CHE544 SEPARATION PROCESS

ASSIGNMENT 1

GROUP MEMBERS: NURUL SYAFIQAH BINTI AHMAD ANUAR 2018437144

NUR FATIHAH BINTI MOHD NORDIN 2018207862
SYARIDAH NOR HAZWANIE BINTI MAT 2018425408
JAIDIN
NABILA SOFEA BINTI ZAWAWI 2018680438

GROUP: EH2204G

LECTURER: DR. UMMI KALTHUM IBRAHIM

DATE OF SUBMISSION: 22 MAY 2020

Declaration
We hereby declare that this report is the result of our own work except for quotations
and summaries which we have been duly acknowledged.

………………………………..…. ...…….…………………..……
NURUL SYAFIQAH BT AHMAD NUR FATIHAH BT MOHD
ANUAR NORDIN
(2018437144) (2018207862)

…………………………………… ...…….…………………..……
SYARIDAH NOR HAZWANIE NABILA SOFEA BT ZAWAWI
BT MAT JAIDIN (2018680438)
(2018425408)
Table of Contents

Title Pages

Chapter 1:
1–5
Introduction and Process Background

Chapter 2:
6-7
Process Flow Diagram (PFD)

Chapter 3:
Mass Balance 8 - 12

Chapter 4:
Conclusion 13

References 14 - 15

Appendix 16
 1. Chapter 1: Introduction and Process Background

1.1 Introduction

Acetic acid, having the chemical formula of CH3COOH is a simple carboxylic acid. It
serves countless purposes industrially, used in the production of plastic bottles, wood
glue and other synthetic material (National Center for Biotechnology Information, 2020).
Whilst domestically, it is most commonly seen in food and cleaning agents (National
Center for Biotechnology Information, 2020). This particular chemical also goes by the
name of ethanoic acid and has molecular weight of 60.05 g/mol. Having the boiling point
of 117.9oC (National Center for Biotechnology Information, 2020), it typically exists in a
liquid phase at room temperature. Physically, it is most recognizable as colorless and
has a distinct acidic smell (National Pollutant Inventory, 2018).

Figure 1. The chemical structure depiction of acetic acid

However, according to Patil (2014), the dumping of wastewater by the industry

containing acetic acid, formic acid and propionic acid is harmful to both the industry and
the environment. Hence, comes the absolute importance of recovering these acids from
wastewater of a particular process whilst aiming for a sustainable development. Patil
(2014) also highlighted some methods deemed conventional for this very purpose,

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namely ion exchange, fractional distillation and liquid-liquid extraction. In this case, the
proposed method chosen for acetic acid recovery is the liquid-liquid extraction.

Liquid-liquid extraction is an extraction process otherwise known as liquid extraction or

solvent extraction. Like any other extraction process, liquid-liquid extraction aims to
separate one or more components in a mixture, in which the two phases exist in liquid,
however are chemically different and ultimately promote separation (Geankoplis, 2018).
In other words, these particular solutes are separated according to their solubilities in
different liquids. It is also useful for the separation of mixture whereby the components
have close boiling points. According to Geankoplis, the same process is utilized in the
pharmaceutical industry where penicillin is separated from fermentation mixtures.

Coming back to the ultimate goal, which is to separate acetic acid from wastewater,
liquid-liquid extraction is especially feasible as water and acetic acid boil at almost the
same temperature, (100oC for water and 117.9oC for acetic acid). According to Fair
(2010), liquid-liquid extraction has the potential for energy reduction and the ability to
handle materials that are sensitive to temperature if compared to distillation. Hence, the
need to design a liquid-liquid extraction process specifically for the separation of acetic
acid from wastewater, in which 99% of purity is to be recovered.

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 1.2 Process Background

In the process background, a few aspects will be discussed such as the process flow,
design goals, constraints with the process selection and the proposed technique. As per
the introduction, the chosen process to achieve the recovery of acetic acid from dilute
aqueous solutions is the liquid-liquid extraction (LLE).

Figure 2. Process flow for multistage liquid-liquid extraction

Figure 3: Process flow for multistage liquid-liquid extraction

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The feed stream will contain wastewater in which the acetic acid in it will be recovered
through the liquid-liquid extraction process. The solvent that is used in this process to
separate acetic acid from water is isopropyl ether. This is because acetic acid and
isopropyl ether are miscible with each other while water and isopropyl ether are not.
Therefore, most of acetic acid from the water will leave the extract stream with isopropyl
ether while water will mostly exit through the raffinate stream along with very little
fraction of acetic acid and the solvent.

