HF Alkylation & NExOCTANE Technology

Table of Contents

1. Abstract...1
1.1. Objectives
2. Gasoline Market Assessment.2
2.1. Gasoline Price Volatility and Elasticity of Demand for Gasoline
3. Literature Survey..5
3.1. HF composition for Alkylation
3.2. Evolution of a More Reliable Gasket for HF Alkylation Units
3.3. New process analysis tool for HF alkylation
3.4. Block Flow Diagram for HF Alkylation
3.5. Solid Acid Catalyst Alkylation Technology
4. Introduction to Alkylation.7
4.1. Alkylation Reaction
4.1.1. Alkylation using Sulphuric Acid as a Catalyst
4.1.2. Alkylation using Hydrofluoric Acid as a Catalyst
5. HF Alkylation.8
5.1. Introduction
5.2. Background
5.3. Significance
5.4. Process Chemistry
5.5. Alkylation Feed Stocks
5.6. Process Description.13
5.7. Process Variables
5.8. Alkylation Products
6. NExOCTANE Technology for Isooctane Production.18
6.1. Introduction to MTBE
6.2. Introduction to NExOCTANE
6.3. Process Chemistry
6.4. Cost-Effective Technology
6.5. NExOCTANE Process Description21
7. Environmental Considerations..22
7.1. Effluent Treatment
7.2. Effluent Gases
7.3. Liquid Effluents
7.4. Solid Effluents
8. Safety Issues in Alkylation Units...24
9. Modifications & Recommendations..24
9.1. Aerosol Potential
9.2. Mitigation
9.3. HF Modifiers
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HF Alkylation & NExOCTANE Technology

9.4. Advances in HF Alkylation Technology

10. Distillation Column P&ID..26
10.1.
P&ID Description
11. Conclusions33
12. References..34

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List of Figures and Tables

FIGURE 2.2: Gasoline Production and Consumption in Pakistan

FIGURE 2.3: Gasoline Production and Consumption Worldwide
FIGURE 2.4: Pakistan Gasoline Imports by Year
FIGURE 2.5: Pakistan Gasoline Exports by Year
FIGURE 2.6: Pakistan Crude Oil Reserves
FIGURE 3.4: Block Flow Diagram for HF Alkylation
TABLE 3.1: Features of Solid Acid Catalyst Alkylation Technology
FIGURE 5.4.1: HF alkylation primary reactions
FIGURE 5.4.2: Initiation reactions
FIGURE 5.4.3: Propagation reactions
FIGURE 5.4.4: Isomerization
FIGURE 5.4.5: Other reactions
TABLE 5.5.1: Compositions of Alkylate from Pure-Olefin Feed stocks
FIGURE 5.6.1: Process Flow Diagram C4 of HF Alkylation Process with NExOCTANE
TABLE 5.7.1: Range of Operating Variables in HF Alkylation
TABLE 5.8.1: HF Alkylate Properties
FIGURE 6.3.1: Dimerization Reaction
FIGURE 6.3.2: Hydrogenation
FIGURE 6.5.1: Integration OF NExOCTANE in a Refinery
TABLE 6.5.2: Typical Utility Requirements

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1. Abstract:

HF Alkylation & NExOCTANE Technology

In todays world, the demand of gasoline is increasing day by day due to increase in
the number of auto-mobiles on the roads. The gasoline obtained by the crude
distillation is not enough to meet the current worldwide demand. So there is a need of
a method so that the less useful products of crude distillation can be converted to
gasoline in the refinery. Keeping in view the worlds gasoline demand alkylation
process units were primarily introduced by UOP and Philips. The alkylation
process uses the almost worthless olefins as raw materials from FCC (fluid
catalytic cracking) units in the refinery and converts them into the much more
useful and valuable products like gasoline and LPG.
The emergence of catalytic reforming techniques gave a vital tool for the production of
high-quality gasoline but the motor fuel produced in these operations is mainly aromatic
based and is characterized by its high sensitivity. The production of low sensitivity
gasoline components was required. A consequence of all these requirements was the
expansion of these alkylation operations.
Furthermore, the phase-out of MTBE (Methyl-ter-butyl-ether) which is used as an antiknock agent and oxygenate in gasoline (due to water pollution) has rendered the
already existing MTBE processing units useless. Hence, a suitable process is required
that can replace the MTBE and can give high octane number products. Isooctane has
been recognized essentially as a cost-effective alternative to MTBE [7]. It utilizes
same isobutylene feed that was used in MTBE production and it offers excellent
blending value and production of isooctane can be obtained in a low-cost renovation of
an existing plant of MTBE.
The NExOCTANE technology was developed for the isooctane production. This
technology is cost effective and also replaces MTBE effectively. NExOCTANE process
can be combined with HF Alkylation process to produce high quality gasoline which is
free from MTBE.
1.1 Objective:
The aim of this report is to combine the Alkylation process and NExOCTANE
technology to produce high octane gasoline which is free from environment threatening
MTBE and is also cost-effective. Both Alkylation and NExOCTANE processes are
explained in detail in this report along with modifications which would enhance the
safety of the Alkylation process.

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HF Alkylation & NExOCTANE Technology

2. Gasoline Market Assessment:

Factors affecting gasoline retail price:
The cost for the production, transportation, and selling gasoline to consumers includes:
Crude oil cost
Refining costs and profits
Distribution and marketing costs and profits
Taxes
2.1 Gasoline Price Volatility and Elasticity of Demand for Gasoline:
The volatility in Gasoline price impacts on consumers' price elasticity of gasoline
demand. Results displayed that prices volatility decreases consumer demand for the
gasoline in intermediate run. It is found that consumers seem to be less elastic in
response to variations in gasoline price when gasoline price volatility is either medium
or high, in contrast to when it is low. Likewise, it was found that when variance in
econometric model is controlled, the gasoline price elasticity of demand is lesser in
magnitude in the long run [1].

