Olefins Conversion Technology Applications

Jose de Barros, ABB Lummus Global, USA ABSTRACT

The olefins market is quite energetic and mobile. Polyethylene and polypropylene demands continue to grow. The relative growth rates of PE and PP result in regional mismatch in the ethylene/propylene requirements. The Olefins Conversion Technology (OCT) licensed by ABB Lummus Global provides the feedstock and product flexibility needed to face the ever-changing demand for light olefins. The Olefins Conversion Technology is a family of proprietary processes utilizing a simple fixed bed catalyst system to inter-convert olefins to maximize plant profitability. The catalyst is highly selective and flexible to operate over a broad range of temperatures and pressures. This paper will discuss Olefins Conversion Technology and illustrate specific industry applications. OCT strategically varies the production rates of ethylene, propylene and butenes. When integrated with an ethylene plant, OCT provides flexibility to save feedstocks while varying light olefins production rates. The typical ethylene plant production range of 0.4 to 0.6 propylene to ethylene ratio can be extended to greater than 1. OCT achieves these goals at reduced capital and operating costs when compared to conventional ethylene plants. In refinery applications, OCT coupled with ABBs patented Low Pressure Recovery (LPR) process allows refiners to recover and upgrade fuel gas to propylene. Numerous industry sources of C4 feedstock can be refined with OCT to improve plant propylene production margins. The low cost applications provide refining flexibility to strategically optimize feed/product balances to meet varying market demands and maximize profits. OCT is the lowest capital and operating cost production route commercially available.

Olefins Conversion Technology Applications

Demand for the light olefins ethylene and propylene are forecasted to increase over the next decade. However, the demand for these light olefins will increase at different rates. Global propylene demand is forecasted to increase 6 to 8% per year, which exceeds the global ethylene demand growth forecast of 4 to 6% per year. Due to numerous upstream and downstream market factors such as NGL and crude prices, downstream product prices (particularly polyethylene and polypropylene), butadiene demand, gasoline prices and plant operating rates the relative demands and prices are constantly fluctuating and quite dynamic throughout the various regions of the world. The four commercially proven routes to propylene production are: Steam cracking Fluid catalytic cracking (FCC) Propane dehydrogenation Metathesis of ethylene and butylene

As shown in Figure 1, the majority of propylene is currently produced in steam crackers and FCC units. In these processes, propylene is produced as a byproduct of ethylene production or transportation fuels. Historically, FCC units balanced the propylene demand fluctuations by varying severity. The other technology routes will start playing a greater role in fulfilling the increasing demand for propylene. Propylene via propane dehydrogenation is typically considered in areas where there is ample low cost propane available as feedstock. Metathesis is emerging as the low capital/low energy production option that can stand alone or be integrated with FCC units or steam crackers for improved flexibility and performance. With the demand for propylene outpacing the demand for C4s, the metathesis process offers the potential for significant improvement in a steam crackers or FCC units operating margins by reducing C4 product and increasing propylene production.

World Propylene Sources

> 50 Million Tons/yr

Steam Cracker

FCC

C3 Dehydro/Metathesis

Figure 1 Propylene Souces (Worldwide)

Olefins Conversion Technology

The Olefins Conversion Technology (OCT) from ABB Lummus Global converts normal butylenes and ethylene to polymer grade propylene via metathesis. Two main equilibrium reactions (Figure 2) take place: metathesis and isomerization. Propylene is formed by the metathesis of ethylene and butene-2, and butene-1 is isomerized to butene-2 as butene-2 is consumed in the metathesis reaction. In addition to the main reactions, numerous side reactions between olefins also occur. Ethylene feed can be polymer grade ethylene or a dilute ethylene stream. Any saturated hydrocarbons, such as ethane and methane, do not react. The technology can be used with a variety of C4 streams including mixed C4s produced by FCC or steam cracking, or C4 raffinate from butadiene extraction or MTBE production. Based on the reaction stoichiometry, three tons of propylene are produced from two tons of butylene and one ton of ethylene.

