ACRYLIC ACID

PROCESS
Chemical Engineering fundamental

DECEMBER 1ST, 2014

MAHDI AGHAJANMOLAEI
B00265677
0

Table of Contents
Introduction:....................................................................................................2
Nature of the reaction:..................................................................................3
Production:......................................................................................................3
Catalysts:.........................................................................................................6
By-Products:....................................................................................................6
Materials:.........................................................................................................7
Discussion and Modification:........................................................................7
Health & Safety Precautions & Potential Hazards:..................................8
References:......................................................................................................9
Bibliography:.................................................................................................10

Introduction:
The majority of plants manufacture acrylic acid by the catalytic oxidation of
propylene. This compound is an organic compound with the formula
CH2=CHCO2H which is used in several industrial applications and it attracts a
wide range of industries for painting, chemical fibres and adhesives. However,
the highest growing use of acrylic acid is in the production of superabsorbent
polymers. In addition, more than 65% of acrylic acid is used to produce
Acrylate esters (Glauser, 2007).
Acrylic acid can seriously damage the environment when released in industrial
effluents due to its high toxicity (A. Eftaxias a, 2001). The toxicity can be
reduced by combination of mechanisms e.g. biodegradation, oxidation, and
volatilisation.

Nature of the reaction:

Production:
The propylene market price is closely tied to the prices of crude oil due to the
use of crude oil derivatives such as naphtha via steam cracking, and vacuum
gas oil via fluid catalytic cracking as a feedstock for making propylene.
Alternative feedstock for making acrylic acid have been considered, that
might appeal in the long term e.g. glycerol (https://www.shokubai.co.jp,

n.d.).
Nearly all companies produce acrylic acid via the two-stage oxidation of the
propylene.

Propylene is first oxidised to acrolein and then acrolein oxidised to acrylic

acid. Please see below:

C 3 H 6 O2 C 3 H 4 O H 2 O

Acrolein:

Acrylic Acid:

1
C 3 H 4 O O2 C 3 H 4 O2
2

Propylene is fed to the reactor either from cracking of naphtha or from a

storage tank. Steam is then added to provide stability for the exothermic
heat of the process. Therefore, a feed mixture of air, steam and propylene
is fed to the reactor. After the production of acrolein, it is essential to cool
the products to below 100C to avoid further oxidation. This is achieved by
introducing the product[s] to a quenching tower where the reaction is
rapidly quenched. The product[s] can be cooled down to 40 o C, however
to avoid further oxidation temperature should not exceed 310 0 C.
To be more efficient, an additional recovery of acrylic acid and the byproduct, acetic acid, can take place in an absorber.
The liquid stream, stream [S-8], leaving the absorber contains dilute
aqueous acid, and is connected to the liquid-liquid extraction section in
the extraction tower to purify the acid. The organic phase leaving the
extraction tower, stream[S-10], contains all of the acrylic acid and
essentially there is no water or other components which is fed to tower
[distillation tower].
Final purification takes place in a distillation tower to produce 99% purified
acrylic acid as the bottom product and acetic acid is produced as the top
product. Acrylic acid is then cooled and collected. If the acrylic acid
temperature exceeds 90C, spontaneous polymerisation would occur.
Several heating and cooling constraints are important in order to avoid
explosive conditions and runaway reactions.

Figure 1

Table 1:
Code
S
V
E-10
5

Name
Stream
Valve
Fluid
pump

Catalysts:
The homogeneous catalysts are avoided due to their toxic contamination.
Most companies prefer heterogeneous catalysts based in noble and oxidemetals (Chemie and deHan, 2003). One of the disadvantages of using
noble metals can be the cost factor; noble metals significantly increase
the process cost. Oxides metals such as titanium and nickel are found to
be, in some cases, highly unstable (Shende and Levec, 2000). In this
process catalysts are being used in two oxidation processes:
Stage 1: propylene to acrolein
Stage 2: acrolein to acrylic acid.
Wide range of catalyst can be used in stage one e.g. Iron, Cobalt. However
heavy oxides e.g. tellurium and arsenic oxides are used for second stage.
(Krik-Othmer, 1978)

By-Products:
Some typical side reactions are given below which occur as a result of
oxidation of reactant and product:

In Reactor:

9
C 3 H 6 O2 3CO2 3H 2 O
2

Acrolein to produce carbon dioxide and acetic Acid:

3
C 3 H 4 O O2 C 2 H 4 O2 CO2
2
7
C 3 H 4 O O 3CO2 2 H 2 O
2

Acetic acid uses varied, it is one of the most important reagents. It commonly
used as a solvent for many industrial processes.