2.2 Gasoline Production and Consumption in Pakistan:

Source: Ref 2

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2.3 Gasoline Production and Consumption Worldwide:

Source: Ref 2

2.4 Pakistan Gasoline Imports by Year:

Source: Ref 2

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2.5 Pakistan Gasoline Exports by Year

Source: Ref 2

2.6 Pakistan Crude Oil Reserves:

Source: Ref 2

2.7 Latest gasoline products prices in Pakistan [2]:

Unleaded Premium PKR 116.74/L
Unleaded-Hi Octane PKR 137.72/L
E10 Gasoline PKR 110.26/L

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HF Alkylation & NExOCTANE Technology

3. Literature Survey:

3.1 HF composition for Alkylation:

There is a requirement for safe means for storing and distributing hydrofluoric acid when
it is used in alkylation as a catalyst. In this development, acid is absorbed in co-polymer
of a polyacrylamide and a polyacrylate which is semi-solid or solid.
3.2 Evolution of a More Reliable Gasket for HF Alkylation Units:
The need to reduce flange face corrosion, overcome handling issues and enhance
sealing performance has directed to the development of a new kind of gasket for using
in Hydrofluoric (HF) Alkylation Units to substitute the standard spiral-wound type. Now,
carbon steel flange face can be secured from aggressive HF acid corrosion and
resulting scaling of iron fluoride, complemented by an increase in the reliability and
fsealability of flange joints [13]. The advantages include a decrease in costly flange
damage, possible leakage and the related unit shutdowns required for repairs. This
particular feature highlights the stages in the growth of the new gasket design
3.3 New process analysis tool for HF alkylation:
ABB Process Fourier Transform Infrared Analyzer for Hydrofluoric Acid Alkylation
Process Unit Optimization mutually developed with ConocoPhillips [3], aids petroleum
refineries to operate HF alkylation units more safely and efficiently, while making an
important contribution to the operational and the environmental risk mitigation [14].
3.4 Block Flow Diagram for HF Alkylation:

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HF Alkylation & NExOCTANE Technology

3.5 Solid Acid Catalyst Alkylation Technology:

Neste Oil, Lummus Technology and Albemarle Catalysts have established and
demonstrated an alkylation technology that is now being offered for license. AlkyClean
process employs robust zeolite catalyst formulation that is coupled with a novel reactor
processing system to yield a product of high quality alkylates.
Total installation cost of the facility is appreciably lower than the current liquid-acid
processes. With no presence of chlorides or liquid acids in the system, no treatment of
product or disposal of chlorides or acids is required. Lack of corrosive acids in system
and mild operating conditions allow for the carbon steel construction of the equipments.
TABLE 3.1: Features of Solid Acid Catalyst Alkylation Technology
Process Features
Process benefits
Robust, true-solid-acid
Eliminates corrosive liquid acid use and associated safety
catalyst
concerns.
Tolerant to feedstock impurities, changes in feedstockolefin
composition, and process upsets (e.g., water spikes)
Removes safety risks
associated with
liquid acids

Low pressure, liquid

phase operation in
the temperature range
of 50C-90C
Does not produce acid
soluble oil
by-product
No emissions to air,
water, or ground

Lower maintenance and monitoring requirements,

Eliminates costs associated with mitigation (acid dump and
water spray systems), disposal of acids or chlorides, and vapor
suppression additives
Eliminates costly refrigeration requirements associated with
H2SO4 units.
Carbon steel construction material results in lower costs.

Improves alkylate yield.

No by-product disposal requirement.

Environmentally friendly process.

Source: Ref 5

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4. Introduction to Alkylation:

In petroleum refining industry the term alkylation is used for the reaction of an
isoparaffin with lower molecular weight olefins to produce higher molecular weight
isoparaffins [5].
The alkylation process that is of commercial importance involves low temperature for
alkylation performed in the presence of hydrofluoric acid or either sulphuric acid.
4.1 Alkylation Reaction:
In the process of alkylation by using sulphuric acid or hydrofluoric acid as catalysts
olefins react with only isoparaffines such as isopentane or isobutane (having tertiary
carbon atoms).Commercially only isobutane is used because isopentane has high
octane number and its vapor pressure is low.
The two processes used for alkyation are:
1. Alkylation using Sulphuric Acid as a catalyst
2. Alkylation using Hydroflouric Acid as a catalyst
4.1.1 Alkylation using Sulphuric Acid as a Catalyst:

This process does not require additional equipment as needed in the case of
hydrofluoric acid process for the recovery and neutralization of the hydrofluoric acid
in different streams.
Drying is advantageous but not necessary in sulphuric acid process. Free water
that drops out of the chilled feed is removed by only feed coalesces.
Safety and maintenance cost is less in comparison to hydrofluoric acid process.
Self-alkylation occurs at lesser extent in this process.
Less harmful for the environment.

4.1.2 Alkylation using Hydrofluoric Acid as a Catalyst:

Less capital and total operating costs in comparison to sulphuric acid process.
Instead of refrigeration cooling water can be used.
For emulsions smaller settling devices are required.
Reactor designs are smaller and feasible.
Hydrofluoric acid is completely regenerated.
Disposal of spent acid is not necessarily required.
Less turbulence and agitation is required.
Operation is more flexible relative to external ratio of isobutene to olefin,
temperature, etc.
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5. HF Alkylation
5.1 Introduction:

HF Alkylation process for the production of motor fuel catalytically combines isobutane
with light olefins, which are the mixtures of butylenes and propylenes to form a
branched-chain paraffinic fuel. The alkylation reaction is carried out in the presence of
Hydrofluoric acid under specific conditions which are selected to maximize yield and
quality of alkylate. The alkylate product has excellent antiknocking properties and has
high-octane because of high percentage of highly branched paraffins. Alkylate is a low
sulphur, clean-burning, low RVP gasoline blending component and it does not have
aromatic or compounds.
5.2 Background:
In the mid of 1950s, the development and acceptance of more-sophisticated and highperformance automotive engines placed a stress on the petroleum refiner in order to
increase both gasoline production and to improve the quality of motor fuel. The
emergence of catalytic reforming techniques gave a vital tool for the production of highquality gasoline [7]. However, the motor fuel which is produced in these operations is
mainly aromatic based and is characterized by its high sensitivity (that is, the spread
between motor and research octane number). Due to the fact that automobile
performance is more closely and completely related to road, rating of octane
(approximately the average of motor and research octanes), the production of low
sensitivity gasoline components was required. A consequence of all these requirements
was the expansion of these alkylation operations. Refiners started broadening the olefin
feeds range to both new and existing alkylation units to involve propylene and
occasionally butylenes as well as amylenes. In the beginning of 1960s, the HF
Alkylation process had virtually replaced motor fuel polymerization units for the new
installations of plants.
HF Alkylation process has got more importance in the refining situation of the 2000s. Its
importance is further increased due to the phase-out of MTBE and the increased
emphasis on the low-sulfur gasoline. The alkylation process is critically important in the
quality motor fuels production including many environmental gasoline blends. The
process facilitates refiners with a handy tool of unmatched economy and good
efficiency, one that will help refiners in strengthening and maintaining their position and
status in the gasoline production and marketing.
5.3 Significance:
The HF alkylation process is of vital importance to the present day. It plays a very
important role in production one of the most essential feeds to the final gasoline blend.

