ALKYLATION &

POLYMERIZATION
Alkylation
Alkylation is the process of producing gasoline range material (alkylates)
from olefins such as propylene, butylenes, amylene and isobutene.
The process combines an unsaturated light hydrocarbon with isobutane to
produce alkylate.





(Source: U.S. Energy Information Administration)
In practice only isobutane is used because isopentane has a sufficiently;
1. High octane number
2. Low vapor pressure to allow it to be effectively blended directly into
finished gasolines.
Either sulfuric or hydrofluoric acid is used as the catalyst for the alkylation
reaction. Alkylate is high in octane but has low volatility and can be added to
motor gasoline.
High octane hydrocarbons are needed to help prevent auto ignition of gasoline
(knocking) in an engine.
Each catalyst also has different operating conditions (like temperature and
pressure) along with different safety considerations.
Sulfuric acid is a liquid at unit operation conditions, while hydrofluoric acid is a
gas at unit operating conditions.
The current trend towards elimination of methyl tertiary butyl ether (MTBE) has
resulted in in increased attention to alkylation technology.
The addition of an alkyl group to any compound is an alkylation reaction, but in
petroleum refining terminology the term alkylation is used for the reaction of the
reaction of low molecular weight olefins with an isoparaffin to form higher
molecular weight isoparaffins.

Polymerization
Polymerization in petroleum refining is the process of converting light olefin gases
including ethylene, propylene, and butylene into hydrocarbons of higher
molecular weight and higher octane number that can be used as gasoline
blending stocks.
Polymerization combines two or more identical olefin molecules to form a single
molecule with the same elements in the same proportions as the original
molecules.
Polymerization may be accomplished thermally or in the presence of a catalyst at
lower temperatures.
Both processes used to make gasoline components from materials that are too
light to be otherwise used in gasoline.


Catalyst (H2SO4 & HF)
In alkylation processes, it using hydrofluoric or sulfuric acids as catalysts
From a safety and environmental standpoint, H2SO4 has a clear advantage over
HF. In some areas of the world, HF is no longer considered an acceptable option
for a new unit due to concerns over safety.
HF is an acute poison that may immediately and permanently damage lungs and
the corneas of the eyes.



Source:www.dupont.com alkylation
process
Table 1:Light Olefin Alkylate Octane
Feed Availability and Product Requirements

Historically, butylenes from the FCC were
the traditional olefins fed to the alkylation
unit.
Today, alkylation units are using a broader
range of light olefins including propylene,
butylenes and amylenes.
Alkylate composition and octane from
pure olefins are quite different for each
catalyst as shown in Table 1.
Catalyst and chemical costs


Catalyst and chemical costs favor HF units, with the main difference being acid
cost. Although HF is more expensive, much less is used and can be regenerated
on site.
The operating cost of H2SO4 alkylation depends heavily on reactor design, feed
pretreatment, residual contaminants, and the cost and availability of H2SO4
regeneration.
Presently, refiners can either regenerate the catalyst on site or send it to an
outside regenerator.
H2SO4 vs. HF Summary
From a safety and environmental standpoint, H2SO4 has a clear advantage over
HF.
The actual choice for a particular refinery is governed by a number of site-specific
factors, which require a detailed analysis.
UNIT INVESTMENT
UTILITY COSTS
CATALYST & CHEMICALS
SAFETY/ENVIRONMENTAL CONSIDERATIONS
PRODUCT QUALITY
FEED TYPE/ISOBUTANE AVAILABILITY
Typical modern refinery processes for producing gasoline blending
components are given below:
Catalytic Naphtha Reforming - converts saturated, low octane
hydrocarbons into higher-octane products containing about 60%
aromatics.
Fluidised Catalytic cracking FCC - breaks larger, higher-boiling
hydrocarbons into gasoline range product containing 30% aromatics and
20-30% olefins.
Isomerisation - raises gasoline fraction octane by converting straight
chain hydrocarbons into branched isomers.

Alkylation - reacts gaseous olefin streams with isobutane to produce
liquid high octane iso-alkanes.

