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SNOW: Styrene from Ethane and Benzene

Article  in  Studies in Surface Science and Catalysis · December 2007

DOI: 10.1016/S0167-2991(07)80182-0

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SNOW: Styrene from Ethane and benzene
A.B. Editor et al. (Editors)
© 2005 Elsevier B.V./Ltd. All rights reserved. 1

Chapter 1

SNOW: Styrene from Ethane and Benzene

Domenico Sanfilippoa, Guido Caponea, Alberto Cipellia, Richard Pierceb,

Howard Clarkb, Matt Pretzb
a
Snamprogetti S.p.A. Viale DeGasperi 16 - S. Donato Milanese, 20097, Italy
b
The Dow Chemical Company, 2301 N. Brazosport Blvd., B-250 Freeport, TX 77541-
3257 U.S.A.

1. Introduction

Styrene is one of the most important monomers for the production of polymers,
resins and rubbers. Styrene production exceeds 25 Million MT/y. The biggest
consumer of Styrene monomer (SM) is Polystyrene (PS). Other major
derivatives are expanded polystyrene (EPS), SB Latex, SB Rubber, styrene
block co-polymers (eg ABS, MBS, SBS) and unsaturated polyester resins. SM
is a commodity and a lower production cost is a critical factor in the value chain
of its derivatives. The styrene market has been growing at a rate of 4.4% yearly
for the last several decades. It is expected that worldwide capacity will expand
by 5.5 million MT over the next five years
In the current art there are two commercial routes for the synthesis of SM:
a) The classic and largely applied EB/SM route: in a first step ethylbenzene
(EB) is formed by alkylation of benzene with ethylene in the presence of acid
catalyst (typically a zeolite). EB is catalytically dehydrogenated to SM in the
second step. Unconverted EB is recycled back to the dehydrogenation section.

C6H6 + CH2=CH2  C6H5-CH2-CH3  C6H5-CH=CH2 + H2 (1)

b) Alternatively and to a lower extent (<20% of the SM market) SM is co-

produced together with propylene oxide (PO/SM route). The EB synthesis is
followed by the EB peroxidation with the formation of the hydroperoxide. This
latter reacts in a further step with propylene forming propylene oxide (PO) and
ethylbenzyl alcohol that is dehydrated to styrene in a final step.
EB+O2C6H5-CHOOH-CH3+C3H6PO+C6H5-CHOH-CH3 SM+H2O (2)
2 D, Sanfilippo et al.

The conventional EB/SM route utilizes benzene and ethylene as raw materials
and the core is represented by the EB catalytic dehydrogenation step. The
continuous effort during several decades for improving this process in the areas
of reactor technology and catalyst technology has brought it to a high degree of
maturity and there is today little room for further improvement.

2. The innovative SNOW technology

The SNOW technology has been jointly developed by Snamprogetti and Dow
(SNOW = SNamprogetti + DOW) and represents a technological and economical
breakthrough in the Styrene Industry.
The SNOW technology is innovative as concerns many factors: raw materials,
reactor design, heat supply system, catalyst, feed composition.
a) Raw materials and reaction scheme
The SNOW complex is fed with benzene and ethane, which is
dehydrogenated in the same reaction system for EB dehydrogenation to produce
the stoichiometric amount of ethylene necessary for the benzene alkylation (Fig.
1). In an alternative version the SNOW Unit can be fed with ethylene and
benzene, similarly to the conventional technology (Fig 2: Ethylene Option).
The two Options (ethane or ethylene feed), allow the maximization of profit
according to the location, price and availability of the raw materials.
The Ethane Option can add value to stranded or limited use gas streams. Ethane
is a significant component of Natural Gas, and is also contained in some
refinery and petrochemical streams (FCC and crackers off gas, by-product of
liquid feed crackers). SNOW provides an opportunity to monetize Natural Gas
without the need of an associated Ethylene Project, which may be attractive in
some locations. Additionally, since this Option decouples SM production from
Steam Cracker it becomes possible to build a new SM unit (or retrofit an
existing conventional one) in refinery/petrochemical complexes without the
need of debottlenecking the Steam Cracking plant.
E th a n e
E th yl S e p a ra tio n
D eEhth
ydylb
ro e
gn e ze
n antio
en &SStyre
tyrennee
B enzene B e n ze n e S tyre n e
D e h yd
S ero
c tio
g enn a tio n P uu rific
P rific aa tio
tio nn
P ro c e s s
C 2 R e c yc le E B R e c yc le

Fig. 1: Conceptual block diagram of SNOW technology (Ethane Option)

