SCHOOL OF CHEMICAL ENGINEERING

Acrylonitrile Plant –
Mass and Energy
Balance
Mini Design Project
Mohammed Hassan Gohar - 938940

This report aims to calculate mass and molar flow rates and the compositions of each
stream involved in a simplified SOHIO process, one of the most common industrial routes
for the production of 40,000 tonnes per year of acrylonitrile. The possibility of heat
integration and recycle has also been discussed.
Chemical Engineering Mohammed Hassan Gohar Task 2

1] Introduction
Acrylonitrile is the chemical compound with the formula CH2CHCN. It is used widely in industry,
particularly as a monomer for plastic production. Its most common production process is via the
SOHIO process. The diagram below shows a simplified process for acrylonitrile manufacture. [1].

The compound is distinguishable due to its pungent smell and its colourless nature as well as often
being seen as yellow due to impurities. [1].

Acrylonitrile is commonly known as ACN which is used in the manufacture of polyacrylonitrile for
acrylic fibre, this can be used in clothing, household items and industrial markets and applications
for example carbon fibre. The main feed required to produce nylon, adiponitrile is also
manufactured by the use of acrylonitrile. Acrylonitrile ACN also be used to produce plastics that are
impermeable to gases and are ideal for shatterproof bottles for the use of cosmetics and chemicals.
[1].

Acrylonitrile is the most produced nitrile. In recent years, in line with demand of acrylonitrile,
production has increased. In 2005 annual production was 90 million metric tons; in 2007 production
has been as high as 100 million tons. [2].

ACN

vent 12
HCN 14
6

4 5
H2 O
Q
C3
steam 11

16 ACoN C4

H2 O 7
10 13
C1
1 2 3

15

Propene NH 3 air
C2
waste
8

Figure 1: Simplified process flow diagram for acrylonitrile manufacture. [3].

During this report, the mass and molar flow rates and the composition of each stream to produce
40,000 tonnes of acrylonitrile per year will be calculated by using data provided to work logically
through the process.

1
Chemical Engineering Mohammed Hassan Gohar Task 2

2] Contents

1] Introduction……………………………………………………………………………………………………………….………………… 1

2] Contents…………………………………………………………………………………………………………………….………………… 2

3] Mass and Energy Balance……………………………………………………………………………………………………….....3-4

4] Heat Integration and Recycling…………………………………………………………………………………..………………5-6

5] Conclusion……………………………………………………………………………………………………………………………………..6

6] Nomenclature…………………………………………………………………………………………………………………………….….7

7] References………………………………………………………………………………………………………………………………….…8

8] Flow Rates and Compositions……………………………………………………………………………………………………..…9

2
Chemical Engineering Mohammed Hassan Gohar Task 2

3] Mass and Energy Balance

As 40,000 tonnes per year of acrylonitrile (ACN) is produced, stream 14 can be calculated first. An
assumption that needs to be made is that for 40,000 tonnes to be produced, the plant runs
continuously for the year which has 365 days in that year.

The amounts of the various products (tonnes per year) can be converted to kg/s to give the mass
flow rates in the following way:

( 40,000∗1000)/(365∗24∗60∗60)=1.268 kg /s

The molar mass of ACN is 53g, therefore the molar flow rate ACN is found by:

Molar Flow Rate=( Mass Flow Rate )/(Molar Mass)

1.268/53=0.0239 kmol/ s

It is known that in stream 14, the mass flow rate of ACN has a purity of 99.70wt%, hydrogen cyanide
(HCN) has 0.01wt% and acetonitrile (ACoN) 0.05wt%. Therefore the mass flow rate of HCN and ACoN
is found by:

( Mass Flow99.7
Rate of ACN
)∗wt % of compound
Therefore for HCN the formula used to calculate its mass flow rate was:

1.268
( 99.7)∗0.01=0.000127 kmol /s

The amount produced per year of HCN and ACoN was calculated by

( Mass1000
Flow Rate
)∗60∗60∗24∗365
Mass Flow Rate
The molar flow rates were found by Molar Flow Rate=
Molar Mass

NH3 and H2o make up the remaining constitution with 0.24wt%.