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HF Alkylation & NExOCTANE Technology

With the increase in number of fluid catalytic cracking (FCC) units used in refineries its
significance has increased [23].
The FCC is used to add value to the heavy products produced in crude distillation. In
FCC heavy feeds are catalytically cracked into lighter products such as FCC gasoline
and light cycle oil, which can either be used after hydrotreating or directly in final
gasoline blending operations. The drawback of this FFC is that light olefins, like butene
and propene, are produced in FCC operations. These are products basically worthless
as feedstock. In the same way, in any crude distillation a large amount of light end
products like butane can be produced that has very limited use. Normal-butane can
easily be transformed into iso-butane, and in iso-butane form it can joins the C 3 or C 4
olefins (butene or propene) produced by FCC as the joint feeds to the HF alkylation
process [23].
The HF alkylation performs the critical role of improvement of these byproducts to highvalue product (alkylate), which is then used as a component of gasoline blending. This
task of utilizing the C 4 olefins produced from the FCC and the C 4 iso-alkanes produced
from the distillation of crude oil and changing them, through the process of catalytic HF
alkylation (an altered Friedel-Crafts reaction), into iso-octanes, continues to has major
importance in refining of petroleum.
5.4 Process Chemistry:
General:
In this process of HF Alkylation, HF acid is the catalyst that stimulates the isoparaffinolefin reaction. In this process, olefins react with only isoparaffins having tertiary carbon
atoms, such as isopentane or isobutane. In practice, only isobutane is used due of the
fact that isopentane has a high octane number and it also has a vapor pressure that has
historically permitted it to be blended directly into the finished gasolines. However,
where the environmental regulations have reduced the allowed gasoline vapor
pressure, isopentane is being removed from the gasoline, and refiner concern in
alkylation of this material with light olefins, particularly propylene, is increasing.
The real reactions occuring in the alkylation reactor are several and are comparatively
complex. In practice, the main product from a single olefin contains only a fraction of
alkylate because of the number of concurrent reactions that are probable in the
alkylation environment.
Reaction Mechanism:
Alkylation is one of the definitive examples of a reaction or reactions continuing via
carbenium ion mechanism. These reactions comprises of an initiation step followed by a
propagation step and may comprise of an isomerization step. In addition, polymerization
step and cracking steps may also be involved. Though, these side reactions are
commonly not desirable. HF alkylation primary reactions are shown in Fig 5.4.1.

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HF Alkylation & NExOCTANE Technology

Initiation: The initiation step produces the tertiary butyl cations that will then carry on
the alkylation reaction. This step is shown in Fig 5.4.2.
Propagation: Propagation reactions include the tertiary butyl cation reacting with olefin
to form larger carbenium ion, which then extracts a hydride from the molecule of
isobutane. The hydride extraction produces the isoparaffin along with a new tertiary
butyl cation for carrying on the reaction chain. This step is shown in Fig 5.4.3.

FIGURE 5.4.1: HF alkylation primary reactions

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HF Alkylation & NExOCTANE Technology

Isomerization: Isomerization is very important in the production of good octane quality

from feed that is rich in 1-butene. The isomerization of 1-butene is preferred according
to thermodynamic equilibrium. Allowing 1-butene to isomerize to 2-butene decreases
the production of dimethylhexanes and enhances the production of trimethylpentanes.
Several recent HF Alkylation units, particularly those processing only butylenes, have
olefin isomerization units at upstream that isomerize the 1-butene to 2-butene. (Fig
5.4.4)

FIGURE 5.4.2: Initiation reactions

Other Reactions: The polymerization reaction results in heavier paraffins production,

which are undesirable because they decrease alkylate octane and they increase
endpoint of alkylate. Minimization of this reaction is accomplished by right choice of
reaction conditions. (Fig 5.4.5)

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HF Alkylation & NExOCTANE Technology

FIGURE 5.4.3: Propagation reactions

FIGURE 5.4.4: Isomerization

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FIGURE 5.4.5: Other reactions

Hydrogen Transfer: The hydrogen transfer reaction is most noticeable with propylene
feed. This reaction initiates via the carbenium ion mechanism. In the first reaction
isobutane reacts with propylene to produce propane and butylene. After that the
butylene is alkylated with isobutane to produce trimethylpentane. From octanes view
point, this reaction can be a desirable one because trimethylpentane has considerably
higher octane than the dimethylpentane usually formed from propylene. Though, two
molecules of isobutane are needed for each alkylate molecule, so from economics point
of view this reaction may be undesirable.