Among all the options for lead phase out, Catalytic Naphtha
Reforming and Fluidized Catalytic Cracking have been the most
commonly employed processes in refineries to provide gasoline blending
high-octane components.

Olefin polymerization
o Olefin polymerization to - obtain polymer gasoline with good octane
numbers.
o RON of the polymer gasoline product < reforming and alkylation.
Comparatively poor quality but for the sake of enhancing octane
number, polymerization is carried out.
o Polymer gasoline product quality : Polymerization < alkylation unit.
o Typical feedstock for polymerization process are C3 and C4
olefins that are obtained from catalytic cracking.
o The end product from polymerization reactor is a dimer or a trimer
of the olefins.
o Polymerization combines two or more identical olefin molecules
to form a single molecule with the same elements in the same
proportions as the original molecules.
o Polymerization may be accomplished thermally or in the presence
of a catalyst at lower temperatures.

Caustic wash: C3-C4 olefin feed subjected to caustic wash to remove H2S
and other sulphur compounds (such as mercaptans). These tend to poison
the catalyst.
Water scrubbing: Eventually water scrubbing is carried out to remove
dissolved impurities and generate waste water.

Polymerization reactor: The reaction mixture is heated, compressed and fed
to a polymerization reactor. The reactor design is a shell and tube type
design where catalyst is placed in the tube for the reaction to take place and
cooling water is circulated in the shell side to control the temperature
increase due to the exothermic reaction.

Fractionation: Subsequently, the reactor product is fed to a depropanizer and
debutanizer to produce propanes, butanes and polymer gasoline. The
polymeric product is further stabilization using hydrogenation stabilizer
which converts any freely available double bonds to single bonds. The end
product is polymer gasoline.

The propane produced is partially recycled to the reactor and the other part
taken out as a product.

Comprises of four basic steps

1. Carbonium ion formation : Here, olefin reacts with acid catalyst to yield carbonium ion.



2. Additon reaction : Carbonium ion reacts with olefin to generate intermediate carbonium
ion.


3. Regeneration : The intermediate carbonium ion converts to the dimer and
generates back the proton on the catalyst surface.






4. Isomerization : Straight chain proton substituted olefins convert to isomeric
carbonium ions.

Catalysts used: Acid catalysts (H2SO4 ) are used.

Temperature: 150 220oC are used. Too high temperatures give
tar deposits.

Pressure: 25 100 atms.

Polymerization ties two or more olefins together to make
polymer gasoline.
The double bond in only one olefin is changed to a single bond
during each link between two olefins. This means the product
will still have a double bond.
For gasoline, these polymer stocks are good for blending
because olefins tend to have higher octane numbers than their
paraffin homologs.


http://nptel.ac.in/courses/103103029/11
ALKYLATION
The addition of an alkyl group to any compound is an alkylation
reaction but in petroleum refining terminology the term alkylation
is used for upgrade light olefins (from FCC and cokers viz
breakers) and isobutene into a highly branched paraffins.
In an alkylation process, olefins are reacted with isoparaffins to
yield alkylate product.
The basic purpose of alkylation is to enhance the octane number
of the feed stock.
For instance, octane number of butane alkylate is about 92 97.
This is due to the formation of a hydrocarbon with side chain
arrangement of carbon and hydrogen atoms.
Although alkylation can take place at high temperatures and
pressures without catalysts, the only processes of commercial
importance involve low temperature alkylation conducted in the
presence of either sulphuric or hydrofluoric acid.

Reaction Mechanism
Three basic reaction steps to achieve alkylation

1. Carbonium ion formation: In this reaction, alkene reacts with a proton (acid
catalyst) to produce a proton substituted olefin. The proton substituted olefin
reacts with isoparaffin to generate a reactive carbonium ion and alkane.




2. Carbonium ion intermediate formation: In this reaction, the carbonium ion
formed in step 1 reacts with the olefin to produce an intermediate carbonium ion.

3. Regeneration of carbonium ion: In this reaction, the intermediate carbonium ion
reacts with the isoparaffin to produce alkylate product and carbonium ion. Thus
carbonium ion is again regenerated to take part in step 2 reactions along with
other additional unreacted olefin molecules.