Chemistry
Main Reactions
Ethylene + Butene-2 Butene-2
Figure 2 OCT Process Chemistry Figure 3 is a simple process flow diagram of the Lummus OCT process. Fresh C4s plus C4 recycle are mixed with ethylene feed plus recycle ethylene and sent through a guard bed to remove trace impurities from the mixed feed. The feed is heated prior to entering the vapor phase fixed-bed metathesis reactor where the equilibrium reaction takes place. The reactor is regenerated in-situ on a regular basis.
Guard Bed Ethylene Feed Metathesis Reactor Recycle Ethylene Ethylene Column Propylene Column Lights Purge

2 Propylene Butene-1

Propylene Product

C4 Plus Purge C
4

Feed

C4 Recycle

Figure 3 - OCT Process Flow Schematic As mentioned previously, the catalyst promotes the reaction of ethylene and butene-2 to form propylene and simultaneously isomerizes butene-1 to butene-2. The per-pass conversion of butylene is greater than 60% with overall selectivity to propylene exceeding 90%. The product from the metathesis reactor contains mainly propylene and unreacted feed.

Reactor effluent is sent to the ethylene recovery tower where the unreacted ethylene is recovered and recycled to the reactor. The C2 tower bottoms is processed in the C3 tower to produce propylene product and a C4 recycle stream. Purge streams containing non-reactive light material and C4s and heavier are also produced. Depending on the quantity of isobutylene in the C4 feed, the unit design may include a deisobutanizer to extend reactor runlength between regenerations and reduce OCT unit throughput, resulting in an overall lower capital cost plant. The deisobutanizer is a catalytic distillation tower that isomerizes butene-1 to butene-2 (CDIsom) to maximize recovery of OCT feed. The deisobutanzer option is evaluated on a case by case basis. Ultra-high purity propylene exceeding polymer grade specification is produced without a propylene fractionation system since the only source of propane is that contained in the C4 and ethylene feeds. OCT was originally developed by Phillips Petroleum and was first commercialized in 1965. Due to the propylene demand at that time, this unit processed propylene to produce ethylene and butylenes. A second unit that is still operating at Lyondell Petrochemical in the USA was commissioned in 1985 to produce propylene. ABB Lummus Global engineered both of these units. In 1996, Lummus acquired the technology from Phillips. Currently there is a unit under construction by Lummus for BASF Fina in the USA as part of the worlds largest single train olefins plant. When combined with a steam cracker or FCC unit, the OCT process is a proven, low cost product flexibility tool to increase propylene production and upgrade excess butylenes for greater total product value.

Refinery Applications
In current market conditions, FCC unit profitability is significantly enhanced by the increased flexibility to operate at higher propylene production rates and recoveries. It is currently feasible to double or triple FCC propylene yields by utilizing combinations of customized catalysts, higher severity operation, enhanced FCC design features and improved recovery facilities. Selective Component Cracking (SCC) is Lummuss maximum olefins catalytic cracking process. In this high olefin production mode, though the yield of gasoline decreases, the octane number increases. As the yield of propylene increases, the ethylene yield also increases. Ethylene recovery followed by butylene/ethylene metathesis to propylene can improve overall FCC plant economics.

30 25 20
Yield Wt% 15

10 5 0 FCC FCC ++ SCC + OCT

Figure 4 - FCC Propylene OCT Results

ABB Lummus Global has patented a low cost low-pressure-recovery (LPR) flow scheme for ethylene recovery in cat cracking units that does not sacrifice reliability, flexibility or safety. (See Figure 5). In this process, typically greater than 95% of the ethylene is recovered from the FCC offgas stream that is normally used as fuel gas. There are a number of offgas contaminants that need to be removed when recovering cat cracker ethylene; the presence and quantity of these contaminants will vary with crude source and FCC design and operation. Some typical impurities and their concentration range are shown in Table 1. The impurities are removed by a combination of proven processing steps, including caustic/water wash, adsorbtion, hydrogenation or fractionation.

