New Catalytic Process For Production of Olefins: 1. Theme Description

New Catalytic Process for
Production of Olefins
Author: Marcello De Falco, Associate Professor, University
UCBM – Rome (Italy)
1. Theme description
Olefins, mainly ethylene (C2H4) and propylene (C3H6), are key
intermediate and feedstock for the production of a wide number
of chemical products, as the polyolefins (polyethylene – PE,
polypropylene – PP), Mono-ethylene glycol (MEG), Ethylene
Oxide (EO) and derivatives, Propylene Oxide (PO) and
derivatives, Polyvinyl chloride (PVC), ethylene dichloride
(EDC), Styrene, Acrylonitrile, Cumene, Acetic Acid, etc.
At the present, the worldwide demand of ethylene/propylene is

more than 200 million tons per year but the conventional
processes suffer for a series of problems as the high cost and
low conversion efficiency.
In the following, the traditional technologies, i.e. the

Thermal Steam Cracking and the Fluid Catalytic Cracking, are
firstly presented. Then the innovation in the olefins
production are described and assessed.
2. Olefins production conventional

processes
The most used olefins industrial production processes are:
Thermal Steam Cracking (TSC);

Fluid Catalytic Cracking (FCC).
TSC is a thermal process by which a feedstock, typically

composed by naphtha, ethane or propane, is heated up in a
furnace composed by both a convection and radiant section, and
mixed with steam to reduce the coke formation. The steam
addition depends on the TSC feedstock (from 0.2 kg steam to kg
of hydrocarbon for ethane to 0.8 kg steam to kg of hydrocarbon
for naphtha).
Then the products (ethylene, propylene, butadiene, hydrogen)

are quickly cooled down to avoid subsequent reactions
(quenching) and then are separated by means of a series of
operations (refer to Figure 1).
The reactions structure involved in thermal cracking is

complex and, generally, is based on a free radical mechanism.
Basically, two types of reactions are supported in a thermal
cracking process:
primary cracking, with the initial formation of paraffin

and olefins;
secondary cracking, with the formation of light products
rich in olefins are formed.
TSC is an energy intensive process: the specific energy

consumption per kg of produced olefin is 3.050 kcal/kg.
FCC is a multi-component catalytic system, where the catalyst

pellets are “fluidized” thanks to the inlet steam flow-rate
and the cracking process is supported at lower temperature
than TSC. A typical block diagram is shown in Figure 2, while
a FCC reactor drawing is reported in Figure 3.
Olefins production traditional technologies suffer from

inefficiency due to high temperature/high energy costs,
complex and expensive separation units and significant CO 2
emissions.
As a consequence, a strong interest towards the development of
more flexible, more efficient with a lower environmental
impact and less expensive catalytic olefin production
technologies is growing.
In the following, some of the most interesting technologies

developed during the last years are presented and described.
Fig. 1 – Thermal Steam Cracking plant layout [1]

Fig. 2 – Fluid Catalytic Cracking block diagram [2]
Fig. 3 – FCC reactor drawing [2]
3. Innovative Technologies
Advanced Catalytic Olefins (ACO)
The Advanced Catalytic Olefins (ACO TM ) technology has been

developed by Kellogg Brown & Root LLC (KBR) and SK Innovation
Global Technology. The process is an FCC-type with an improved
catalyst able to convert the feedstock in larger quantities of
ethylene and propylene, with a higher share of propylene than
conventional processes (the ratio of produced propylene to
produced ethylene is 1 versus 0.7 of the commercial
processes). The ACO process produces 10-25% more olefins than
the traditional FCC processes, with a reduction of consumed
energy per unit of olefins by 7-10% [3].
The plant configuration is composed of 4 sections:

riser/reactor, disengager, stripper and regenerator. Figure 4
shows a simplified process scheme, while Figure 5 illustrates
a picture of the first ACO commercial demonstration unit,
installed in South Korea and with a production capacity of 40
kta of olefins.
Fig. 4 – ACO plant process scheme [3]