It is known that the separation unit block recovers 95% of ACN in the feed, therefore the ACN
content in stream 13 can be found by:

Mass Flow Rate of ACN after Separation

=ACN content ∈stream 13
0.95

3
Chemical Engineering Mohammed Hassan Gohar Task 2

It is known that the mass ratio in stream 4 of ACN:HCN:ACoN is 1000:50:15, it is assumed that ACN
loss is negligible between streams 4 – 13, therefore the mass flow rates for HCN and ACoN can be
calculated, for example to calculate the mass flow rate of HCN:

( Mass Flow1000
Rate of ACN
)∗50=0.067 kg /s
The mass flow rates can be converted into molar flow rates for stream 4. Streams 1 2 and 3 can then
be calculated using the ratios shown in equations 1 2 and 3.

Equation 1: C3H6 + NH3 + 1.5o2  CH2CHCN + 3H2o

Equation 2: CH2=CH-CH3 + 3NH3 + 3O2  3HCN + 6H2O

Equation 3: 2CH2=CH-CH3 + 3NH3 + 1.5O2  3CH3-CN + 3H2O

N.B] Equation 1 is the main reaction in the SOHIO process, equation 2 is the side reaction producing
HCN and equation 3 is the side reaction producing ACoN.

By using equation 1, it can be seen that propene, ammonia and ACN are in the same stoichiometric
ratios, therefore the molar flow rates are the same, however for example there are 3 moles of water
to 1 mole of ACN therefore the flow rate of the water would be calculated by:

Flow Rate of ACN∗3=Molar Flow Rate of water

Another assumption that is needed to be made is on the composition of air. It is assumed that air is
made up of 79% nitrogen and 21% oxygen. This allows air molar flow rate to be calculated by first
finding the flow rate for oxygen, and then dividing this by 21, and multiplying this by 100.

Propene, ammonia and air totals are found and the values are divided through by 0.85, the reason
for this is only 85% of the propene is converted as stated, and therefore air is multiplied by 1.25 as it
is stated that air is in excess of 25%.

An energy balance is used using the following equations:

Equation 4: Q=mCp∆T

Equation 5: Q=mL

Equation 6: C0p = C1 + C2 [C3/T / sinh(C3/T)]2 + C4[C5/T / cosh(C5/T)]2. [4].

NB] The symbols are defined in the nomenclature section.

The specific heat capacity is found using equation 6, allowing equation 4 to be solved using the
temperatures provided. A simultaneous equation is used to find the mass of water in equation 5
using a latent heat of 2257 kJkg-1[5]. There are further assumptions that there is no loss in the
separator C4 shown in figure 1 and that the maximum amount of HCN is in stream 14. The ratio of

4
Chemical Engineering Mohammed Hassan Gohar Task 2

ammonia to water remains consistent throughout the process, therefore a suitable assumption that
the concentration of ammonia dissolved in water is uniform allows the compositions of ammonia
and water to be found. All values for the streams have thus been calculated and inputted into the
excel table figure 2 attached and the compositions also worked out.

4] Heat Integration and Recycling

Heat integration and recycling are techniques adopted to reduce wastage and improve the efficiency
of processes. Energy costs in refinery plants range can range up to around 50 million pounds per
annum. Hence small changes in efficiency even to the scale of possibly 2% can have massive financial
savings. Usually 10 – 15% savings is made within the present economic criteria. However if changes
such as installation of new gas turbines is taken into effect then savings of more than 30% can be
observed. [6].

A well-known example of heat integration being used is with the energy company SASOL. The
following table describes the energy usage of the company [Figure 3]. [6].

ENERGY
(MW)
 Current energy usage 3 500
 Theoretical energy required 1 940
 Energy usage with defined projects 2 40

Figure 3. [6]

A project identified at SASOL was the adding of new process heat exchangers to minimise utility
consumption.

The energy savings for the site are broken down into four basic categories as follows:
1. Operating Changes 6%
2. Process Heat Integration 6%
3. Utility Systems 9%
4. Process/Utility Interfaces 79% [6].