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HF Alkylation & NExOCTANE Technology

5.5 Alkylation Feed Stocks:

Iso-butane and oelifins are used feedstocks in the alkylation unit. The sources of olefins
mainly are coking operations and catalytic cracking. Propene and butenes are the most
commonly used olefins, but pentenes (amylenes) are also used in some units. Some
refineries also use pentenes feed to decrease the vapor pressure of FCC (fluid catalytic
cracking) gasoline and as the result the bromine number in the final blend of gasoline is
reduced. Alkylation of pentenes is also used to decrease the C 5 olefin content of final
gasoline blend and it also decreases the effect of C 5 olefin on ozone depletion and
causes less visual pollution in the environment.
Dehydrogenation of paraffins can yield olefins and isobutane provided to alkylation feed
unit is produced by commercial cracking of heavy paraffins. Catalytic crackers and
hydrocrackers produce a large amount of the isobutene that is provided in alkylation unit
but it can also be obtained from crude distillation, natural gas processing, and catalytic
reformers. Normal butane can be isomerized in some cases to provide additional
isobutane to the feed of alkylation unit.
TABLE 5.5.1: Compositions of Alkylate from Pure-Olefin Feed stocks

Source: Ref 7
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HF Alkylation & NExOCTANE Technology

5.6 Process Description:

The HF alkylation of olefins with iso-butane is complicated because it consists of many

simple addition reactions as well as various side reactions. Products of primary reaction
are the isomeric paraffins which contain carbon atoms that are the sum of carbon atoms
of isobutane and carbon atoms of the corresponding olefin. Though, secondary
reactions such as isomerization, destructive alkylation, hydrogen transfer, and
polymerization also occur, which result in the formation of secondary products which
can be lighter or heavier than the primary products of alkylation. The factors which
promote the primary and secondary reaction mechanisms are different, as well as the
response of each reaction to any changes in operating conditions are different. Not
every secondary reaction is undesired reaction; for example, they also make the
formation of isooctane from amylenes or propylenes possible. In an ideal design and
operation, primary reactions should dominate, but not to the complete elimination of
secondary reaction. For the HF Alkylation, the optimal combinations of product yield,
quality and plant economy are attained with the reactor system operates at coolingwater temperature and in the presence of excess of isoparaffin and with feedstocks free
from contaminants and a vigorous, intimate acid-hydrocarbon contact. To ensure good
alkylate quality and minimize acid consumption, the feeds to the alkylation unit are dried
first and are of low sulfur content. Generally, a simple desiccant-drying system is
provided in the unit.
Reactor Section:
Dried and treated olefin feed along with makeup and recycle isobutene is charged to the
reactor section of the plant. This combined feed enters the shell of the reactor through
several nozzles placed to maintain a uniform temperature in the entire reactor. The
removal of heat of reaction is done by a heat exchange with a large amount of coolant
which flows through the tubes that have a little rise in temperature. If cooling water is
used, then it is available for further use somewhere in the unit. The effluent coming from
the reactor then enters into the settler, and the settled acid is recycled back to the
reactor.
Distillation Section:
The hydrocarbon phase, also containing the dissolved HF acid, flows out from the
settler and it is preheated and then charged to the isostripper. Dried saturate field
butane feed is also fed to the isostripper. The alkylate product is recovered from bottom
of the column. Any normal butane that may enter the unit is withdrawn as a sidecut.
The isobutane which does not react is also recovered as a sidecut and recycled to the
reactor. The overhead of isostripper consists mainly of propane, HF acid, and
isobutane. A drag stream of the overhead material is sent to the HF stripper to strip the
acid. From the HF stripper the overhead is recycled to the isostripper overhead system
to recover isobutane and the HF acid. A portion of the HF stripper bottom stream is
used as material for flushing. A net bottom stream from the isostripper is withdrawn and
then defluorinated.
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LEGEND
R= Reactor
S1 & S2= Settlers
I= Isostripper
AR= Acid Regenerator
HS= HF Stripper
AT= Aluminia Treater
KT= KOH Treater

LEGEND

= Rector Section

= Dimerization Section

= Distillation Section

= Product Recovery Section

= Acid Regeneration Section

= Hydrogenation Section

ADR= Adiabetic Reactor

PR= Product Recovery
TBR= Trickle Bed Reactor

= Neutralization Section

iC4 to Akylation

iC4
Raffinate

Unreacted iC4

ADR

S2

Dried iC4
Makeup

PR
Dried Saturate
C4's
HF Acid

iC4
Recycle

Cooling
Water
in

Cooling
Water
out

HS

nC4

S1

TBR

AR
Dried
Oeilfin
Feed

Iso-Octene

Settled
Acid

Isobutylene
Feed

H2

AT

Acid
Return

Acid
Recycle
Polymer & CBM
to
Neutralization

Iso-Octane

KT
KT

Propane
Alkylate

KT

nC4
FIGURE 5.6.1: Process Flow Diagram C4 of HF Alkylation Process with NExOCTANE Technology

HF Alkylation & NExOCTANE Technology

Acid Regeneration Section:

A slipstream of some circulating HF acid is regenerated internally so a desired level of
acid purity is maintained. This method significantly reduces overall acid consumption.
An acid regenerator column is also present for start-ups after changes or in the event of
a process upset or contamination of feed.
Neutralization Section:
When the normal butane or propane from the HF unit is used as liquefied petroleum
gas, defluorination is suggested because of the potential breakdown of combined
fluorides during the process of combustion which results in potential corrosion of
burners. Defluorination is also essential when the butane is to be charged to an
isomerization unit. After defluorination, the butane and propane products are treated
with potassium hydroxide (KOH) for the removal of any free HF acid.
Scrubbing and auxiliary neutralizing equipment is included in plant design to ensure that
all materials exiting the unit during normal and emergency operations are acid-free.
5.7 Process Variables:
The most significant process variables are:

Reaction temperature
Acid strength
Isobutane concentration
Olefin space velocity.

Any change in these variables affects both product yield and quality. Typical HF
alkylation operating conditions are shown in Table 5.7.1.
Reaction Temperature: Reaction temperature has lesser effect using hydrofluoric
acid. In hydrofluoric acid alkylation increase in the temperature of the reactor from
60 to 125F degrades the quality of alkylate up to three octane numbers In
hydrofluoric acid alkylation, temperature is less important and reactor temperatures
are generally in the range of 70 to 100F [6].
Acid Strength: Acid strength has variable effects on the quality of alkylate
depending on the effectiveness of the mixing in the reactor and the water content
present in the acid. In hydrofluoric acid alkylation the alkylate having the highest
octane number is obtained in the acidity range of 86 to 90%. Commercial operations
generally have concentrations of acid between 83 and 92% hydrofluoric acid and
contain water less than 1% [6].
Isobutane Concentration: Isobutane concentration is usually expressed in terms of
the isobutane/olefin ratio. High ratios of isobutane/olefin increase the octane
number and the yield, and decrease side reactions and consumption of acid. In
industrial practice the ratio of isobutane/olefin on the reactor charge varies from 5:1
to 15: 1. In reactors having internal circulation to enhance the reactor feed ratio,
internal ratios are from 100:1 to 1000:1.
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Olefin Space Velocity: Olefin space velocity is stated as the volume of olefin that is
charged per hour to the acid volume in the reactor. Decreasing the olefin space
velocity decreases the quantity of high-boiling hydrocarbons formed, increases the
octane of the product, and reduces acid consumption. Olefin space velocity is one
technique of stating reaction time
TABLE 5.7.1: Range of Operating Variables in HF Alkylation

