Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

DEHYDROGENATION

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DEHYDROGENATION

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.

Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

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 throughout the world.

PROCESS DESCRIPTION
The UOP Oleflex process is best described by separating the technology into three different 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.

*Trademark and/or service mark of UOP.

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UOP OLEFLEX PROCESS FOR LIGHT OLEFIN PRODUCTION 5.4

DEHYDROGENATION

FIGURE 5.1.1

Oleflex process flow.

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 C3-C4 or C4-C5 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 condensed in the cold separation system and directed to a separator. Two products come from the Oleflex product recovery section: separator gas and separator 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 paraffin, 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

*Trademark and/or service mark of UOP.

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UOP OLEFLEX PROCESS FOR LIGHT OLEFIN PRODUCTION

UOP OLEFLEX PROCESS FOR LIGHT OLEFINS

5.5

FIGURE 5.1.2

Oleflex regeneration section.

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 typically 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 interrupting 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 propanerich 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 propylene and hydrogen; the result is a propylene mass selectivity in excess of 85 wt %. Two product streams are created within the C3 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

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UOP OLEFLEX PROCESS FOR LIGHT OLEFIN PRODUCTION 5.6

DEHYDROGENATION

FIGURE 5.1.3

C3 Oleflex plant.

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 created 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 overhead 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 substituted 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 C5 dehydrogenation complex varies according 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 condensate, 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 reactions are selective to isobutylene and hydrogen. On a mass basis, the isobutylene selectivity

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UOP OLEFLEX PROCESS FOR LIGHT OLEFIN PRODUCTION

UOP OLEFLEX PROCESS FOR LIGHT OLEFINS

5.7

FIGURE 5.1.4

MTBE production facility.

is 88 wt %. Two product streams are created within the C4 Oleflex unit: a hydrogen-rich vapor product and a liquid product rich in isobutane and isobutylene. The C4 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 economics. Given the more favorable C4 and C5 olefin equilibrium, butylene and amylene production 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 selectivity 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 metric ton (MT) of propylene requires approximately 1.2 MT of propane. An overall mass balance for the production of polymer-grade propylene from C3 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

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UOP OLEFLEX PROCESS FOR LIGHT OLEFIN PRODUCTION 5.8 TABLE 5.1.1 Calculations
DEHYDROGENATION

Utility, Feed, and Product Valuations for Economic

Utility values Fuel gas Boiler feed water Cooling water Electric power $2.80/million Btu $0.45/klb $0.12/kgal $0.05/kWh Feed and product values C3 LPG (94 LU % propane) Propylene (99.5 wt %)
Note: MT metric tons; SCF

$11.10/million kcal $1.00/MT $0.03/m3 $0.05/kWh

$0.35/gal $0.19/lb
standard cubic feet.

$180/MT $420/MT

TABLE 5.1.2 Plant

Material Balance for a 350,000-MTA Propylene Flow rate, MT/h Flow rate, MTA 440,000 350,000 90,000 440,000

Feed: C3 LPG (94 LV % propane) Products: Propylene (99.5 wt %) Fuel by-products Total products
Note: MT/h

55.00 43.75 11.25 55.00

metric tons per hour; MTA

metric tons per annum.

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

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UOP OLEFLEX PROCESS FOR LIGHT OLEFIN PRODUCTION

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 Electric power Boiler feed water Cooling water Fuel gas Net utilities
Note: MTA

Consumption 6,500 kW 10 MT/h 6,000 m3/h (13.1 million kcal/h)

$/h 325 10 180 145

$/MTA C3 7.43 0.23 4.11 3.31 15.08

metric 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 $/year Propylene product Propane feedstock Net utilities Catalyst and chemicals Fixed expenses Total
Note: MTA

million $/year 79.2 5.3 3.8 7.0 95.3

metric tons.

$/MT C3 226.3 15.1 10.9 20.0 272.3

147.0 147.0

metric tons per annum; MT

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 driver 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 workload 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

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UOP OLEFLEX PROCESS FOR LIGHT OLEFIN PRODUCTION 5.10

DEHYDROGENATION

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 investment is approximately 24 percent for a plant producing 350,000 MTA of propylene.

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