Fig. 5 – ACO Commercial Demonstration unit installed in Ulsan
(South Korea)
PCC Process
The Propylene Catalytic Cracking is a fluid solids naphtha

cracking process patented by Exxon Mobil and based on an
optimization of catalyst, reactor design and operating
conditions set able to modulate the reactions selectivity,
leading to crucial economic benefits in comparison with the
conventional processes.
The PCC process is able to produce directly the propylene at

the chemical grade concentrations, thus avoiding the expensive
fractionation units. Moreover, the specific operating
conditions allows the minimization of aromatics
production [4].
Exxon is testing the innovative solutions on tailored pilot

facilities.
Indmax FCC Process
The Indmax process, developed by the Indian Oil Corporation,

is able to convert heavy feedstock to light olefins. It is a
FCC-type process where the reactions are supported by a
patented catalyst, able to reduce the contact time and thus
leading to higher selectivity to light olefins (ethylene and
propylene).
Another crucial characteristic of I-FCC process is the high

production flexibility: the process can be easily adjusted to
modulate the output, maximizing propylene, gasoline or
producing combinations (propylene and ethylene or propylene
and gasoline) [5].
Aither Chemicals’ catalytic process
Aither Chemicals, a company located in the U.S., developed an

innovative catalytic cracking process for the production of
ethylene, acetic acid, ethylene derivatives as ethylene oxide
(EO) and ethylene glycol (EG), polyethylene (PE, LLDPE, HDPE),
acetic acid derivatives as acetic anhydride, ethylene-acetic-
acid derivatives such as vinyl acetate monomer (VAM), ethyl
vinyl acetate (EVA) and other chemicals and plastics [6]. The
process uses oxygen instead of water steam and, globally,
needs much lower energy (-80%) and produces 90% less carbon
dioxide, being more environmentally sustainable.
Moreover, the CO2 and CO streams are captured at the outlet of

the catalytic process and utilized for producing chemicals and
polymer, thus nullifying the GreenHouse Gases emissions.
The production volumes foreseen for the innovative process are
224 ktons of ethylene, 112 ktons of acetic acid, 30 ktons of
CO2 and 15 ktons of CO.
Methane-to-olefins processes
Many research efforts are devoted to find new routes and

process configurations to convert directly natural gas to
olefins by low temperature reactors.
There are two possible methane-to-olefins (MTO) processes:
Indirect process, by which methane is converted into

syngas, methanol or ethane and then olefins are
produced;
Direct process, by which olefins are directly produced
from the methane in a single conversion step composed by
modified Fischer-Tropsch reaction.
Even if the direct route seems to be more interesting, at the

present not a good light olefins selectivity has been
obtained [7] and the MTO processes are more energy intensive
than the conventional cracking technologies. The only pre-
commercial scale application has been developed by UOP and
Total Petrochemicals in Feluy (Belgium): the plan is an
indirect process able to produce ethylene and propylene
through methanol and syngas.
Fig. 6 – MTO plant in Feluy, Belgium [8]
Some interesting patents have been produced on the MTO

topic [9], [10], [11], as well some accurate scientific
publications on important international journals [12], [13],
[14].
Propane Dehydrogenation
The company UOP developed an innovative Propane

Dehydrogenation (PDH) process able to produce ethylene and
propylene at lower cost thanks to a lower energy usage and a
more stable platinum-based catalyst [15]. The process, called
Oleflex, is divided in three sections: the reaction,
consisting of four radial-flow reactors, the product
purification and the catalyst regeneration. Fig. 7 shows a
process layout. Currently, 6 Oleflex units are installed and
produce more than 1.250.000 MTA of propylene worldwide.
Fig. 7 – UOP’s Oleflex process layout [8]
Shell Higher Olefins Process
The Shell Higher Olefins Process (SHOP) is an innovative

olefins production technology, developed by Royal Dutch Shell,
based on a homogeneous catalyst and used for production of
linear α – olefins (from C4 to C40) and internal olefins from
ethene.
The process architecture consists of three steps:
Oligomerization (conversion of a monomer or a mixture of

monomers into an oligomer, temperature = 90–100°C,
pressure = 100–110 bar, polar solvent);
Isomerization (molecules rearrangement reaction by a
metal catalyst, 100–125° C and 10 bar);
Methathesis (alkenes are converted into new products by
breaking – up and reformation of C-C double bonds by an
alumina-based catalyst, 100–125° C and 10 bar) [17].
At the present, SHOP is widely applied and the worldwide

production capacity is 1.190.000 t of linear alpha and
internal olefins per year.
Catalytic Partial Oxidation of ethane
ENI and the Italian research centre CNR developed an ethylene

production process through Short Contact Time – Catalytic
Partial Oxidation (CPO) of ethane.
The process is supported by a patented monolithic catalyst

able to improve the ethylene yield up to 55 wt.% [18].
At the present, the technology has been validated trough a