Source: Ref 8

5.8 Alkylation Products:

The products exiting the alkylation unit also include the normal butane and propane in
addition to the alkylate stream that may enter with the unsaturated and saturated feed
streams as well as a small fraction of tar that is formed by polymerization reactions.
The product streams leaving the HF alkylation unit are:
1. C 5 + alkylate (See Table 5.3)
2. LPG grade propane liquid
3. Tar
4. Normal butane liquid
Merely about 0.1% by volume of the olefin feed is converted into the undesirable tar.
This is not truly a tar rather it is thick dark brownish oil comprising of complex mixtures
of conjugated cyclopentadienes with side chains.

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TABLE 5.8.1: HF Alkylate Properties [9]

6. NExOCTANE Technology for Isooctane Production

6.1 Introduction to MTBE:
MTBE (methyl-t-butyl ether) belongs to a group of chemicals that are commonly known
as fuel oxygenates. Oxygenates are added to fuel so that oxygen content the fuel can
be increased. MTBE is also used in gasoline to somewhat lessen ozone levels and
carbon monoxide caused by automobile emissions. MTBE substitutes the use of lead as
an anti-knock agent and octane enhancer [11].
MTBE gives water an unpleasant taste even at very little concentrations, and hence it
can pollute large amount of groundwater even at a concentration of 5 15 g/l [10].
MTBE is often introduced into the water-supply aquifers by gasoline having MTBE
spilled onto the ground or by underground leakage of storage tanks at gasoline stations.
Its higher persistence and water solubility cause it to travel rapidly than many other
constituents of gasoline when released into water storage.
6.2 Introduction to NExOCTANE:
Issues regarding environment are threatening the use of MTBE in gasoline in the United
States in future. Since the late 1990s, concern related to have ground and drinking
water contamination have aroused with MTBE usage due to gasoline leakage from
underground storage tanks and from two-cycle engines exhaust. In California
numerous cases of drinking water pollution with MTBE have been reported. So, the
elimination of MTBE in gasoline was mandated in California. The U.S. Senate had
similar law, which eliminated MTBE in the 2006 to 2010 time frame [9].

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HF Alkylation & NExOCTANE Technology

With MTBE phase-out imminent, U.S. refiners faced the challenge of replacing the lost
octane value and the lost volume of MTBE in gasoline pool. Also, the utilization of idled
MTBE facilities and isobutylene feedstock resulted in persistent problems of
unrecovered and underutilized capital for the producers of MTBE.
Isooctane has been recognized essentially as a cost-effective alternative to
MTBE. It utilizes same isobutylene feed that was used in MTBE production and it offers
excellent blending value. Furthermore, production of isooctane can be obtained in a
low-cost renovation of an existing plant of MTBE.
The NExOCTANE technology was developed for the isooctane production. In this
process, isooctane is produced by the dimerization of isobutylene, which can be
hydrogenated for isooctane production. Both products are remarkable gasoline blend
stocks with ominously higher product value than polymerization or alkylate gasoline.
6.3 Process Chemistry:
The main reaction in the NExOCTANE process for the production of isooctane is the
dimerization of isobutylene over the acidic ion-exchange resin catalyst. The dimerization
reaction produces two isomers of isooctane or trimethylpentene (TMP), specifically, 2,
4, 4-TMP-1 and 2, 4, 4-TMP-2; reactions are shown in Fig 6.3.1.

FIGURE 6.3.1: Dimerization Reaction

TMP also reacts with isobutylene to produce trimmers and tetramers; etc. Production of
these oligomers is suppressed by polar components containing oxygen in the reaction
mixture.
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HF Alkylation & NExOCTANE Technology

NExOCTANE process uses alcohol and water as retarders. Acidic sites on the ionexchange resin are blocked by these polar components (alcohol and water), thereby
increasing the selectivity and controlling the catalyst activity to the formation of dimers.
The conditions of the process in the dimerization reactions are adjusted to maximize
high-quality isooctane product yield.
A little amount of C 7 and C 9 components along with other C 8 isomers will be produced
when additional olefin components such as propylene, isoamylene and n-butenes that
exist in the reaction mixture. In the process of NExOCTANE, these reactions are very
slow in comparison to the dimerization reaction of isobutylene and therefore only a
small percentage of these
Isooctene can be hydrogenated resulting in the formation of isooctane, according to the
following reaction:

FIGURE 6.3.2: Hydrogenation

6.4 Cost-Effective Technology:

Iso-octene is formed by the dimerization of the oelifin isobutylene feedstock by a
relatively low cost renovation of the existing MTBE production unit; hence the
technology is cost effective and also replaces MTBE in an effective manner. In a
hydrogenation unit, iso-octene can be further processed to produce saturated isooctane [24].
The main features of NExOCTANE process are:
Long-Life Dimerization Catalyst: The catalyst gives substantially longer run
lengths and superior performance than standard resins to decrease the operating
costs. Dimerization catalyst system is based on acidic ion-exchange resin that is
specifically designed for the dimerization of isobutylene and is exclusively
available for the NExOCTANE process.
State-of-the-Art Hydrogenation Technology: Hydrogenation technology that is
low cost and features trickle bed design based on catalysts commercially
available, using once-through hydrogen operation, which removes the cost of a
hydrogen recycle compressor.
Low-Cost Plant Design: Dimerization reactors are fixed bed and liquid phase
reactions take place. Recovery of product in already existing MTBE unit
distillation equipment reduces the capital investment.
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HF Alkylation & NExOCTANE Technology

6.5 NExOCTANE Process Description:

The NExOCTANE process unit consists of two independent sections: dimerization

section and hydrogenation section. Isooctene is formed as the result of dimerization of
isobutylene which occurs in the dimerization section, and then, the isooctane can be
produced by hydrogenation of isooctane which occurs in the hydrogenation section.
Hydrogenation and dimerization are independently functioning sections.
The integration of this process into the refinery is same as that of the MTBE processing
unit. Furthermore, NExOCTANE process selectively reacts with isobutylene and a C 4
raffinate is formed which is used for direct processing in an alkylation unit.

