CHAPTER 5.

1
UOP OLEFLEX PROCESS FOR
LIGHT OLEFIN PRODUCTION
Joseph Gregor and Daniel Wei
UOP LLC
Des Plaines, Illinois
INTRODUCTION
The UOP* Oleflex* process is catalytic dehydrogenation technology for the production
of light olefins from their corresponding paraffin. An Oleflex unit can dehydrogenate
propane, isobutane, normal butane, or isopentane feedstocks separately or as mixtures
spanning two consecutive carbon numbers. This process was commercialized in 1990,
and by 2002 more than 1,250,000 metric tons per year (MTA) of propylene and more
than 2,800,000 MTA of isobutylene were produced from Oleflex units located through-
out the world.
PROCESS DESCRIPTION
The UOP Oleflex process is best described by separating the technology into three dif-
ferent sections:

Reactor section

Product recovery section

Catalyst regeneration section

Reactor Section
Hydrocarbon feed is mixed with hydrogen-rich recycle gas (Fig. 5.1.1). This combined
feed is heated to the desired reactor inlet temperature and converted at high monoolefin
selectivity in the reactors.
5.3
*Trademark and/or service mark of UOP.
Source: HANDBOOK OF PETROLEUM REFINING PROCESSES
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The reactor section consists of several radial-flow reactors, charge and interstage
heaters, and a reactor feed-effluent heat exchanger. The diagram shows a unit with four
reactors, which would be typical for a unit processing propane feed. Three reactors are
used for butane or isopentane dehydrogenation. Three reactors are also used for blends of
C
3
-C
4
or C
4
-C
5
feeds.
Because the reaction is endothermic, conversion is maintained by supplying heat
through interstage heaters. The effluent leaves the last reactor, exchanges heat with the
combined feed, and is sent to the product recovery section.
Product Recovery Section
A simplified product recovery section is also shown in Fig. 5.1.1. The reactor effluent
is cooled, compressed, dried, and sent to a cryogenic separation system. The dryers
serve two functions: (1) to remove trace amounts of water formed from the catalyst
regeneration and (2) to remove hydrogen sulfide. The treated effluent is partially con-
densed in the cold separation system and directed to a separator.
Two products come from the Oleflex product recovery section: separator gas and sep-
arator liquid. The gas from the cold high-pressure separator is expanded and divided into
two streams: recycle gas and net gas. The net gas is recovered at 90 to 93 mol % hydrogen
purity. The impurities in the hydrogen product consist primarily of methane and ethane.
The separator liquid, which consists primarily of the olefin product and unconverted paraf-
fin, is sent downstream for processing.
Catalyst Regeneration Section
The regeneration section, shown in Fig. 5.1.2, is similar to the CCR* unit used in the
UOP Platforming* process. The CCR unit performs four functions:

Burns the coke off the catalyst

Redistributes the platinum

5.4 DEHYDROGENATION
FIGURE 5.1.1 Oleflex process flow.
*Trademark and/or service mark of UOP.
UOP OLEFLEX PROCESS FOR LIGHT OLEFIN PRODUCTION
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UOP OLEFLEX PROCESS FOR LIGHT OLEFINS 5.5