Figure 4 shows the savings made by different companies to a greater extent that have also employed
the heat integration methods.

5
Chemical Engineering Mohammed Hassan Gohar Task 2

Figure 4. [7]

To reduce the energy requirement of a process, many different parameters can be altered such as
the separation column operating pressures, flow rates, reactor conversion. The number of
parameters is so large to accurately predict the exact parameters that help reduce energy
consumption. However we can apply the thermodynamic rules governed by heat integration to
identify changes that have positive impact on energy consumption. This is known as the ‘plus-minus
principle’. We are therefore able to tell which modifications in the process will be favourable and
which will be disadvantageous. [6].

The water and ammonia from stream 9 in this process could be recycled saving potentially 1 million
tonnes of water per year and over 2500 tonnes of ammonia per year. This can be done by
concentrating the contaminant in the water stream by the use of evaporation. This concentrated
stream can be disposed of or the ammonia can be re used in the process. The water in the stream
will need to be purified by biological waste water plant treatment. [9]

The air can be recycled from stream 6, and used with stream 9 and a packed air stripper to purify
water and extract as much ammonia a possible. This is known as air stripping, and products are
currently on the market that increases the contact between the water and the gas improving process
efficiency. [8].

The ammoxidation process is a highly exothermic reaction. Heat produced from the reaction could
be used to generate high pressure steam which can be used to drive air compressors and provide
energy to downstream separation units. [9].

5] Conclusion
The SOHIO process long remains the most prominent method of manufacturing ACN due to its
effective process. 40,000 tonnes can be produced in the ways described in the report, however there
are many ways in which this process could benefit and should therefore look to explore further into
for example the recycling of water which could potentially save over 1 million tonnes of wasted
water. These improvements will ensure the SOHIO process will withstand the current needs of
today’s climate.

6
Chemical Engineering Mohammed Hassan Gohar Task 2

6] Nomenclature
ACN: Acrylonitrile

HCN: Hydrogen Cyanide

ACoN: Acetonitrile

NH3: Ammonia

H20: Water

C3H6: Propene

Q= Heat transferred kJ

m= mass of air kg

Cp= specific heat capacity kJ/kgK

T= Temperature (K)

L= latent heat kJ/kg

Cn= correlation coefficient

7
Chemical Engineering Mohammed Hassan Gohar Task 2

7] References
[1] No Author. Acrylonitrile - Process [Internet]. 2010 [cited 2010 Oct 17]. Available from
http://www.ineostechnologies.com

[2] No Author. Acrylonitrile Trend [Internet]. 2010 [cited 2010 Oct 17]. Available from
http://fuyue.bloggum.com/post/acrylonitrile-bullish-trend-in-2010-was-in-short-supply.html

[3] Robbins, P. Task 2: Acrylonitrile Plant – Mass and Energy Balance [Internet]. 2010 [cited 2010
Oct 17]. Available from:
http://bham.blackboard.com/webct/urw/lc4904741148061.tp4904741168061/cobaltMainFrame.do
webct

[4] Alexandre C. Dimian and Costin Sorin Bildea (2008). Chemical Process Design Computer- Aided
Case Studies. Wiley-VCH

[5] D.W. Green, R.H. Perry. Perry’s Chemical Engineers Handbook (8th edition), 2008 2:156, Beijing

[6] Linhoff March. The Methodology and Benefits of Total Site Pinch Analysis [Internet]. 2007
Available from: http://www.linnhoffmarch.com/pdfs/TotalSiteMethodology.pdf Accessed on 18th
November 2009

[7] BROWN, K. J, 1988.Process Integration Initiative. A Review of the Process Integration

Initiatives Funded under the Energy Efficiency R&D Programme. Energy Technology
Support Unit (ETSU), Harwell, Oxon, UK.

[8] A.Wong (2004). Lantec Ammonia Removal- Water Purification in Packed Bed Air Stripper.
[online] Available from www.lantecp.com [Accessed 17th October 2010]

[9] No Author (Feb 2003). European Commission Large Volume Organic Chemical Industry.[online]
Available from bvt_organische-grundchemikalien_zf.pdf [Accessed 17 th October 2010]