To sum it up, the goal of this liquid-liquid extraction design is to extract acetic acid from
water. This is a crucial process in any production plant that produces acetic acid as a
waste product, as acetic acid may endanger an ecosystem if it is dumped incorrectly.
Other than that, recovering acetic acid enables it to be recycled into the system that
needs it, which reduces the consumption of input for manufacturing.

However, liquid-liquid extraction has a few drawbacks or disadvantages. According to

Wolska (2006), liquid-liquid extraction (LLE) process requires a large volume of solvent
and the solvent needs to be of high purity. Scott (1995) also stated that extractor
designs are sensitive to the changes in flow rate as it may cause flooding and loading
problems.

Despite these drawbacks, LLE is still preferable over fractional distillation due to the
proximity of boiling points of water (100oC) and acetic acid (117.9oC) where they will
form an azeotropic mixture. Moreover, distillation demands for a large amount of energy
per unit of product (Kiss, 2012). In contrast to this, Wu (2016) stated that LLE has an
ability to achieve a high capacity of extractant and generally also has high selectivity of
separation. It is also cheap and energy efficient (Pal, 2017).

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As far as safety of the process is concerned, LLE itself is not a process with a potential
hazard as it does not operate at a high temperature or pressure. In fact, temperature
and pressure plays no role in the extraction as the driving force of the extraction is the
miscibility of the solute in the solvent. However, the solvent used, which is isopropyl
ether, otherwise known as diisopropyl ether, is classified as flammable and irritant, as
seen in National Center for Biotechnology Information (NCBI). However, these hazards
also apply to other chemicals if precautionary steps aren’t taken. For instance, acetic
acid in high concentration is corrosive.

Lastly, Kislik (2012) described LLE as friendly to the environment. This is because
providing the equipment and flows are correctly and carefully designed, no water and air
pollution will occur. For the same reason, Kislik also stated that it could potentially
replace other processes that are proven to pose a threat to the environment.

To separate the solvent from acetic acid, rectification is carried out.

Figure 4. Process flow for rectification

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 2. Chapter 2: Process Flow Diagram (PFD)

Equipment Key

E01 Extraction

S02 Raffinate Stripping

D03 Rectification Distillation

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The acetic acid and the ether are fed into the extraction as a liquid solution that
contains the desirable compound (acetic acid) that is to be separated together
with other compounds. It is fed at 100kg/h and as for the pure solvent (water) are
fed at 2500kg/h. The pure solvent needed to be used as it does not contain any
impurities in order to remove the ether from the system

At the extract stream, which is known as the desirable stream that the solvent-
rich product of the operation which contains the acetic acid, high no mol of the
solvent and ether. The mass flow rate of the exit extract stream is 297kg/h.

At the raffinate stripping, the raffinate stream contains the 3 liquid compounds
acetic acid, solvent and ether. It is the residual liquid from which solutes has
been removed.

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 3. Chapter 3: Mass Balance

3.1 LLE Column

Total Mass Balance Equation

MassIn = MassOut
Lo + VN+1 = LN + V 1

Component A Balance,
LoXAo + VN+1YAN+1 = LNXAN + V1YA1

Assuming,

Lo = 1000 kg/h VN+1 = 2500 kg/h

XAo= 0.3
XBo = 0.7
XCo= 0

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Therefore,
Acetic acid in feed = 0.3 x 1000 kg/h
= 300 kg/h

To achieve 99% acetic acid recovery,

Acetic acid in extract = 0.99 x 300 kg/h
= 297 kg/h

Assuming the fraction of acetic acid leaving in extract is YA1 = 0.1,

V1 (0.1) = 297 kg/h

V1 = 2970 kg/h

From equilateral triangle diagram for acetic acid-water-isopropyl ether system and on
extract layer when YA1 = 0.1,

YB1 = 0.06
YC1 = 0.84

Since 99% of acetic acid leaves in the extract stream, the remaining 1% must leave in
the raffinate stream.

Therefore,
Acetic acid in raffinate = 0.01 x 300 kg/h

= 3 kg/h

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Total mass balance,
MassIn = MassOut
Lo + VN+1 = LN + V 1
1000 + 2500 = LN + 2970
LN = 530 kg/h

Therefore,
XAN = (3 kg/h)/(530 kg/h)
= 0.00566

From equilateral triangle diagram for acetic acid-water-isopropyl ether system and on
raffinate layer when XAN = 0.00566,

XBN = 0.99
XCN = 0.00434

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 Figure 3. Equilateral triangle diagram of acetic acid-water-isopropyl ether system

Total stages required are approximately five (5) stages.