Removes the excess moisture

Reduces the catalyst prior to returning to the reactors

The slowly moving bed of catalyst circulates in a loop through the reactors and the
regenerator. The cycle time around the loop can be adjusted within broad limits but is typ-
ically anywhere from 5 to 10 days, depending on the severity of the Oleflex operation and
the need for regeneration. The regeneration section can be stored for a time without inter-
rupting the catalytic dehydrogenation process in the reactor and recovery sections.
DEHYDROGENATION PLANTS
Propylene Plant
Oleflex process units typically operate in conjunction with fractionators and other
process units within a production plant. In a propylene plant (Figure 5.1.3), a propane-
rich liquefied petroleum gas (LPG) feedstock is sent to a depropanizer to reject butanes
and heavier hydrocarbons. The depropanizer overhead is then directed to the Oleflex
unit. The once-through conversion of propane is approximately 40 percent, which
closely approaches the equilibrium value defined by the Oleflex process conditions.
Approximately 90 percent of the propane conversion reactions are selective to propy-
lene and hydrogen; the result is a propylene mass selectivity in excess of 85 wt %. Two
product streams are created within the C
3
Oleflex unit: a hydrogen-rich vapor product
and a liquid product rich in propane and propylene.
Trace levels of methyl acetylene and propadiene are removed from the Oleflex liquid
product by selective hydrogenation. The selective diolefin and acetylene hydrogenation
step is accomplished with the Hls SHP process, which is available for license through
UOP. The SHP process selectively saturates diolefins and acetylenes to monoolefins
FIGURE 5.1.2 Oleflex regeneration section.
UOP OLEFLEX PROCESS FOR LIGHT OLEFIN PRODUCTION
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without saturating propylene. The process consists of a single liquid-phase reactor. The
diolefins plus acetylene content of the propylene product is less than 5 wt ppm.
Ethane and lighter material enter the propylene plant in the fresh feed and are also cre-
ated by nonselective reactions within the Oleflex unit. These light ends are rejected from
the complex by a deethanizer column. The deethanizer bottoms are then directed to a
propane-propylene (P-P) splitter. The splitter produces high-purity propylene as the over-
head product. Typical propylene purity ranges between 99.5 and 99.8 wt %. Unconverted
propane from the Oleflex unit concentrates in the splitter bottoms and is returned to the
depropanizer for recycle to the Oleflex unit.
Ether Complex
A typical etherification complex configuration is shown in Fig. 5.1.4 for the production
of methyl tertiary butyl ether (MTBE) from butanes and methanol. Ethanol can be sub-
stituted for methanol to make ethyl tertiary butyl ether (ETBE) with the same process
configuration. Furthermore, isopentane may be used in addition to or instead of field
butanes to make tertiary amyl methyl ether (TAME) or tertiary amyl ethyl ether
(TAEE). The complex configuration for a C
5
dehydrogenation complex varies accord-
ing to the feedstock composition and processing objectives.
Three primary catalytic processes are used in an MTBE complex:

Paraffin isomerization to convert normal butane into isobutane

Dehydrogenation to convert isobutane into isobutylene

Etherification to react isobutylene with methanol to make MTBE

Field butanes, a mixture of normal butane and isobutane obtained from natural gas con-
densate, are fed to a deisobutanizer (DIB) column. The DIB column prepares an isobutane
overhead product, rejects any pentane or heavier material in the DIB bottoms, and makes
a normal butane sidecut for feed to the paraffin isomerization unit.
The DIB overhead is directed to the Oleflex unit. The once-through conversion of
isobutane is approximately 50 percent. About 91 percent of the isobutane conversion reac-
tions are selective to isobutylene and hydrogen. On a mass basis, the isobutylene selectivity
5.6 DEHYDROGENATION
FIGURE 5.1.3 C
3
Oleflex plant.
UOP OLEFLEX PROCESS FOR LIGHT OLEFIN PRODUCTION
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is 88 wt %. Two product streams are created within the C
4
Oleflex unit: a hydrogen-rich
vapor product and a liquid product rich in isobutane and isobutylene.
The C
4
Oleflex liquid product is sent to an etherification unit, where methanol reacts
with isobutylene to make MTBE. Isobutylene conversion is greater than 99 percent, and
the MTBE selectivity is greater than 99.5 percent. Raffinate from the etherification unit is
depropanized to remove propane and lighter material. The depropanizer bottoms are then
dried, saturated, and returned to the DIB column.
PROPYLENE PRODUCTION ECONOMICS
A plant producing 350,000 MTA of propylene is chosen to illustrate process econom-
ics. Given the more favorable C
4
and C
5
olefin equilibrium, butylene and amylene pro-
duction costs are lower per unit of olefin when adjusted for any differential in feedstock
value. The basis used for economic calculations is shown in Table 5.1.1. This basis is
typical for U.S. Gulf Coast prices prevailing in mid-2002 and can be used to show that
the pretax return on investment for such a plant is approximately 24 percent.
Material Balance
The LPG feedstock is the largest cost component of propylene production. The quantity of
propane consumed per unit of propylene product is primarily determined by the selectivi-
ty of the Oleflex unit because fractionation losses throughout the propylene plant are small.
The Oleflex selectivity to propylene is 90 mol % (85 wt %), and the production of 1.0 met-
ric ton (MT) of propylene requires approximately 1.2 MT of propane.
An overall mass balance for the production of polymer-grade propylene from C
3
LPG
is shown in Table 5.1.2 for a polymer-grade propylene plant producing 350,000 MTA,
based on 8000 operating hours per year. The fresh LPG feedstock is assumed to be 94 LV %
propane with 3 LV % ethane and 3 LV % butane. The native ethane in the feed is rejected in
the deethanizer along with light ends produced in the Oleflex unit and used as process fuel.
The butanes are rejected from the depropanizer bottoms. This small butane-rich
UOP OLEFLEX PROCESS FOR LIGHT OLEFINS 5.7
FIGURE 5.1.4 MTBE production facility.
UOP OLEFLEX PROCESS FOR LIGHT OLEFIN PRODUCTION
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stream could be used as either a by-product or as fuel. In this example, the depropanizer
bottoms were used as fuel within the plant.
The Oleflex process coproduces high-quality hydrogen. Project economics benefit
when a hydrogen consumer is available in the vicinity of the propylene plant. If chemical
hydrogen cannot be exported, then hydrogen is used as process fuel. This evaluation
assumes that hydrogen is used as fuel within the plant.
Utility Requirements
Utility requirements for a plant producing 350,000 MTA of propylene are summarized
in Table 5.1.3. These estimates are based on the use of an extracting steam turbine to
drive the Oleflex reactor effluent compressor. A water-cooled surface condenser is used
on the steam turbine exhaust. A condensing steam driver was chosen in this example for
the propane-propylene splitter heat-pump compressor.
Propylene Production Costs
Representative costs for producing 350,000 MTA of polymer-grade propylene using the
Oleflex process are shown in Table 5.1.4. These costs are based on feed and product
5.8 DEHYDROGENATION
TABLE 5.1.2 Material Balance for a 350,000-MTA Propylene
Plant
Flow rate, Flow rate,
MT/h MTA
Feed:
C
3
LPG (94 LV % propane) 55.00 440,000
Products:
Propylene (99.5 wt %) 43.75 350,000
Fuel by-products 11.25 90,000
Total products 55.00 440,000
Note: MT/h metric tons per hour; MTAmetric tons per annum.
TABLE 5.1.1 Utility, Feed, and Product Valuations for Economic
Calculations
Utility values
Fuel gas $2.80/million Btu $11.10/million kcal
Boiler feed water $0.45/klb $1.00/MT
Cooling water $0.12/kgal $0.03/m
3
Electric power $0.05/kWh $0.05/kWh
Feed and product values
C
3
LPG (94 LU % propane) $0.35/gal $180/MT
Propylene (99.5 wt %) $0.19/lb $420/MT
Note: MT metric tons; SCF standard cubic feet.
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values defined in Table 5.1.1. The fixed expenses in Table 5.1.4 consist of estimated
labor costs and maintenance costs and include an allowance for local taxes, insurance,
and interest on working capital.
Capital Requirements
The ISBL erected cost for an Oleflex unit producing 350,000 MTA of polymer-grade
propylene is approximately $145 million (U.S. Gulf Coast, mid-2002 erected cost).
This figure includes the reactor and product recovery sections, a modular CCR unit, a
Hls SHP unit, and a fractionation section consisting of a depropanizer, deethanizer,
and heat-pumped P-P splitter. The costs are based on an extracting steam turbine driv-
er for the reactor effluent compressor and a steam-driven heat pump. Capital costs are
highly dependent on many factors, such as location, cost of labor, and the relative work-
load of equipment suppliers.
Total project costs include ISBL and OSBL erected costs and all owners costs. This
example assumes an inclusive mid-2002 total project cost of $215 million including:

