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Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 1.3

UOP ALKYLENE PROCESS FOR MOTOR FUEL ALKYLATION


Cara Roeseler
UOP LLC Des Plaines, Illinois

INTRODUCTION
The UOP Alkylene process is a competitive and commercially available alternative to liquid acid technologies for alkylation of light olefins and isobutane. Alkylate is a key blending component for gasoline having high octane, low Reid vapor pressure (RVP), low sulfur, and low volatility. It is composed of primarily highly branched paraffinic hydrocarbons. Changing gasoline specifications in response to legislation will increase the importance of alkylate, making it an ideal clean fuels blend stock. Existing liquid acid technologies, while well proven and reliable, are increasingly under political and regulatory pressure to reduce environmental and safety risks through increased monitoring and risk mitigation. A competitive solid catalyst alkylation technology, such as the Alkylene process, would be an attractive alternative to liquid acid technologies. UOP developed the Alkylene process during the late 1990s, in response to the industrys need for an alternative to liquid acid technologies. Early attempts with solid acid catalysts found some to have good alkylation properties, but the catalysts also had short life, on the order of hours. In addition, these materials could not be regenerated easily, requiring a carbon burn step. Catalysts with acid incorporated on a porous support had been investigated but not commercialized. UOP invented the novel HAL-100 catalyst that has high alkylation activity and long catalyst stability and easily regenerates without a hightemperature carbon burn. Selectivity of the HAL-100 is excellent, and product quality is comparable to that of the product obtained from liquid acid technologies.

ALKYLENE PROCESS
Olefins react with isobutane on the surface of the HAL-100 catalyst to form a complex mixture of isoalkanes called alkylate. The major constituents of alkylate are highly branched trimethylpentanes (TMP) that have high-octane blend values of approximately
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UOP ALKYLENE PROCESS FOR MOTOR FUEL ALKYLATION 1.26


ALKYLATION AND POLYMERIZATION

100. Dimethyl hexanes (DMH) have lower-octane blend values and are present in alkylate at varying levels. Alkylation proceeds via a carbenium ion mechanism, as shown in Fig. 1.3.1. The complex reaction paths include an initiation step, a propagation step, and hydrogen transfer. Secondary reactions include polymerization, isomerization, and cracking to produce other isoalkanes including those with carbon numbers which are not multiples of 4. The primary reaction products are formed via simple addition of isobutane to an olefin such as propylene, butenes, and amylenes. The key reaction step is the protonation of a light olefin on the solid catalyst surface followed by alkylation of an olefin on the C4 carbocation, forming the C8 carbocation. Hydride transfer from another isobutane molecule forms the C8 paraffin product. Secondary reactions result in less desirable products, both lighter and heavier than the high-octane C8 products. Polymerization to acid-soluble oil (ASO) is found in liquid acid technologies and results in additional catalyst consumption and yield loss. The Alkylene process does not produce acid-soluble oil. The Alkylene process also has minimal polymerization, and the alkylate has lighter distillation properties than alkylate from HF or H2SO4 liquid acid technologies. Alkylation conditions that favor the desired high-octane trimethylpentane include low process temperature, high localized isobutane/olefin ratios, and short contact time between the reactant and catalyst. The Alkylene process is designed to promote quick, intimate contact of short duration between hydrocarbon and catalyst for octane product, high yield, and efficient separation of alkylate from the catalyst to minimize undesirable secondary reactions. Alkylate produced from the Alkylene process is comparable to alkylate produced from traditional liquid acid technologies without the production of heavy acid-soluble oil. The catalyst is similar to other hydroprocessing and conversion catalysts used in a typical refinery. Process conditions are mild and do not require expensive or exotic metallurgy.

C4 C4 = High C8 C4 =

Low

Temperature

High

i-C4

C8 TMP 100 RON


M in or

Isomerized C8 DMH 60 RON

Isobutane/Olefin Ratio Minor i-C4


M in or

C12 C20 Low

C12 C20 90 RON

C5 C7 Cracked Products 60-93 RON

Low
FIGURE 1.3.1 Reaction mechanism.