Feed From FCC

Acid Gas Removal

Drying

Adsorbents and Acetylene Conversion

To Recovery Refrigeration

Offgas to Fuel Ethane Wash Ethane

Chilling and Demethanization Cs

2

C2 minus

Deethanization

Ethylene Fractionator

C plus 3 Ethylene Propylene Recovery

Figure 5 - Low Pressure Recovery Block Flow Diagram Table 1 Offgas Impurities CO, mol % H2S, ppm Acetylene, ppm Water Arsine, ppb Mercury, ppb Ammonia, ppb Nitriles, ppb Nitrogen Oxide Typical Range .05 1.1 50 100 3 100 --0 100 0 300 5 10 0 - 100 ---

Adding the LPR unit results in simple payouts typically less than two years, with excellent returns over the historical range of ethylene prices. LPR upgrades ethylene in FCC offgas from fuel value to product value. Most refineries with operating FCCs have the infrastructure in place for handling propylene product but not ethylene product. So the LPR process can also be used to recover ethylene for further processing via metathesis with refinery C4s to maximize propylene. The LPR/OCT combination further improves the economics over the LPR unit alone. Figure 6 illustrates the IRR over a range of product values for ethylene recovery only and propylene production via LPR/OCT. Adding the OCT to the LPR unit increases IRR 10 to 20% even after considering that historically propylene price ranges 0.8 to 0.85 of ethylene price. This is because the major feed in producing propylene is

butylene, which is significantly lower in price than either ethylene or propylene. The OCT unit combined with FCC maximizes high propylene production flexibility.

Increasing IRR Propylene Production from Offgas via an OCT unit

Propylene Ethylene Ethylene Recovery from Refinery Offgas. No OCT unit

300

350

400

450

500

550

600

650

Ethylene or Propylene Price $/MT

Figure 6 - Refinery Offgas Olefin Recovery Effect of Propylene and Ethylene Prices on IRR

Steam Cracker Applications

OCT combined with a steam cracker can significantly vary the propylene-to-ethylene product ratio and improve overall plant economics. The most recent project is the BASF Fina Petrochemicals plant in Port Arthur, Texas. The steam cracker is designed to produce over 950,000 metric tons per annum (MTA) ethylene and over 544,000 MTA propylene. The OCT unit will add more than 300,000 MTA additional propylene. Typical steam crackers with liquid feedstocks operate with a propylene-to-ethylene ratio range of 0.45 to 0.65 depending upon cracking severity. The mixed C4 product stream contains butadiene, butylenes and butanes. Butylenes can be reacted with ethylene via metathesis to increase the propylene-to-ethylene ratio. If butadiene is not required as a product, it can be selectively hydrogenated to butenes to provide additional butylene feed for metathesis. The steam cracker /OCT combination can result in propylene-to-ethylene ratios exceeding 1.1 as determined by the quantity of butylenes that are available for conversion in the OCT unit.

S team Cracker P ropylene

1.2 1 0.8 C 3-/C 2- R atio 0.6 0.4 0.2 0 M ax C 2M ax C 3+ OCT

Figure 7 - Steam Cracker Propylene OCT Results

Table 2 illustrates three operating scenarios. Case 1 recovers C4s as a mixed C4 product. This is typical of an operation where butadiene is a desired product for recovery. Case 2 hydrogenates and recycles the C4s to cracking. The naphtha feed requirement is reduced. This operating scenario has become more popular in recent years as butadiene demand has not kept pace with ethylene growth rates. However, this option reduces the quantity of hydrogen available for product sales. A more economic variation of Case 2 is to selectively hydrogenate the butadiene to butylenes to produce metathesis feed. This is shown in Case 3. The propylene/ethylene product ratio increase from 0.55 for Cases 1 and 2 to 0.94 for Case 3. This option requires more naphtha feed but 73% of the incremental naphtha feed is converted to propylene via metathesis. The IRR improves by 3 5% depending upon product price scenarios. Table 2 - Material Balance Comparison

Case Case Description

1 Stand-alone Steam Cracker Exported C 4s 2088

2 Stand-alone Steam Cracker No Exported C 4s 1810

3 Steam Cracker integrated with an OCT Unit 2213 +403*

Feedstock, kta Naphtha Feed Products, kta Methane Fuel Gas PG Ethylene PG Propylene Mixed C 4s Pygas Fuel Oil Acid Gas Total 389 760 418 263 196 60 2 2088 393 760 418 0 181 56 2 1810 437 760 713 0 235 66 2 2213 +295*