ISBL erected costs for all process units

OSBL erected costs (off-site utilities, tankage, laboratory, warehouse, for example)

Initial catalyst and absorbant loadings

UOP OLEFLEX PROCESS FOR LIGHT OLEFINS 5.9
TABLE 5.1.3 Net Utility Requirements for a 350,000-MTA
Propylene Plant
Utility cost
Utility requirements Consumption $/h $/MTA C
3
Electric power 6,500 kW 325 7.43
Boiler feed water 10 MT/h 10 0.23
Cooling water 6,000 m
3
/h 180 4.11
Fuel gas (13.1 million kcal/h) 145 3.31
Net utilities 15.08
Note: MTAmetric tons per annum; MT/h metric tons per hour.
TABLE 5.1.4 Cost for Producing 350,000 MTA of Polymer-Grade
Propylene Using the Oleflex Process
Costs
Revenues, million
million $/year $/year $/MT C
3
Propylene product 147.0
Propane feedstock 79.2 226.3
Net utilities 5.3 15.1
Catalyst and chemicals 3.8 10.9
Fixed expenses 7.0 20.0
Total 147.0 95.3 272.3
Note: MTAmetric tons per annum; MT metric tons.
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Technology fees

Project development including site procurement and preparation

Overall Economics
Because the feedstock represents such a large portion of the total production cost, the
economics for the Oleflex process are largely dependent on the price differential
between propane and propylene. Assuming the values of $180/MT for propane and
$420/MT for propylene, or a differential price of $240/MT, the pretax return on invest-
ment is approximately 24 percent for a plant producing 350,000 MTA of propylene.
5.10 DEHYDROGENATION
UOP OLEFLEX PROCESS FOR LIGHT OLEFIN PRODUCTION
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