Contact Time

High

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UOP ALKYLENE PROCESS FOR MOTOR FUEL ALKYLATION


UOP ALKYLENE PROCESS FOR MOTOR FUEL ALKYLATION

1.27

Reactor temperature, isobutene/olefin ratio, contact time, and catalyst/olefin ratios are the key operating parameters. Feeds to the Alkylene unit are dried and treated to move impurities and contaminants such as diolefins, oxygenates, nitrogen, and sulfur. These contaminants also cause higher acid consumption, higher acid-soluble oil formation, and lower acid strength in liquid acid technologies. Diolefin saturation technology, such as the Huels Selective Hydrogenation Process technology licensed by UOP LLC, saturates diolefins to the corresponding monoolefin and isomerizes the 1-butene to 2-butene. The alkylate formed by alkylating isobutane with 2-butene is the preferred 2,2,3-TMP compared to the 2,2-DMH formed by alkylating isobutane with 1-butene. The olefin and isobutane (Fig. 1.3.2) are combined and injected into a carbon-steel riser reactor with continuous catalyst reactivation (Fig. 1.3.3) to maintain a constant catalyst activity and minimize catalyst inventory. This provides constant product quality, high yield, and high on-stream efficiency. Liquid-phase hydrocarbon reactants transport the catalyst around the reactor circuit where velocities are low relative to those of other moving catalyst processes. The reaction time is on the order of minutes for the completion of the primary reactions and to minimize secondary reactions. The catalyst and hydrocarbon are intimately mixed during the reaction, and the catalyst is easily disengaged from the hydrocarbon product at the top of the reactor. The catalyst is reactivated by a simple hydrogenation of the heavier alkylate on the catalyst in the reactivation wash zone. Hydrogen consumption is minimal as the quantity of heavy alkylate on the HAL-100 catalyst is very small. The reactivation process is highly effective, restoring the activity of the catalyst to nearly 100 percent of fresh. The liquid-phase operation of the Alkylene process results in less abrasion than in other catalyst circulation processes due to the lubricating effect of the liquid. Furthermore, the catalyst and hydrocarbon velocities are low relative to those in other moving catalyst processes. This minimizes the catalyst replacement requirements. Catalyst circulation is maintained to target catalyst/olefin ratios. A small catalyst slipstream flows into a separate vessel for reactivation in vapor phase with relatively mild conditions to remove any last traces of heavy material and return the catalyst activity to essentially the activity of fresh catalyst. Alkylate from the reactor is sent to a downstream fractionation section, which is similar to fractionation sections in liquid acid process flow schemes. The fractionation section recycles the unconverted isobutane back to the reactor and separates out the final alkylate product.

Light Ends

Light Ends Propane n-Butane Alkylate

Olefin Feed

Feed Pretreatment H2 Butane Feed H2

Reactor Section Isobutane Recycle

Fractionation Section

Butamer Unit optional Butane Feed


FIGURE 1.3.2 Alkylene process flow scheme.

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UOP ALKYLENE PROCESS FOR MOTOR FUEL ALKYLATION 1.28


ALKYLATION AND POLYMERIZATION

Alkylene Reactor

Light Ends Fractionation Section LPG

i-C4 / H2 Reactivation Wash Zone Olefin Feed Reactivation Vessel H2 Alkylate

Feed Pretreatment Section Isobutane Recycle


FIGURE 1.3.3 Alkylene process flow diagram.