E t h y le n e EB SM
E th y l S e p a r a tio n
E th y lb e n z e n e
B enzene B en zene & S ty re n e S ty re n e
D e h y d r o g e n a tio n
P ro c e s s P u r if ic a tio n
E B R e c y c le
Fig. 2: SNOW Technology (Ethylene Option)
Snow: Styrene from Ethane and Benzene 3

b) Reactor Design
Dehydrogenation of ethylbenzene to styrene and as well of ethane to
ethylene is an endothermic, equilibrium-controlled reaction. Maximum
conversion increases with temperature. In order to achieve reasonable economic
conversion per pass, temperatures exceeding 600°C are a prerequisite.
Since the equilibrium conversion of ethane and EB are significantly different
for a specific set of conditions, a suitable process design allows SNOW Ethane
Option to produce per pass as much ethylene as EB converted.
The core of the SNOW technology is the reaction system, characterized by the
use of fluidized beds with circulating catalyst, similarly to the well known and
largely applied FCC technology (Fig. 3). The SNOW reactor is of Riser type,
where the catalyst is fast moving upwards, entrained by the co-current
hydrocarbons stream at a gas velocity of 4-20 m/s. Catalytic reactions are
performed rapidly (1-5 seconds) in the riser. Temperature ranges between 590
and 700°C according to the feed type and riser level. Conventional technologies
operate at EB partial pressures lower than one atmosphere (vacuum and steam
dilution) to get a higher driving force and better selectivities. This is not
required with SNOW.

Product Gas

Flue Gas

Nitrogen
Catalyst

Fuel
Air

Nitrogen
Catalyst
Reactor
Regenerator
Catalyst

Hydrocarbon Feed

Fig. 3: SNOW reaction section

The products leave the disengaging zone after complete removal of the catalyst
with a cyclone system. The reactor effluent is processed using conventional
separation technology. EB can be produced using conventional technology.
4 D, Sanfilippo et al.

c) Heat Supply System

The catalyst exiting the reactor is conveyed to the Regenerator (fig. 3), a
bubbling fluidized bed where the initial catalyst activity is restored by burning
the minor carbonaceous deposits built up on the catalyst surface during the
reaction time and restructuring the active sites. Air is fed to the regenerator
bottom countercurrently to the down-flowing catalyst. Flue gas leaves the
disengaging zone of the regenerator through a cyclones system.
As already mentioned, the dehydrogenation of EB and ethane are highly
endothermic:
C6H5-CH2-CH3  C6H5-CH=CH2+H2 Hr = 28.1 kcal/mole, 264 kcal/kg (1)

CH3-CH3  CH2=CH2 + H2 Hr = 32.7 kcal/mole, 1086 kcal/kg (2)

The endothermicity results in a high heat demand and requires high heat fluxes
at temperatures higher than 590°C along the reaction coordinates. In the SNOW
technology this heat is supplied by the heat capacity of the circulating catalyst:
"hot" catalyst, heated up in the regenerator at a temperature higher than that
required for reaction, goes to the reactor. The catalyst cools down in the riser
reactor during the reaction and flows back "cold" to the regenerator. Indeed in
order to satisfy the heat balance and generate the heat necessary to the reaction
loop in the regenerator some fuel is catalytically burnt, preferentially the
hydrogen rich off gas of the process is used. It increases significantly the carbon
efficiency of the process because of the low CO2 emissions in the flue gas.
The high surface of catalyst ensures a very efficient heat exchange directly in
the process side without any intermediate wall. Of course heat is recovered from
the reactor/regenerator effluents. Since the heat generation in the reaction loop
takes place through catalytic combustion of fuel gas at relatively low
temperature, SNOW is characterized by very low CO/NOx emissions.

d) Catalytic System Design

Conventional dehydrogenation technologies in the prior art have selected
promoted iron oxide as a unique catalyst to be operated under low EB partial
pressure and a significant dilution with steam.
For the SNOW project several candidates as active phase have been considered
and tested. The chosen formulation is based on promoted Gallium oxide.
Gallium systems are little known in scientific and patent literature. A new
chemistry and catalysis has been developed for the SNOW technology.
When duly promoted, gallium catalyst performance is excellent for ethane as
well as EB dehydrogenation. The catalyst is so active that it is possible to
operate it with very short contact time, typical of a fast riser reactor. The
selectivities to ethylene and styrene respectively are so high that no steam
dilution is required. Thus the SNOW technology has the unique advantage of
avoiding the steam cycle (generation, condensation, heat exchangers etc.). This
Snow: Styrene from Ethane and Benzene 5

