use it when you know how much
of the reactants will be converted into products. As mentioned
in the section on conversion reactions, it can handle multiple
reactions which may be ranked to occur simultaneously or
sequentially. Reactions with the same ranking are
simultaneous and the total conversion of the same reactant
can not exceed 100% (all subject to limiting reagents, of
course). The product of one reaction can be the reactant of
another reaction.

Quirks of the Conversion Reactor: Though the specified

conversion cannot exceed 100%, the actual conversion can.
This is because the actual conversion is the percentage
conversion over the original amount of base component
present. However, if that base component is the product of a
lower ranked (meaning reacts first) reaction, there may be
more available than was originally there. This allows the
actual conversion to exceed the specified conversion (it's still
behaving correctly, so don't panic). The conversion could thus
opens be much greater than 100%. You can see this in my
conversion example. If none of the base component was
initially present, the actual conversion field will remain blank.
Conversely, if the base component of a reaction is a reactant
in an earlier occuring reaction, or if there are limiting
then, reagents, the actual conversion will be less than the specified
conversion. If the reaction producing the base component of
another reaction is ranked equally with it, the second reaction
would not convert any of the component produced by the first
reaction, but would only convert the specified percentage of
the original amount present. Ranking cannot be changed
locally in the reactor. It may only be altered in the reaction set
on the global level.

Not Accessible from the Object Palette. exploring the results that the General Reactor gives you. The
Can only be reached via the Unit Ops
View (obtainable by pressing <F12>, "Add \\Hartsook\Hysys\SAMP403.
an Operation" under the Flowsheet Menu,
or from the Unit Ops Page of the
Workbook.
The General Reactor is like a combination of the CSTR and
the Equilibrium Reactor. If you put in all kinetic style
reactions, it acts like a CSTR. If you put in all equilibrium
reactions, it acts like an Equilibrium Reactor. The General
Reactor, unlike any other type of reactor available to you, will
also allow you to mix equation types. You can combine
kinetic and equilibrium reactions into one reaction set (you
still cannot combine conversion reactions with any other type,
though you can attach a conversion reaction set to the general
reactor as well). That set will then be a mixed type and can be
attached to the general reactor. Unfortunately, verifying the
accuracy and method is somewhat involved (though not
necessarily difficult). I leave it to you to investigate this.
Rather than create an example for you. This time I simply
added the General Reactor to my file comparing all the other
reactors. That way, you may use all the reactions and reaction
sets that were created for the other examples as a way of
name of the file is AllReactors.hsc and it is located under
Quirks of the General Reactor: A strange problem,
somehow tied into the number of product streams attached,
results if you try to attach an equilibrium set immediately
after a conversion set. It fails to find a solution even if it had
done so before. If something like this happens to you click off
then back on again the Act as a Separator when cannot
solve button and it should solve.
The same quirks of the CSTR apply when using any kinetic
reactions in your reaction set.