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 liq-
uid acid technologies for alkylation of light olefins and isobutane. Alkylate is a key blend-
ing component for gasoline having high octane, low Reid vapor pressure (RVP), low
sulfur, and low volatility. It is composed of primarily highly branched paraffinic hydro-
carbons. 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 regula-
tory 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 indus-
try’s need for an alternative to liquid acid technologies. Early attempts with solid acid cat-
alysts 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, requir-
ing 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 high-
temperature 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

1.25
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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 com-
plex 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 propy-
lene, 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, form-
ing 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 alky-
late 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 con-
tact of short duration between hydrocarbon and catalyst for octane product, high yield, and
efficient separation of alkylate from the catalyst to minimize undesirable secondary reac-
tions. 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.

+ Low Temperature High

C4

C4 =
High
+
i-C4
C8 C8 Isomerized C8
TMP DMH
100 RON 60 RON
C4 =
M
in
or

Isobutane/Olefin
Ratio
Minor

or
in
M

i-C4
+ +
C12 – C20 C12 – C20 C5 – C7
Low Cracked Products
90 RON 60-93 RON

Low Contact Time High

FIGURE 1.3.1 Reaction mechanism.

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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 ris-
er 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 cat-
alyst 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 hydro-
carbon product at the top of the reactor. The catalyst is reactivated by a simple hydro-
genation 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 slip-
stream flows into a separate vessel for reactivation in vapor phase with relatively mild con-
ditions 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 simi-
lar 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

Olefin Feed Reactor Fractionation n-Butane

Feed Pretreatment Section Section
Alkylate
Isobutane
H2 H2 Recycle
Butane
Feed
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

Light
Alkylene Ends
Reactor
LPG
Fractionation
Section

i-C4 / H2
Reactivation Reactivation Alkylate
Wash Zone Vessel

H2
Olefin
Feed

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 recy-
cle 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, cata-
lyst stability, and economic impact results in a process technology competitive with tradi-
tional 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 block-
age of the active sites by heavy hydrocarbons. These heavy hydrocarbons are significant-
ly 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 hydro-
carbons are combined in the total alkylate product pool and are accounted for in the alky-
late properties from the Alkylene process.
The buildup of heavy hydrocarbons on the catalyst surface is a function of the operat-
ing 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

C5
100
C6-C7
C8
80 C9+
Product Distribution, LV-%

60

40

20

0
HF H2SO4 Alkylene

RON 95.7 96.6 97.0

MON 94.2 93.6 94.2
Temp, °F 100 50 77
Temp, °C 38 10 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 regen-
eration (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 lit-
tle 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 mini-
mize high olefin concentration at the feed inlet to the riser. The catalyst is quickly sepa-
rated 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 sec-
tion 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 reac-
tor 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 con-
sistent 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 react-
ed 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 inte-
gration 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 paraf-
fin 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 buty-
lene-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 prod-
uct 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 today’s refiner.

SUMMARY

Future gasoline specifications will require refiners to maximize the use of assets and rebal-
ance 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 7064 7064
C4 paraffin makeup 9194 2844
C5⫹ alkylate, BPSD 8000 8000
C5⫹ alkylate RONC 95.0 95.0
USGC EEC, million $ 43.0 43.7
Utilities Base 0.96*Base

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UOP ALKYLENE™ PROCESS FOR MOTOR FUEL ALKYLATION 1.31

TABLE 1.3.2 Comparison of Alkylation Options

Alkylene ⫹ HF ⫹ On-site regeneration

Butamer Butamer H2SO4 ⫹ Butamer
Total feed from FCC, BPSD 7064 7064 7064
C5⫹ alkylate, BPSD 8000 7990 7619
C5⫹ alkylate
RONC 95.0 95.2 95.0
MONC 92.9 93.3 92.2
(R ⫹ M) / 2 94.0 94.3 93.6
C5⫹ alkylate D-86, °F
50% 213 225 21
90% 270 290 29
Utilities, $/bbl C5 ⫹ alkylate 174 0.70 1.32
Acid cost, $/bbl — 0.08 0.01
Catalyst cost, $/bbl 0.60 0.02 0.02
Metals recovery, $/bbl 0.03 0.00 0.00
Chemical cost, $/bbl 0.03 0.02 0.02
Variable cost of production, $/bbl 2.39 0.82 1.37
Fixed cost, $/bbl 1.97 2.43 3.53
Total cost of production, $/bbl 4.37 3.25 4.90
Estimated erected cost, million $ 43.5 40.5 63.3

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 tech-
nologies. Recent developments propel the Alkylene process technology into the market-
place 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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