aspect is particularly important because it allows significant benefits in energy

saving and CO2 emission reduction. Coke formation is very low and the catalyst
circulation provides a continuous regeneration from coke build up.
The commercial catalyst is a microspheroidal, attrition resistant, high heat
capacity solid, synergistically designed and developed together with the reactor
engineering. Catalyst PSD (Particle Size Distribution) and mechanical
properties have been optimized for the use in a fluidized bed and make this
catalyst more resistant than the typical FCC catalysts.
The SNOW technology allows, like in the other fluidized bed processes, the
continuous make up of fresh catalyst, maintaining its "equilibrium" activity
stable over the time. No turndown for catalyst substitution is required and no
aging from Start-Of-Run to End-of-Run conditions is present.

3. SNOW Technology development steps

Snamprogetti and Dow joined their effort for developing the SNOW technology
in early 2000. The initial technology development and engineering skills of
Snamprogetti [1-3], and the complementary styrene production and marketing
expertise of Dow have been integrated[4-7]. R&D activity has been carried out
initially in microreactors and bench scale units. Results have been validated at
pilot plant level utilizing a DCR (Davison Cracking Reactor), typically adopted
for FCC catalyst testing.
The next step has been the construction and operation on a Dow site of a PDU
(Process Demonstration Unit, fig. 8) that has allowed testing all aspects of the
new technology including process yields, conversion and economics, SM
product quality for derivatives application, reactor and catalyst reliability and so
on. The PDU is on a scale intended to prove critical unit operations in both
performance and reliability. The capacity (feed rates in the 500+ kg/hr range) is
of sufficient size to minimize the risk of scale-up of critical unit operations. The
PDU operates at the same conditions as a world scale unit, but has allowed
enough variation around process parameters in order to optimize the process.
Hydrodynamics have been modeled and demonstrated in large scale mock ups
(cold flow models). Catalyst production has been successfully scaled up from
laboratory formulations to commercial scale manufacture. Several tens of tons
of catalyst have been produced in full scale equipment. The PDU operation has
validated the catalyst performances, the scale up criteria and the whole process.

4. Final considerations

The Dow Chemical Company and Snamprogetti S.p.A. have synergistically

developed a new route to produce SM from ethane and benzene (SNOW
”Ethane Option") or ethylene and benzene (SNOW ”Ethylene Option") which
Dow/Snamprogetti will be uniquely offering in the market to styrene producers.
 6 D, Sanfilippo et al.

Relative Cost 1000 = Conventional EBSM

1000
950
900
Capital Charge
850 Depreciation
800 Fixed Costs
750 Net Utilities
Net Raw Materials
700
650
600
550
500
EBSM SNOW Ethylene SNOW Ethane Feed
Feed
Fig. 4: Example of economics of SNOW (Ethane/Ethylene Options) relative to conventional
The innovative SNOW process is expected to enable significant cost savings in
both versions from benzene-ethane and from benzene-ethylene.
Fig. 4 reports an example of the SNOW advantage versus the conventional
EB/SM route. Of course the advantage may change with the plant location due
to the different valorization of raw material, energy and equipment cost.
The "Ethane Option" moves away from the conventional Styrene production
process and raw materials, captures ethane-ethylene price differential and
eliminates the need for upstream investment in ethylene production at a steam
cracker or ethylene purchases and offers greater location flexibility.
The "Ethylene Option" offers significant advantage in investment cost versus
conventional approach.
SNOW will use less energy (no dilution steam) and emit less CO2 than
competing processes (no fuel gas, instead burns H2 produced in the process).

Acknowledgements
The mentioned authors are the iceberg tip of an impressive number of
colleagues in Dow and Snamprogetti and EniTecnologie that have been working
in this project around the World with competence, passion, and creativity.
References:
1. F. Buonomo, D. Sanfilippo, R. Iezzi, E. Micheli USP 5,994,258 and USP 6,242,660 (1997)
to Snamprogetti
2. F. Buonomo, G. Donati, E. Micheli, L. Tagliabue USP 6,031,143 (1997) to Snamprogetti
3. D. Sanfilippo, R. Iezzi USP 6,841,712 (1999) to Snamprogetti
4. I. Miracca, G. Capone USP 7,094,940 (2001) to Snamprogetti
5. D. Sanfilippo, A. Bartolini, R. Iezzi US Appl. 2004/0259727 to Snamprogetti
6. D. Sanfilippo, I. Miracca, G. Capone, V. Fantinuoli US Appl. 2005/01776016
7. W. Castor, S. Hamper, M. Pretz, S. Domke WO 2005/077867 to Dow

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