FIGURE 6.5.1: Integration OF NExOCTANE in a Refinery

Dimerization Section:
The dimerization of isobutylene occurs in adiabatic reactors dimerization over fixed
beds of acidic ion-exchange resin catalyst. The quality of product, specifically the
fractions of oligomers and dimers, is controlled by the recirculation of alcohol from the
recovery of product section to the reactors. In the dimerization reactors, alcohol is
produced through the reaction of a small quantity of water present in the olefin feed
although make water may also be added. In the reactor feed the alcohol content is kept
at a sufficient level typically so that the isooctene product contains fewer than 10%
oligomers.
Product Recovery Section:
In the dimerization product recovery step the isooctene product is separated from the
unreacted portion of the feed which is C 4 raffinate and also produces a concentrated
stream of alcohol for recirculation to the dimerization section. The C 4 raffinate is free
from oxygenates and is further suitable for processing in an HF alkylation unit.
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HF Alkylation & NExOCTANE Technology

Hydrogenation Section:

In the dimerization section the isooctene formed is further processed to produce the
saturated isooctane product in a hydrogenation unit. This unit can also be designed to
minimize sulfur content in the product in addition to saturating the olefins. This section
consists of a product stabilizer and trickle-bed hydrogenation reactor(s). The purpose of
the product stabilizer is to eradicate lighter components and unreacted hydrogen in
order to produce a product with a specified vapor pressure.
The utilities required for the NExOCTANE process are summarized as follows:
TABLE 6.5.2: Typical Utility Requirements

Source: Ref 7
7. Environmental Considerations:
7.1 Effluent Treatment:
In Alkylation units system of effluent-treatment, large amount of the neutralized HF acid
must ultimately leave the system as alkali metal fluoride. Due to its very low solubility in
water, CaF 2 is the desired final product. Effluent having HF acid can be treated with
lime [CaO-Ca(OH) 2 ] slurry or solution, or it can be indirectly neutralized in a KOH
system to form the required CaF 2 product.
KOH neutralization system presently used involves two-stage process. Since HF acid is
neutralized by the aqueous KOH, soluble potassium fluoride (KF) is formed, and the
KOH is progressively depleted. Periodically, some amount of KF containing the
neutralizing solution is withdrawn to KOH regenerator. In this particular vessel, lime
slurry reacts with KF to form insoluble CaF 2 and thus regenerates KF to KOH.
Regenerated KOH is returned to the system, and solid CaF 2 is routed to neutralizing
basin [7].
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HF Alkylation & NExOCTANE Technology

7.2 Effluent Gases:

HF Alkylation unit utilizes two separate gas vent lines for maintaining acidic gases
separation from non-acidic gases until acidic gases can be scrubbed free of the acid.
Acidic Hydrocarbon Gases: The acidic hydrocarbon gases are originated from those
sections of the unit where HF acid exists. These gases may possibly evolve during
upset of unit, particularly during a shutdown, or during maintenance period in which all
these acidic gases are fractionally or completely removed from process vessels or
equipment. Gases from acid vents and also from acid pressure relief valves are piped to
separate closed relief system for neutralization of acid contained in gas. The acid free
gases are afterwards routed from this section of acid-scrubbing to refinery non-acid flare
system, where these gases are disposed of correctly by burning.
Non-Acidic Hydrocarbon Gases: These gases are produced from the sections of unit
in which HF acid is not present. Non-acidic gases from the process vents and relief
valves are made to discharge into refinery non-acid flare system, where these nonacidic gases are disposed of by burning. Material that is released to flare is mostly
hydrocarbon in nature. Possibly, small amount of the inert gases are also included.
Obnoxious Odours and Fumes: The only particular area from which all these
potentially objectionable fumes can originate is units neutralizing basins. In order to
stop discharge of these odorous gases to surroundings, neutralizing basins are covered
tightly and are equipped with a gas scrubber to get rid of any offensive odours. Gas
scrubber use either activated charcoal or water as scrubbing agent. However, in
aforementioned system of neutralization, the odours from basin are basically nonexistent because main cause of these odours is handled in separately closed vessels.
7.3 Liquid Effluents:
To ensure the segregation of the non-acid from the possibly acid-containing water
streams, the HF Alkylation unit is equipped with two separate sewer systems.
Acidic Waters: Any possible HF which contains water streams (rainwater runoff which
is in wash water and acid area), the heavy hydrocarbons, and also possibly spent
neutralizing media are then directed through acid sewer system to neutralizing basins
for neutralizing any acidic material. In basins, lime is used in converting the incoming
soluble fluorides to CaF 2 .
Liquid Process Effluents (Hydrocarbon and Acid): Acid effluents and hydrocarbons
originate from minor undesirable process side reactions and also from any other feed
contaminants that are introduced to unit. The undesirable by-products produced in this
way are finally rejected from Alkylation unit in acid regeneration column as bottom
stream.
7.4 Solid Effluents:
Neutralization Basin Solids: Neutralization basin solids largely consist of CaF 2 and
the unreacted lime. All of the HF-containing liquids that are directed to neutralizing
basins having ultimately any contained soluble fluorides are converted to insoluble
CaF 2 . Disposal of all of this solid material is done on batch basis. Vacuum truck is
usually used to remove fluoride-lime sludge from pit. This sludge has conventionally
been disposed of in landfill after analysis to assure that appropriate properties are met.