Materials:
There are several columns, exchangers, pumps, vessels, and other
miscellaneous equipment in the extraction column. Heat Exchangers are
essential for this reaction. The cost depends on the size and the required
type. Reactor and distillation tower consist of many small tubes, carrying a
heat transfer medium. Since acrylic acid and acetic acid have boiling
points of 141.8 C and 117 C respectively. Distillations for this
separation process must take place under vacuum.

Discussion and Modification:

Deionised water can be added into stream, [S-5], to slightly cool down the
product before it reaches the quenching tower. Deionised water also can
be used in the absorber to prevent the reaction from over-heating.
Moreover, in a wide range of chemical processes, molten salt is fed into
the reactor to cool down the temperature inside the reactor. However, this
is disadvantageous as it can be an additional cost for the process.
Since acrylic acid has a trend to polymerise, hydroquinone can be injected
throughout the system to make the reaction more efficient. The waste gas
from the absorber can be recycled to stream, [S-6]. If the operation would
take place at temperatures between 180 and 200 C, this would be
relatively more convenient since the feed stream temperature is usually
between 180-190 C. Hence, no additional heating/cooling source is
necessary to maintain the above mentioned temperature. This in turn,
would increase the profitability and reduce the cost[s] involved.

Health & Safety Precautions & Potential

Hazards:
Acrylic acid and acetic acid are extremely hazardous and they can cause
long term injuries. They are a strong irritant to the skin, eyes, and mucous
membranes in humans, inhalation has been observed to produce nose and
eye irritation, lungs internal bleeding, and degenerative changes in the
liver and kidneys. The liquid may cause blindness if splashed into the eye
(Technology Transfer Network - Air Toxics Web Site, 2000).
Eye protection, non-vented and designed specifically to protect against
chemical splash goggles should be worn (www.basf.com, n.d.). Hand
protection such as chemical resistant gloves, protective arm sleeves,
aprons, full body coveralls, boots e.g. steel toe safety shoes, and head
coverings are essential to wear. The material should be resistant to acrylic
acid e.g. Butyl rubber of 0.4 to 0.6 mm thickness (www.basf.com, n.d.).
Hence it is essential for all workers to follow all the above health and
safety guidelines.

References:
-A. Eftaxias a, J. F. (2001). Applied Catalysis B: Environmental 33 (2001) 175
190. Kinetic modelling of catalytic wet air oxidation of, p. 175190.

- Fluka Chemie and Riedel-deHan, 2003. Scientific Research. Madrid, p. 4546.

- Kirk-Othmer, 1978. Encyclopedia of Chemical Technology, A-Alkanolamines

(Volume 1). Volume 1 Edition. Wiley-Interscience. p. 339

- Sittig, M, 2002. Handbook of Toxic and Hazardous Chemicals and

Carcinogens, 4th ed. Vol 1 A-H Norwich, NY: Noyes Publications, p. 2243

- Acrylic Acid | Technology Transfer Network Air Toxics Web site | US EPA.
2014. Acrylic Acid. [ONLINE] Available
at:http://www.epa.gov/ttnatw01/hlthef/acrylica.html. [Accessed 15th Nov
2014].

-Acrylic Acid Product Safety Summary |basf.2014. Available at:

http://www.basf.com/group/corporate/us/e/function/conversions:/publish/content/about
-basf/worldwide/northamerica/USA/sustainability/rc/docs/Acrylic_Acid_Product_Safety_Summary.pdf.
[Accessed 15th Nov 2014].

-Acrylic Acid| Product Safety Assessment DOW.2014. Available

at:http://msdssearch.dow.com/PublishedLiteratureDOWCOM/dh_048a/0901b803
8048a3cd.pdf?filepath=productsafety/pdfs/noreg/23300269.pdf&fromPage=GetDoc [Accessed 15th Nov 2014].

Bibliography:
9

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Carcinogens. 2nd ed. Park Ridge, NJ: Noyes Publications( Noyes Data
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- Sittig, M, 2002. Handbook of Toxic and Hazardous Chemicals and
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