ALKYLENE PERFORMANCE
HAL-100, the Alkylene process catalyst, has high acidity to promote desirable alkylation reactions. It has optimum particle size and pore distribution to allow for good mass transfer of reactants and products into and out of the catalyst. The catalyst has been commercially produced and demonstrates high physical strength and very low attrition rates in extensive physical testing. Catalyst attrition rates are several orders of magnitude lower than those experienced in other moving-bed regeneration processes in the refining industry. HAL-100 has been demonstrated in a stability test of 9 months with full isobutane recycle and showed excellent alkylate product qualities as well as catalyst stability. Performance responses to process parameters such as isobutane/olefin ratio, catalyst/olefin ratio, and process temperature were measured. Optimization for high performance, catalyst stability, and economic impact results in a process technology competitive with traditional liquid acid technologies (Fig. 1.3.4). Typical light olefin feedstock compositions including propylene, butylenes, and amylenes were also studied. The primary temporary deactivation mechanism is the blockage of the active sites by heavy hydrocarbons. These heavy hydrocarbons are significantly lower in molecular weight than acid-soluble oil that is typical of liquid acid technologies. These heavy hydrocarbons are easily removed by contacting the catalyst with hydrogen and isobutane to strip them from the catalyst surface. These heavy hydrocarbons are combined in the total alkylate product pool and are accounted for in the alkylate properties from the Alkylene process. The buildup of heavy hydrocarbons on the catalyst surface is a function of the operating severity and the feedstock composition. The reactivation conditions and the frequency of vapor reactivation are optimized in order to achieve good catalyst stability as well as commercially economical conditions.

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UOP ALKYLENE PROCESS FOR MOTOR FUEL ALKYLATION


UOP ALKYLENE PROCESS FOR MOTOR FUEL ALKYLATION

1.29

100

Product Distribution, LV-%

80

C5 C6-C7 C8 C9+

60

40

20

0 HF RON MON Temp, F Temp, C 95.7 94.2 100 38 H2SO4 96.6 93.6 50 10 Alkylene 97.0 94.2 77 25

FIGURE 1.3.4 Catalyst comparison: mixed 4 olefin feed.

ENGINEERING DESIGN AND OPTIMIZATION


The liquid transport reactor for the Alkylene process was developed by UOP based on extensive UOP experience in fluid catalytic cracking (FCC) and continuous catalyst regeneration (CCR) technologies. Novel engineering design concepts were incorporated. Extensive physical modeling and computational fluid dynamics modeling were used to verify key engineering design details. More than 32 patents have been issued for the Alkylene process technology. The reactor is designed to ensure excellent mixing of catalyst and hydrocarbon with little axial dispersion as the mixture moves up the riser. This ensures sufficient contact time and reaction time for alkylation. Olefin injection nozzles have been engineered to minimize high olefin concentration at the feed inlet to the riser. The catalyst is quickly separated from the hydrocarbon at the top of the riser and falls by gravity into the reactivation zone. The catalyst settles into a packed bed that flows slowly downward in the upper section of the vessel, where it is contacted with low-temperature hydrogen saturated isobutane recycle. The heavy hydrocarbons are hydrogenated and desorbed from the catalyst. The reactivated catalyst flows down standpipes and back into the bottom of the riser. The reactor section includes separate vessels for reactivating a slipstream of catalyst at a higher temperature to completely remove trace amounts of heavy hydrocarbons. By returning freshly reactivated catalyst to the riser continuously, catalyst activity is maintained for consistent performance. The UOP Butamer process catalytically converts normal butane to isobutane with high selectivity, minimum hydrogen consumption, and excellent catalyst stability. When the Butamer process is combined with the Alkylene process, n-butane in the feed can be reacted to extinction, thereby reducing the fresh feed saturate requirements. In addition, the

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UOP ALKYLENE PROCESS FOR MOTOR FUEL ALKYLATION 1.30


ALKYLATION AND POLYMERIZATION

increased isobutane concentration in the isostripper reduces the size of the isostripper and allows for a reduction in utilities consumption. A novel flow scheme for the optimal integration of the Butamer process into the Alkylene process was developed. The two units can share common fractionation and feed pretreatment equipment. Synergy of the two units reduces the capital cost requirement for the addition of the Butamer process and reduces the operating cost. Table 1.3.1 illustrates the maximum utilization of the makeup C4 paraffin stream and the utilities savings.