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HF Alkylation & NExOCTANE Technology

Product-Treating Solids: Product treating solids are originated when LPG products
are defluorinated over the activated alumina. Over the time, alumina loses ability to
defluorinate LPG product streams. At this moment, alumina is considered as spent, and
it is replaced with fresh alumina. The spent alumina must be disposed of in agreement
with applicable regulations or it must be sent to alumina vendor for recovery.
Miscellaneous Solids: The porous material such as wood, wiping cloths, pipe
coverings, and the packings that are alleged of coming into contact with the HF acid are
placed in specifically provided disposal cans for the removal and are then periodically
burned.
During normal unit operations these solids may originate or during maintenance period.
Staging of wood and other use of wood in area are kept to a minimum level. Before
being removed from the acid area the metal staging must be neutralized.
8. Safety Issues in Alkylation Units:
The alkylation unit consists of two main process hazards:
1) Light hydrocarbons in large volumes which are extremely flammable and possibly
explosive if released.
2) Toxic and corrosive acid catalyst.
Both hydrofluoric acid and sulphuric acid alkylation units have same volumes of
hydrocarbon with similar risks, but the risks accompanying each acid are different. From
the aerosol tendencies to mitigating the effects of leakage to personal protective
equipment, HF alkylation needs much stricter precautions because of its greater
potential to cause damage.
9. Modifications & Recommendations:
9.1 Aerosol Potential:
HF has a boiling point of 66.92oF (19.4C) at atmospheric pressure and it vaporizes in
the incident of a leak to the atmosphere. The scientific HF release tests accompanied in
1986 in the Nevada desert astonished the researchers when 100% liquid HF that was
released led to the formation of a white, dense and rolling cloud of toxic gas. This cloud
rapidly expanded and concentrations toxic gas was measured at distances of about five
to ten kilometers downwind of the release point. Therefore, unless mitigated, release of
HF in a refinery will place the refinery workers and the surroundings in severe danger.
Several HF accidents have occurred in recent years. The most prominent was in 1987
that occurred at Marathon Oil Company refinery situated in Texas City, Texas. This
incident needed a 50 square block area nearby the refinery to be exiled with over 900
people needing medical treatment for injuries caused by the accident. Luckily there
were no fatalities, since this was a minor release of HF vapor only.

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9.2 Mitigation:

HF Alkylation & NExOCTANE Technology

Due to its tendency to form aerosol, HF spills and leaks carry a greater potential for
causing harm as the vapor resulting from a release cannot be contained easily.
Furthermore, the possibility for an HF leakage exists throughout the unit. API RP 751
calls for the installation of various protective systems for mitigating the effects of a
potential release of HF acid. Reliable instruments that speedily detect the release of HF
are recommended. These may comprise of closed-circuit TV and point sensors [12].
Water sprays of high volume capable of "knocking down" the cloud of HF acid are also
recommended. For mitigating 90% of an HF release, a 40:1 ratio of water to HF is
required. Provisions must be ensured for the potential of handling a large amount of HFcontaminated runoff water. This system should be completely tested. Low HF inventory
should be maintained, requiring close scheduling with the HF suppliers. Finally, a quick
acid deinventory system is recommended. This would displace acid from the leaking
section of the HF alkylation unit to a safe location, reducing the time the HF is allowed
to leak.
9.3 HF Modifiers:
As HF mitigation systems are activated only once a leakage has taken place and
aerosol has been released, research on HF modifiers shows that would itself decrease
the aerosoling tendency of the HF has been ongoing. There are two technologies that
are close to commercialization. Each technology claims that, when combined with a
40:1 water spray system of mitigation, the overall decrease in aerosol potential should
be about 95-97%.
Additionally, some of the tests have revealed octane increases in the alkylate product
when additives are used. The HF modifier technologies applied needs the installation of
an additive recovery system and additive separation additive recovery system, alkylate
treating section, storage and supply facilities of the additive.
Capital costs are projected to be around U.S $3.6 - 7.0 million. Furthermore, increase in
operating costs is expected [15].
9.4 Advances in HF Alkylation Technology:
UOP has disclosed a new design for enhanced conventional HF alkylation processes.
The new process uses split feed series recycle (SFSR) reactor sections for removing
process heat. It also offers minimized operating cost and octane maximization. The
Alkad process incorporates a vapor suppression additive into the cost-effective HF
alkylation unit, where the additive reduces HF aerosol emissions by 90% using other
mitigation techniques and hardware [15]. The additive does not give off sulfur to the
alkylate product as the Alkad process is claimed to be very tolerant of high sulfur oils
without contaminating the alkylate product. The additive does not adversely affect nor
degrade wastewater treating, and separates cleanly from hydrocarbons. It can also be
easily recovered and recycled into the alkylation unit.
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HF Alkylation & NExOCTANE Technology

10. Distillation Column P&ID

Figure 1

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HF Alkylation & NExOCTANE Technology

10.1 P&ID Description:

Figure 2

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HF Alkylation & NExOCTANE Technology

Figure 3

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HF Alkylation & NExOCTANE Technology

Designer now starts thinking about proper orientation of the nozzles and the
provisions for accessing the points of operation and maintenance.
Considerations of pipeline leaving tower area and adjacent piping shall be
visualized.
First step is to orient manholes possibly all in the same directions.
Levels of the platforms are decided on elevation view based on manholes and
access to the relief valves.
All of the platform levels in proper segments of tower with a ladder location must be
drawn on a plan view. Manhole shall be displayed in proper segment with angle of
orientation, and space for swing of manhole covers taking davit hinge as the center.
The layout should be initiated from top of column with designer visualizing layout as
a whole. There shall be no trouble in dropping the large overhead line straight down
on the side of column, and leaves column at high level and crosses directly to
condenser. It clears the segment at lesser elevations for the piping or for the ladder
from the grade level to first platform.
The flexibility and the thermal load connected with large-dia of overhead lines to
condenser at grade level or at higher level should be considered. Relief valve
protecting tower is generally connected to overhead line. Relief valve discharging to
the atmosphere should be located on highest tower platform.
In closed system of relief-line, Relief-valve must be located on lowest tower platform
above relief -system header. This will ensure shortest relief-valve discharge to flare
header. Entire system of relief-line should be self-draining.
It is better to space platform brackets on tower equally and aligning brackets over
one another for entire length of tower. This will reduce interferences between
structural members and pipings.
Piping and nozzles must meet requirement of process while the platforms must
satisfy the maintenance and the operating needs. Tower piping access, instruments
and valves influence ladders placement.
The condenser and the reboiler lines are available between both sides of manhole
and ladders.

