Reactions With HYSYS

In this module, you will simulate a Synthesis Gas Production facility. This will introduce you to the powerful reaction modelling capability of HYSYS. The production of synthesis gas is an important step in the production of ammonia. Synthesis gas is comprised of hydrogen and nitrogen at a molar ratio of 3:1. The main role of the synthesis gas plant is to convert natural gas, primarily methane, into hydrogen. In most synthesis gas plants, four reactors are used. However, in our simulation five reactors will be used to model this process. This is because the combustor, a single vessel, will be modelled as two reactors in series, with two different reaction types. The first reactor is a Conversion reactor and the second is an Equilibrium reactor.

Reactions and Reactors

There are five different types of reactors that can be simulated with HYSYS, and by using combinations of these five reactors, virtually any reactor can be modelled with HYSYS. The five reactor types are:

Conversion - given the stoichiometry of all the reactions occurring and the conversion of the base component, calculates the composition of the outlet stream. Equilibrium - determines the composition of the outlet stream given the stoichiometry of all reactions occurring and the value of equilibrium constant (or the temperature dependant parameters that govern the equilibrium constant) for each reaction. Gibbs - evaluates the equilibrium composition of the outlet stream by minimizing the total Gibbs free energy of the effluent mixture. CSTR - assumes that the reactor contents are completely mixed in computing the outlet stream conditions, given the stoichiometry for all the reactions that are occurring and the kinetic rate constant (or the temperature dependence parameters for determining the kinetic constant) for each reaction. PFR - assumes that the reaction stream passes through the reactor in plug flow in computing the outlet stream composition, given the stoichiometry of all the reactions occurring and a kinetic rate constant for each reaction.
Note that the required input is different depending on the type of reactor that is chosen. The last two types (CSTR and PFR) must have kinetic rate constants (or the formula to determine the kinetic rate constant) as inputs, as well as the stoichiometry of the reactions. All of the reactor types, except for the Gibbs type, must have the reaction stoichiometry as inputs. The Tank, Separator, and Three Phase Separator Unit Operations can also process reactions if a reaction set is attached.
Note that Kinetic, Kinetic (Rev Eqb), and LangmuirHinshelwood reactions can be modelled in the CSTR, PFR and Separator.

Process Overview

The first step in simulating a synthesis gas plant is choosing an appropriate fluid package. We will be using the Peng Robinson (PR) EOS in this simulation. Add the following components to the simulation: CH4, H2O, CO, CO2, H2, N2, and O2. Press the Add Rxn button, and choose Conversion as the type from the displayed list. Enter the necessary information as shown:

Move to the Basis tab and enter the information as shown:

Repeat Steps 5 and 6 for two more Conversion reactions. Use the following data. 8. Add an Equilibrium reaction by selecting the reaction type as Equilibrium rather than Conversion. Under the Library tab, highlight the reaction with the form CO + H2O --> CO2 + H2. Press the Add Library Rxn button. This adds the reaction and all of the reactions data to the simulation.
When entering the values for the Stoichiometeric Coefficients, it is important to remember that "Products are

positive and Reactants are negative."

Name Reaction Base Component Conversion (%)

Rxn-2 CH4 + 2H2O --> CO2 + 4H2 Methane 65 Rxn-3 CH4 + 2O2 --> CO2 + 2H2O Methane 100

Adding the Reaction Sets

Once all four reactions are entered and defined, you can create reaction sets for each type of reactor. 1. Still on the Reactions page, press the Add Set button. Call the first set Reformer Rxn Set, and add Rxn-1 and Rxn-2. Reactions are added by highlighting the <empty> field in the Active List group, and selecting the desired reaction from the drop down list. The view should look like this after you are finished:

Create two more reaction sets with the following information: Reaction Set Name Active Reactions
Combustor Rxn Set Rxn-1, Rxn-2, Rxn-3 Shift Rxn Set Rxn-4

Attaching Reaction Sets to the Fluid Package

After the three reaction sets have been created, they must be added to the current fluid package in order for HYSYS to use them. 1. Highlight the desired Reaction Set and press Add to FP. 2. Select the only available Fluid Package and press the Add Set to Fluid Package button. 3. Repeat Steps 1 and 2 to add all three reaction sets (Reformer, Combustor, and Shift). 4. If desired, you can save the Fluid Package with the attached reaction sets. This will allow you to reopen this FP in any number of HYSYS simulations.

Installing the Material Streams

Create four new material streams with the following information: Combustor Steam Name Natural Gas Reformer Steam Air Temp.,oC (oF)
370 (700) 250 (475) <empty> 240 (520) 100% - H2O 16 (60) <empty> 90 (200) 250 (475) <empty> 140 (300)

Pressure, kPa(psia)
3500 (500) 90 (200)

Molar Flow,kgmole/hr(lbmole/hr) MolarComposition

100% - CH4 79% - N2 21% - O2 100% - H2O

Adding the Conversion Reactors

The first reactor in the synthesis gas plant is the Reformer. This reactor will be modelled as a Conversion Reactor. 1. From the Object Palette, click General Reactors. Another palette appears with three reactor types: Gibbs, Equilibrium and Conversion. Select the Conversion Reactor, and enter it into the PFD. 2. Name this reactor Reformer and attach Natural Gas and Reformer Steam as feeds. Name the vapour outlet Combustor Feed and the energy stream as Reformer Q. Even though the liquid product from this reactor will be zero, we still must name the stream. Name the liquid product stream as Reformer LP. 3. On the Parameters page, choose the duty as Heating. On the Details page of theReactions tab, select Reformer Rxn Set as the reaction set. This will automatically connect the proper reactions to this reactor. On the Results page, change the Spec % Cnv value for Rxn-1 to be 40% and for Rxn-2 to be 30 %. The screen should look like this:

On the Worksheet tab, enter a temperature of 930 oC (1700 oF) for the outlet stream Combustor Feed.

The second reactor in a synthesis gas plant is the Combustor. The Combustor will be modelled as a Conversion reactor and an Equilibrium reactor in series. This is because Conversion reactions and Equilibrium reactions cannot occur in reactors of the opposite type, i.e. conversion reactions cannot be associated with equilibrium reactors, and vice versa.

Add another Conversion Reactor with the following data: In This Cell... Enter...
Name Feeds Vapour Product Liquid Product Reaction Set Rxn-1 Conversion Rxn-2 Conversion Rxn-3 Conversion Combustor Combustor Feed, Air,Combustor Steam Mid Combust Combustor LP Combustor Rxn Set 35% (Default Value) 65% (Default Value) 100% (Default Value)