PROCESS 1: Partial Oxidation of Propylene

This process requires propylene, steam, and compressed air that have to be preheated to a
significantly high temperature before going to a reactor. In the reactor, the compounds will undergo partial
oxidation enough to produce more acrolein because further oxidation will yield acrylic acid and other
unwanted substances. The reactor effluent is quickly sent to a quencher to avoid further homogenous
oxidation reactions. Acrolein will then be scrubbed-off with water in the absorber and recovered at the
bottom. The off gas is sent to an incinerator for combustion.

The acrolein recovered will undergo series of distillation with water. Due to several impurities, a
waste water treatment facility must be installed.

PROCESS 2: Catalytic Partial Oxidation of Propylene for Acrolein Production

It is a general version of the process employed by Degussa in Germany and Sohio in USA (as
cited in Ohara et al. 1985) as well as Atochem in France (Etzkorn et al. 1991).

At the beginning of the process, propylene, steam (or inert gas) and air (or oxygen) were mixed in
a pipeline before being fed to a stainless steel reactor. The reactor could either be a fixed or a fluidised
bed, which was usually operated at 300400oC and at inlet pressure of 150-250kPa (Ohara et al. 1985).
Molten salt was usually used for temperature control. Depending on the performance of the catalyst used in
the reactor, the conversion rate of propylene could achieve up to 95%, in which 90% of the initial propylene
was converted to acrolein. However, there were some complete oxidations of the propylene to carbon
dioxides and water, as well as the formation of acrylic acid, acetic acid, acetaldehyde and other possible
minor products. The exit stream of reactor was passed to a quench tower in which the acrylic acid was
condensed and absorbed in a water-based stream. In this way, acrylic acid might be recovered from the
aqueous product stream if desired.

The gas exiting from the quench tower was then fed into an absorber where an aqueous solution of
acrolein was obtained by absorbing the gas in cold water. However part of the off-gas from the absorber
contained non-condensable components, such as un-reacted propylene, carbon oxides, oxygen and
nitrogen. These non-condensable gases were purged as waste gas after it passed through a combustion
system.
 The aqueous solution of acrolein was sent to a stripper (also called a desorption column or an
exchanger), where it was stripped to give crude acrolein. The crude acrolein consisted of low boiling point
compounds, which were mainly acrolein and acetaldehyde. The bottom stream from this column was
cooled and recycled as an absorbent. The crude acrolein stream was then distilled into the first fractionator
to remove acetaldehyde as tops. The bottoms went to another fractionator in which the acrolein itself was
taken as the overhead product. The product typically was up to 98% pure acrolein, with the remaining
consisting of water and trace acetaldehyde (Ohara et al.1985). The bottoms of this last fractionator
comprised higher boiling compounds, which were discarded. In order to minimise polymerisation, the whole
system was stabilised by hydroquinone (Ohara et al. 1985). Pipelines and apparatus were constructed
preferably of stainless steel.

Gas chromatography with a thermal conductivity detector could be utilised to determine the
impurities in acrolein (Ohara et al. 1985; Etzkorn et al. 1991). Hydroquinone could be determined either
colorimetrically by using Millons reagent to form a yellow complex (Ohara et al. 1985) or
spectrophotometrically at 292 nm in methanol after a sample was evaporated to dryness to remove the
interference of acrolein (Etzkorn et al. 1991).

PROCESS 3: Production of Acrolein by Dehydration of Glycerol

Acrolein as an important intermediate for the chemical industry can be produced via dehydration of
glycerol. Current process for the commercial production of acrolein is a single step propylene oxidation in
fixed-bed reactors. The limited reserves of fossil-fuel feedstocks and environmental issues have
encouraged researchers to develop substitutes or additives for fuels such as biodiesel.