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HF Alkylation & NExOCTANE Technology

Figure 4
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HF Alkylation & NExOCTANE Technology

Figure 5

See Fig.4 or 5 for the overall orientation of distillation column.

The line approaching yard or piperack can be turn left or right on the basis of overall
arrangement of plant. Respective segments of all these lines are between ladders
and 180. Segment at 180 is suitable for lines without instruments and valves, this
is that point which is farthest from the manhole platforms.
Sequence of the lines around tower is influenced by the conditions at a grade level.
The piping provisions without the lines crossing over one another gives neat
appearance and generally a more appropriate installation.
Correct relationship between tower internals and process nozzles is very vital. Angle
is generally chosen between radial centreline of the internals and the tower-shell
centrelines.
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HF Alkylation & NExOCTANE Technology

By the proper choice of angle (generally 45 or 90 to piperack) many hours of the

work and the future problems can be saved.
Providing clearance for lifting tackle to all points from which handling is needed, and
good access must be provided.
Interpretation of the process requirements inside tower is generally more exact than
for the exterior piping design.
Internal or external access is very significant. This includes the accessibility of the
connections from platforms and ladders and the internal accessibility through the
shell manholes, the handholes or the removable sections of trays. Opening of
manhole must not be obstructed by internal piping.
The reboiler-line elevations are to be determined by draw off and the return nozzles
and orientation is influenced by the thermal flexibility considerations. The reboiler
lines and overhead lines should be simple and direct.
The Fig (6) shows segments of the tower circumference allotted to the piping,
manholes, nozzles and platform brackets and the ladders as generally
recommended for developing a well-designed layout.

Figure 6

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HF Alkylation & NExOCTANE Technology

11. Conclusions:

The HF alkylation process is of vital importance to the present day. It plays a very
important role in production one of the mostessential feeds to the final gasoline
blend. With the increase in number of fluid catalytic cracking (FCC) units used in
refineries its significance has increased.
The HF alkylation performs the critical role of improvement of the byproducts
from FCC (Fluid Catalytic Cracking) to high-value product (alkylate), which is
then used as a component of gasoline blending.
With MTBE phase-out imminent, U.S. refiners faced the challenge of replacing
the lost octane value and the lost volume of MTBE in gasoline pool. Also, the
utilization of idled MTBE facilities and isobutylene feedstock resulted in persistent
problems of unrecovered and underutilized capital for the producers of MTBE.
Isooctane has been recognized essentially as a cost-effective alternative to
MTBE. It utilizes same isobutylene feed that was used in MTBE production and it
offers excellent blending value. Furthermore, production of isooctane can be
obtained in a low-cost renovation of an existing plant of MTBE. The
NExOCTANE technology was developed for the isooctane production which is a
cost-effective revamp of existing MTBE processing units. The product of
NExOCTANE process is 2, 2, 4 trimethylpentane which has the highest octane
number of 100 among all hydrocarbons so it can blended to give a very high
quality gasoline.
The aim of this report was the production of high octane gasoline which is free
from environment threatening MTBE hence HF Alkylation process and
NExOCTANE technology were combined for this purpose.
For the installation of a new alkylation unit, H 2 SO 4 Alkylation is preferred these
days because it has less safety problems in case of leakages. So, for already
existing HF alkylation plants modifications were proposed to reduce the process
hazards and enhance its safety.

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HF Alkylation & NExOCTANE Technology

References

1. Gasoline price volatility and the elasticity of demand for gasoline, C.-Y. Cynthia Lin,
Lea Prince, United States.
2. www.indexmundi.com/
3. The 12th Worldwide Alkylation Symposium, 49 June 2006, Orlando, FL, USA.
4. Hydrocarbon Processing, Jun 2003, 82 (6), 32
5. V. N. Ipatieff and L. Schmerling, Advances in Catalysis, vol. I (Academic Press, New
York, 1948), pp. 2763.
6. R. E. Payne, Petrol. Refiner. 37(9), 316329.
7. Robert A. Meyers, Handbook of Petroleum Refining Processes, Third Edition,
(McGraw-Hill Book Company, New York, 1960).
8. Petrol. Refiner. 31(9), 156164 (1952).
9. Michael B. Simpson, Michael Kester
10. James H. Gary, Glenn E. Handwerk, Mark J. Kaiser, Petroleum Refining:
Technology and Economics, Fifth Edition.
11. http://en.wikipedia.org/wiki/Methyl_tert-butyl_ether
12. http://water.epa.gov/drink/contaminants/unregulated/mtbe.cfm
13. Conference, 2327 July 2006, Vancouver, BC, Canada. Contact: ASME
International, Three Park Avenue, New York, NY 10016-5990.
14. Volume 2006, Issue 11, November 2006.
15. US 8,153,096, Honeywell International Inc, Morristown, NJ, USA, 10 Apr 2012
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(McGraw-Hill Book Company, New York, 1960), pp. 153163.
17. R. J. Hengstebeck, Petroleum Processing (McGraw-Hill Book Company, New York,
(1959), pp. 218233.
18. Hydrocarbon Process. 49(9), 198203 (1970).
19. V. N. Ipatieff and L. Schmerling, Advances in Catalysis, vol. I (Academic Press, New
York, 1948), pp. 2763.
20. H. Lerner and V. A. Citarella, Hydrocarbon Process. 70(11), 8994 (1991).
21. A. V. Mrstik, K. A. Smith, and R. D. Pinkerton, Advan. Chem. Ser. 5(97), (1951).
22. http://stratfordengineering.com/articles/safety-issues-in-alkylation-units
23. Hydrofluoric Acid Alkylation, ABB and ConocoPhillips develop a critical new process
analysis tool
24. NExOCTANE, Petrochemicals, KBR Technologies

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HF Alkylation & NExOCTANE Technology

Source: Robert A. Meyers, Handbook of Petroleum Refining Processes, Third Edition,

(McGraw-Hill Book Company, New York, 1960)

Source: James H. Gary, Glenn E. Handwerk, Mark J. Kaiser, Petroleum Refining:

Technology and Economics, Fifth Edition.
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HF Alkylation & NExOCTANE Technology

Source: Robert A. Meyers, Handbook of Petroleum Refining Processes, Third Edition,

(McGraw-Hill Book Company, New York, 1960)

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