* 73% of incremental naphtha converted to propylene

In addition to maximizing the propylene-to-ethylene (P/E) ratio of a steam cracker, OCT can also be utilized to optimize steam cracker complexes operating in the conventional P/E range. Table 3 illustrates different naphtha steam cracker options that produce an overall P/E ratio of 0.65. In Case 4, the P/E ratio is controlled by the cracking severity; the 0.65 P/E ratio represents a typical low severity operation on naphtha feed. In Case 5, the severity is increased and the OCT unit is added to react butylenes and ethylene to attain the same 0.65 ratio. A range of values are shown in Case 5 to reflect the results depending upon whether butadiene is recovered as product or selectively hydrogenated to produce more OCT unit feed. Addition of the OCT unit results in a lower cost complex with lower specific energy consumption that in turn results in improved gross and net margins for the steam cracker/OCT combination.

Table 3 Steam Cracker OCT Options

Feedstock Naphtha Severity P/E Naphtha Feedrate C3- from OCT TIC Gross Margin Net Margin Energy BD Benzene Pygas

Case 4 Naphtha Low 0.65 Base -Base Base Base Base Base Base Base

Case 5 Naphtha High 0.65 2 - 5% lower 15 - 28% 5 - 8% reduction <1 - 3% improvement 2 - 6% improvement 8 - 9% lower 17% less 25 - 50% more <2 - 12% less

Since the OCT unit produces propylene, the steam cracker can operate at higher cracking severity while maintaining the same overall P/E ratio. The higher cracking severity processes less feed and produces less byproducts, resulting in a smaller ethylene plant. Since the ethylene plant is the major cost and energy component, the overall result is that the steam cracker/OCT unit combination outperforms the low severity steam cracker. The addition of the OCT unit to the steam cracker improves capital and operating expenses as compared to larger plants operating in the traditional low severity range. In addition to the advantages discussed for grassroots complexes, the OCT unit can also be used as an effective debottlenecking tool. It can be applied to plants currently operating at low severity and looking to increase capacity without sacrificing P/E ratio or for plants operating at high severity and looking to debottleneck for higher capacities and P/E ratios.

Summary
Demand forecasts for ethylene and propylene indicate that the growth rate of propylene will exceed the growth rate of ethylene. The Olefins Conversion Technology (OCT) from ABB Lummus Global provides a low cost solution to expand the propylene flexibility and profitability of the major propylene production processes, namely FCC and steam crackers. In FCC applications, OCT converts byproduct butylenes and ethylene from fuel gas to polymer grade propylene. In steam cracker applications, the potential quantity of butylenes for OCT will vary depending upon how the butadiene contained in the mixed C4s product will be used. OCT can increase steam cracker P/E ratio from the traditional 0.45- 0.65 range to values greater than 1.1. In the traditional range, OCT improves the overall plant material balance and energy consumption, resulting in improved returns on grassroots facilities as well as a powerful debottlenecking option for existing units.

References
1. Steven I. Kantorowicz ABB Lummus Global, Innovative Technologies for Capacity Expansion and Product Flexibility of Steam Crackers, The 11th Ethylene Conference, Maoming, PRC, November 20-23,2000

2. Ronald M. Venner, Triolefins - The Bridge to Profitability, European Petrochemical Technology Conference London, June 21-22, 1999 3. Thi Chang, JV Builds Worlds Largest Single Train Olefins Plant, Oil & Gas Journal, September 20, 1999 4. Frank D. McCarthy and Aivars E. Krumins, Low Pressure Recovery of Olefins from Refinery Offgases, Lummus 8th Ethylene Seminar 5. S. Kantorowicz and M. Shreehan, Olefins Conversion Economics, Lummus 9th Ethylene Seminar 6. S.M. Edwards, Olefins Conversion Technology, Lummus 9th Ethylene Technology Seminar 7. Aivars E. Krumins, Propylene Options, EEPC HSE Conference 2000 8. K.M. Sundaram, E.F. Olszewski and M.M. Shreehan, Ethylene, Kirk-Othmer Encyclopedia of Chemical Technology 4th Edition