Biodiesel is produced through transesterification of vegetable oil and animal fats. The major (10
wt%) by-product in this process is glycerol which contains impurities such as water, methanol, traces of
fatty acids as well as various inorganic and organic compounds. Depending on the type of processes
carried out for the synthesis of biodiesel, the purity of glycerol may vary. Glycerol is used as feedstock or
additives in a variety of applications. Prior to any application, however, crude glycerol has to be purified by
a distillation step. Concerning the costs of distillation, the market value of glycerol has dropped
considerably due to a rapid increase in the production of biodiesel and a lack of market for such an
enormous production capacity. Moreover, due to its origin from biomass, glycerol is a good renewable
starting material compared to fossil-fuel resources, such as propane and propylene.

Glycerol is recognized today as suitable raw material for the industrial manufacture of bioresourced
acrolein. Heating glycerol leads to its decomposition to acrolein, water and by-products. Of course a
suitable catalyst is needed to improve the reaction yield under the operating conditions. Due to the
availability of glycerol from biodiesel synthesis, dehydration of glycerol to acrolein is a potential alternative
to oxidation of propylene.

The reaction involved in order to obtain acrolein from glycerol is:

C3H8O3 C3H4O + 2H2O

glycerol acrolein water

The gas-phase dehydration of glycerol to produce acrolein comprises a separation of heavy

products by flash distillation immediately before the stage of dehydration of the glycerol and a separation of
heavy products by condensation immediately after the stage of dehydration of glycerol.

In the production of acrolein from glycerol, a liquid stream of 99% glycerol and a recycled stream
from the absorption column are mixed, then preheated via a heat exchanger and then conveyed to a flash
distillation column operating under 2.8 bar absolute. A stream of heavy by-products is recovered at the
bottom of the column, in which by-products are eliminated.

The gas phase exiting at the top of this column is conveyed to a heat exchanger, in order to reheat
it to 303C, and is then mixed with a stream of oxygen. This gas stream is fed to a fixed-bed multitubular
reactor which comprises a heterogeneous acid dehydration catalyst and coupled to a molten salt bath
which makes it possible to remove the heat produced by the reactions.

A gas stream exits from this reactor at 314C. This exit stream from the reactor is cooled to 123C
in the heat exchanger first described, which make it possible to recover a liquid stream of heavy products
and a gas fraction. The liquid stream is sent to a thermal oxidizer while the gas fraction is conveyed to an
absorption column.

The absorption column comprises a condenser at the top. A gas phase is recovered at the top and
a liquid phase is recovered at the outlet of the condenser, in which liquid phase is partially withdrawn and
partially recycled back to the column. A side stream is drawn off from the column and is condensed to give
the final product stream of acrolein.

The acrolein-poor liquid stream exiting the bottom of the absorption column is divided into a stream
which is eliminated and the recycled stream as described above.
References:

1. Acarser, M.S. et al. Conceptual Design I: Acrolein Production (Undergraduate Thesis).

EGE University. March 2010. Retrieved from
www.scribd.com/document/126399424/38621213-Project-I-Acrolein-Production
2. Naeem, A. et al. Production of Acrolein by Partial Oxidation of Propylene. University of
Engineering and Technology Lahore. Retrieved from
www.scribd.com/document/265998620/Production-of-Acrolein
3. Devaux, J., Jarrest, s., lozowski, a. and tlili, n. (2012). process for manufacturing acrolein
and/or acrylic acid from glycerol. 0330058A1. Retrieved from
www.google.com/patents/US20120330058
4. Wibawanta, Sandra Anni S. Catalytic Partial Oxidation of Propylene for Acrolein
Production (Masters Thesis). Retrieved from
espace.curtin.edu.au/bitstream/handle/20.500.11937/584/239842_Wibawanta2011.pdf?se
quence=2
TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES
363 P. Casal st., Quiapo, Manila

COLLEGE OF ENGINEERING AND ARCHITECTURE

Chemical Engineering Department
CHE 511: Plant Design
Homework no.2

Submitted by:
Baldecaas, Abigail D.
Lopez, Charmaine A.
Tapales, Maria Aljane

BSCHE V

Submitted to:
Engr. Lina dela Cruz

03 July 2017