bench-scale unit, by which the optimal operating conditions
have been identified. However, the industrial scale
application is not ready yet, since an optimization of the CPO
reactor design and the improvement of the catalyst reliability
are needed.
_______________
[1]
http://nptel.ac.in/courses/103107082/module7/lecture2/lecture2
.pdf
[2]
http://nptel.ac.in/courses/103107082/module6/lecture5/lecture5
.pdf
[3]
http://www.kbr.com/Newsroom/Publications/Articles/Advanced-Cat
alytic-Olefins-ACO-First-Commercial-Demonstration-Unit-Begins-
Operations.pdf
[4] M.W. Bedell, P.A. Ruziska, T.R. Steffens. On-Purpose

Propylene from Olefinic Streams. Davison Catalagram, 94 (2004)
– Special Edition: Propylene –
[5] http://www.cbi.com/images/uploads/tech_sheets/I-FCC-12.pdf
[6]
http://www.aitherchemicals.com/2012/06/21/aither-announces-ope
n-season/
[7] https://www.tut.fi/ms/muo/polyko/materiaalit/aa/apdf/polyk
o_technology_for_the_production_of_olefins.pdf
[8]
http://plasticsengineeringblog.com/2013/02/20/how-shale-gas-is
-changing-propylene/
[9] http://www.google.co.in/patents/US4450310
[10] http://www.google.com/patents/WO2014031524A1?cl=en
[11] http://www.freepatentsonline.com/7091391.html
[12]
http://www.sciencedirect.com/science/article/pii/S036054420800
0042
[13] http://www.hindawi.com/journals/jchem/2013/676901/
[14] http://www.netl.doe.gov/KMD/Cds/disk28/NG7-4.PDF
[15]
http://www.uop.com/?document=uop-olefin-production-solutions-b
rochure&download=1
[16] epg.science.cmu.ac.th/…/article-download.php?id=
[17] http://www.kataliza.chemia.polsl.pl/makro-ic-wyk4a.pdf
[18] L. Basini, S. Cimino, A. Guarinoni “Short Contact Time

Catalytic Partial Oxidation (SCT-CPO) for Synthesis Gas
Processes and Olefins Production”. Ind. Eng. Chem. Res., 2013,
52 (48), 17023–17037.

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New Catalytic Process for

At the present, the worldwide demand of ethylene/propylene is

In the following, the traditional technologies, i.e. the

2. Olefins production conventional

Thermal Steam Cracking (TSC);

TSC is a thermal process by which a feedstock, typically

Then the products (ethylene, propylene, butadiene, hydrogen)

The reactions structure involved in thermal cracking is

primary cracking, with the initial formation of paraffin

TSC is an energy intensive process: the specific energy

FCC is a multi-component catalytic system, where the catalyst

Olefins production traditional technologies suffer from

In the following, some of the most interesting technologies

Fig. 1 – Thermal Steam Cracking plant layout [1]

The Advanced Catalytic Olefins (ACO TM ) technology has been

The plant configuration is composed of 4 sections:

Fig. 4 – ACO plant process scheme [3]

The Propylene Catalytic Cracking is a fluid solids naphtha

The PCC process is able to produce directly the propylene at

Exxon is testing the innovative solutions on tailored pilot

Indmax FCC Process

The Indmax process, developed by the Indian Oil Corporation,

Another crucial characteristic of I-FCC process is the high

Aither Chemicals’ catalytic process

Aither Chemicals, a company located in the U.S., developed an

Moreover, the CO2 and CO streams are captured at the outlet of

Many research efforts are devoted to find new routes and

There are two possible methane-to-olefins (MTO) processes:

Indirect process, by which methane is converted into

Even if the direct route seems to be more interesting, at the

Some interesting patents have been produced on the MTO

The company UOP developed an innovative Propane

Fig. 7 – UOP’s Oleflex process layout [8]

Shell Higher Olefins Process

The Shell Higher Olefins Process (SHOP) is an innovative

The process architecture consists of three steps:

Oligomerization (conversion of a monomer or a mixture of

At the present, SHOP is widely applied and the worldwide

Catalytic Partial Oxidation of ethane

ENI and the Italian research centre CNR developed an ethylene

The process is supported by a patented monolithic catalyst

At the present, the technology has been validated trough a

[4] M.W. Bedell, P.A. Ruziska, T.R. Steffens. On-Purpose

[18] L. Basini, S. Cimino, A. Guarinoni “Short Contact Time

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