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 3.2 Rectification Column for Purification of Acetic Acid.

F=D+W FXF = DXD + WXw

2970 = D + W 2970(0.84) = D(0.99) + W(0.01)
2494.80 = 0.99D + 0.01W
2494.80 - 0.99D = 0.01 W
249480 - 99D =W

2970 = D + 249480 - 99D

D = 2515.4 kg
W = 454.6 kg

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 4. Chapter 4: Conclusion

In conclusion, liquid-liquid extraction is the most suitable option for the recovery of
acetic acid from its dilute aqueous solutions, in which the solvent selected is isopropyl
ether due to its miscibility with acetic acid and its immiscibility with water. To achieve the
recovery of 99%, an extraction column with five (5) stages is required. With the feed
flow rate of 1000 kg/hr and 2500 kg/hr solvent flow rate, 2970 kg/hr of acetic acid is
recovered in the extract. This is made possible due to liquid-liquid extraction having a
high selectivity of separation. Simple distillation is not recommended due to the close
proximity of the boiling points of water and acetic acid. An azeotropic distillation is
required for a mixture of this nature. However, rectification is carried out in another
column to remove solvent from the extract as the solvent has a lower boiling point than
the solute. The composition of acetic acid that comes out from the rectification process
is 0.99, or 99% purity.

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 5. References

Geankoplis, C. J., Hersel, A. A., & Lepek, D. H. (2018). Transport processes and
separation process principles. Harlow: Prentice Hall.

James R. Fair & Jimmy L. Humphrey (1984) Liquid-liquid extraction: possible alternative
to distillation, Solvent Extraction and Ion Exchange, 2:3, 323-352, DOI:
10.1080/07366298408918451

Kislik, Vladimir. (2012). Chapter 13. Advances in Development of Solvents for Liquid–
Liquid Extraction. Solvent Extraction Classical and Novel Approaches. 451-481.
10.1016/B978-0-444-53778-2.10013-5.

Kiss, A. A., Landaeta, S. J. F., & Zondervan, E. (2012). Cyclic distillation - towards
energy efficient binary distillation. Computer Aided Chemical Engineering 22nd
European Symposium on Computer Aided Process Engineering, 697–701. doi:
10.1016/b978-0-444-59519-5.50140-4

National Center for Biotechnology Information (2020). PubChem Database. Acetic acid,
CID=176. Retrieved from
https://pubchem.ncbi.nlm.nih.gov/compound/Acetic-acid

National Center for Biotechnology Information (2020). PubChem Database. ACETIC

ACID, Source=Hazardous Substance Data Bank (HSDB). Retrieved from
https://pubchem.ncbi.nlm.nih.gov/source/hsdb/40#section=Overview

National Center for Biotechnology Information (2020). PubChem Database. Diisopropyl

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 ether, CID=7914. Retrieved from
https://pubchem.ncbi.nlm.nih.gov/compound/Diisopropyl-ether

National Pollutant Inventory (2018). Acetic acid (ethanoic acid), Retrieved from
http://www.npi.gov.au/resource/acetic-acid-ethanoic-acid

Patil, Dr.Kiran & Kulkarni, Bhaskar. (2014). Review of Recovery Methods for Acetic Acid
from Industrial Waste Streams by Reactive Distillation. Journal of Water Pollution
& Purification Research. 1. 1-6.

Pal, D., Thakre, N., Keshav, A., Kumar, A., Singh, D., & Kumari, N. (2017). Liquid-liquid
extraction equilibrium for pyruvic acid recovery: experimental data and modeling.
Brazilian Journal of Chemical Engineering, 34(3), 919–925. doi:
10.1590/0104-6632.20170343s20150276

Scott, K. (1995). Absorption, Desorption And Extraction With Membranes. Handbook of

Industrial Membranes, 633–639. doi: 10.1016/b978-185617233-2/50015-5

Wolska, Lidia & Przyjazny, Andrzej & Namieśnik, Jacek. (2006). Sources of Errors
Associated with the Determination of PAH and PCB Analytes in Water Samples.
Analytical Letters - ANAL LETT. 39. 2317-2331. 10.1080/00032710600755793.

Wu, C., & Tu, X. (2016). Biological and fermentative conversion of syngas. Handbook of
Biofuels Production, 335–357. doi: 10.1016/b978-0-08-100455-5.00012-6

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Appendix

The Solvent Miscibility Table showing miscibilities of two solvents.

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