AREA 6

DESIGN PROJECT 2023

Refining of cracked Bio-naphtha
AREA SIX BACKGROUND AND INFORMATION
Production of acrylonitrile (ACN)

In Area 6, propylene is reacted with air and ammonia to form acrylonitrile. Acrylonitrile is a chemical
compound with the formula C3H3N. The process follows the scheme known as the Sohio process. The
required feedstock – a stream of appropriate purity propylene - is delivered from Area 4.

The product specification of the produced acrylonitrile is given in Table 1.

Table 1 - Acrylonitrile Specification (T < 45°C and P = 200 kPag)

Components Units Guaranteed Values

Acrylonitrile wt% 99.85 min

HCN wt ppm 10 max

Acetonitrile wt ppm 1 max

Water wt ppm 10 max

SOHIO PROCESS

In the Sohio process, reactants are delivered in stoichiometric quantities at 210 kPag and a temperature
of 350-600°C. The catalysts used are mostly based on mixed metal oxides. The reactor is usually based
on a fluidised bed (FB) configuration, using catalyst particles as the main fluidising material.

The main reactions and the side reactions of the process occur in the FB reactor as follows:

CH2 = CH − CH3 + NH3 + 3/2O2 → CH2 = CH − CN + 3H2 O R1

Propylene + Ammonia + 3/2 O2 → Acrylonitrile + 3 H2O

Apart from the above main reaction, side reactions are also possible:

CH2 = CH − CH3 + 1.5O2 → CH2 = CH − CHO + H2 O R2

Propylene + Oxygen → Acrolein + H2O

CH2 = CH − CH3 + NH3 + 4.5O2 → CH3 − CN + 0.5CO2 + 0.5CO + H2 O R3

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Propylene + Ammonia + 4.5 O2 → Acetonitrile + 0.5CO2 + 0.5CO + H2O

CH2 = CH − CHO + NH3 + 0.5O2 → CH2 = CH − CN + 2H2 O R4

Acrolein + Ammonia + 0.5 O2 → Acrylonitrile + 2 H2O

CH3 − CN + 1.5O2 → HCN + CO2 + H2 O R5

Acrolein + 1.5 O2 → Hydrogen cyanide + CO2 + H2O

The synthesis product is cooled by rapidly quenching with water and neutralised using sulphuric acid
to remove unconverted ammonia. Acrylonitrile is then separated from hydrogen cyanide and
acetonitrile by-products, and other heavy impurities in a distillation train. Recovery of ACN, acrolein
and water is often performed to improve process economics and sustainability.

Process diagram is given in Fig. 1.

Figure 1. A simplified block diagram of Area 6 for production and purification of acrylonitrile (ACN).

DESIGN PROBLEM DEFINITION

Students should address the following issues:

• How many fluidised bed reactors are required for safe and robust Area operation, and what
are their key mechanical dimensions?

• Where can propylene, ammonia and air be added to the FB reactor(s)?

• What are the operating conditions of each fluidised bed?

• Choice of catalyst

• Handling and processing of by-products and waste products

DETAILED DESIGN MODELLING

Matlab / Excel/ UniSim model should include the following:

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• A Fluidised bed reactor for reacting propylene with air and ammonia

The model should account for the parallel reaction kinetics, heats of reaction, and pressure drop through
the catalyst bed. A set of kinetic parameters can be taken from [1], while information on modelling
fluidised beds is given in [2]. You will need to introduce simplifications to account for multiple reactions.
Information on heat transfer in fluidised beds is described in [3].

OPTIMISATION, USING DESIGNED MODEL (sensitivity analysis)

The outlet composition of the FB reactor should be examined as a function of the parameters listed
below:

• reactor inlet temperature;

• reactor inlet pressure;

• ratio of incoming reactants.

The results from the sensitivity study should be able to answer the following questions:

• What inlet temperature and pressure have you chosen for the FB reactor and why?

When making and justifying your choice of operating conditions, you must also consider factors relating
to (i) safety, (ii) energy usage, (iii) capital costs, (iv) equipment operability.

Note on UniSim implementation

Modelling fluidised bed reactors from first principles is a non-trivial task: remember that design project
assessors are looking to give credit for a pragmatically-designed unit operation that has been
modelled in a manner that is fit-for-purpose rather than for a piece of bespoke modelling code that
fails to deliver a complete design. An initial model for the reactor system is recommended to be
constructed in UniSim: UniSim does not contain modelling tools for fluidised bed reactors, but one of
the reactor models within UniSim can be used if certain assumptions are made.

REFERENCES

[1] J.R. Hopper, C.L. Yaws, T.C. Ho, M. Vichailak, Waste minimization by process modification, Waste
Management. 13 (1993) 3–14. https://doi.org/10.1016/0956-053X(93)90030-Z.

[2] O. Levenspiel, Chemical Reaction Engineering, Ind. Eng. Chem. Res. 38 (1999) 4140–4143.

[3] J.C. Chen, J.R. Grace, M.R. Golriz, Heat transfer in fluidized beds: design methods, Powder
Technology. 150 (2005) 123–132. https://doi.org/10.1016/j.powtec.2004.11.035.

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