ALKYLENE PROCESS ECONOMICS


The product research octane number can be varied according to the reaction temperature and the isobutane/olefin ratio. Additional refrigeration duty can be justified by higher product octane, depending on the needs of the individual refiner. Higher isobutane/olefin ratio requires higher capital and utilities. Mixed propylene and butylene feedstocks can also be processed with less dependence on operating temperature. However, the alkylate product octane is typically lower from mixed propylene and butylene feed than from butylene-only feed. Processing some amylenes with the butylenes will result in slightly lower octane. Most refiners have blended the C5 stream in the gasoline pool. However, with increasing restrictions on Reid vapor pressure, refiners are pulling C5 out of the gasoline pool and processing some portion in alkylation units. The three cases shown in Table 1.3.2 compare the economics of the Alkylene process with those of conventional liquid acid alkylation. The basis is 8000 BPSD of alkylate product from the Alkylene process. Case 1 is the Alkylene process, case 2 is an HF alkylation unit, and case 3 is a sulfuric acid unit with on-site acid regeneration. All cases include a Butamer process to maximize feed utilization. The Alkylene process has a yield advantage over liquid acid alkylation technologies and does not produce acid-soluble oil (ASO) by-products. In addition, the capital cost of the Alkylene process is competitive compared with existing technologies, and maintenance costs are lower. The HF alkylation unit requires HF mitigation capital and operating costs. The sulfuric acid alkylation unit requires regeneration or transport of large volumes of acid. Overall, the Alkylene process is a safe and competitive option for todays refiner.

SUMMARY
Future gasoline specifications will require refiners to maximize the use of assets and rebalance refinery gasoline pools. The potential phase-out of MTBE will create the need for

TABLE 1.3.1

Alkyene Process Capital Costs Alkylene Alkylene Butamer

Total feed from FCC, BPSD C4 paraffin makeup C5 alkylate, BPSD C5 alkylate RONC USGC EEC, million $ Utilities

7064 9194 8000 95.0 43.0 Base

7064 2844 8000 95.0 43.7 0.96*Base

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UOP ALKYLENE PROCESS FOR MOTOR FUEL ALKYLATION


UOP ALKYLENE PROCESS FOR MOTOR FUEL ALKYLATION

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TABLE 1.3.2

Comparison of Alkylation Options Alkylene Butamer HF Butamer 7064 7990 95.2 93.3 94.3 225 290 0.70 0.08 0.02 0.00 0.02 0.82 2.43 3.25 40.5 On-site regeneration H2SO4 Butamer 7064 7619 95.0 92.2 93.6 21 29 1.32 0.01 0.02 0.00 0.02 1.37 3.53 4.90 63.3

Total feed from FCC, BPSD C5 alkylate, BPSD C5 alkylate RONC MONC (R M) / 2 C5 alkylate D-86, F 50% 90% Utilities, $/bbl C5 alkylate Acid cost, $/bbl Catalyst cost, $/bbl Metals recovery, $/bbl Chemical cost, $/bbl Variable cost of production, $/bbl Fixed cost, $/bbl Total cost of production, $/bbl Estimated erected cost, million $

7064 8000 95.0 92.9 94.0 213 270 174 0.60 0.03 0.03 2.39 1.97 4.37 43.5

clean, high-octane blending components, such as alkylate, to allow refiners to meet pool requirements without adding aromatics, olefins, or RVP. Alkylate from the Alkylene process has excellent alkylate properties equivalent to those of HF acid technology, does not generate ASO, has better alkylate yield, and is a safe alternative to liquid acid technologies. Recent developments propel the Alkylene process technology into the marketplace as a viable option with technical and economic benefits. As the demand for alkylate continues to grow, new alkylation units will help refiners meet the volume and octane requirements of their gasoline pools. The Alkylene process was developed as a safe alternative to commercial liquid acid alkylation technologies.

BIBLIOGRAPHY
Cara M. Roeseler, Steve M. Black, Dale J. Shields, and Chris D. Gosling, Improved Solid Catalyst Alkylation Technology for Clean Fuels: The Alkylene Process, NPRA Annual Meeting, San Antonio, March 2002.

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UOP ALKYLENE PROCESS FOR MOTOR FUEL ALKYLATION

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