To avoid olefin polymerization, high isobutane to olefin ratios are
used.
Typical isobutene to olefin ratios are 5:1 to 15:1
Acid catalysts are used. Primarily sulphuric acid (H2SO4) or
Hydrofluoric acid (HF)are used.
Depending on the acid catalysts choosed the process complexity
varies. We present both process technologies to indicate the
pertinent process complexity.
Reaction operating temperature: 10 - 20C using H2SO4 and 25
40C using HF
Reaction pressure: 4.4 bar for H2SO4 and 7.8 bar for HF.
When H2SO4 is used refrigeration is used.
When HF is used, refrigeration is not used.
Caustic wash: The feed mixture (olefin + C4 compounds) are first subjected to caustic
wash. During caustic wash, sulphur compounds are removed and spent caustic is
recycled back to the caustic wash. Fresh caustic solution is added to take care of the
loss.
Refrigeration: The olefin feed enters a refrigeration unit to reduce the feedstock
temperature.
Alkylation reactor: The reactor is arranged as a series of CSTRs with acid fed in the first
CSTR and feed supplied to different CSTRs. This arrangement is for maximizing the
conversion.
In the alkylation reactor it is important to note that the olefin is the limiting reactant and
isoparaffin is the excess reactant.

The alkylator unit therefore will have two phases in due course of reaction namely the
olefin + isoparaffin mixture which will be lighter and the alkylate stream which will be
heavier and will be appearing as a bottom fraction if allowed to settle.

Since excess isoparaffin is used, the isoparaffin can be easily allowed as a bypass
stream.

Eventually, the alkylate product from the last reactor will be taken out as a heavy
stream.

Thus, the alkylation reactor produces two streams. These are (a) isoparaffin rich organic
phase and (b) alkylate rich phase along with acid and isobutane phases.

These streams should be subjected to further purification.

Phase separator: It so happens that the acid enters the organic rich stream and
will be subjected to phase separation by settling. Similarly, the olefin/isoparaffin
mixture will be also separated by gravity settling. Thus the phase separator
produces three streams namely (a) olefin + isoparaffin rich phase (b) acid rich
stream (c) alkylate rich stream.

Olefin + Paraffin processing: The olefin + paraffin stream is first subjected to
compression followed by cooling. When this stream is subjected to throttling and
phase separation, then the olefin + paraffin rich stream will be generated. The
propane rich stream from this stream is generated as another stream in the phase
separator.

Propane defractionator: The propane rich stream after cooling is fed to a
fractionator where propane is separated from the olefin+isoparaffin mixture. The
olefin+isoparaffin mixture is sent back to mix with the olefin feed.

Caustic wash for alkylate rich stream: The caustic wash operation ensures to
completely eliminate acid concentration from the alkylate.

Alkylate fractionation: The alkylate is fed to a distillation column that is supplied
with isobutane feed and alkylate feeds to produce isobutane as a top product and
alkylate + butane mixture as a bottom product.

Debutanizer: The debutanizer separates butane and alkylate using the concept of
distillation.


The process is similar to the sulphuric acid plant. However,
additional safety issues make the process complex.
The feed is first subjected to drying followed by pre-cooling.

After pre-cooling the reaction mixture the reaction mixture is fed
to a reactor.

Unlike CSTRs in series here impeller reactors are used. The
reactor consists of cooling tubes to absorb the heat generated.

The reaction products enters a settler where oil and the HF are
separated.

Since there can be traces of HF in the oil rich phase and vice-
versa additional processing is followed.

The HF rerun column removes traces of oils from the bulk of the
HF. Thus HF purified will be recycled back to the reactor. The
bottom product thus generated in this unit is acid oils.

A HF stripper is used to remove the HF in lower quantities from
the alkylate product. Eventually, the HF stripper produces HF that
is sent back to the reactor and the alkylate product.

The alkylate product is sent to a deisobutanizer and depropanizer
units. The final alkylate product is produced by using a
deflourinator which is basically a caustic wash or adsorption unit.
Finally n-butane + alkylate is produced as the bottom product.


http://nptel.ac.in/courses/103103029/9
Safety and Health
Alkylation and Polymerization in
Refineries
Extremely Hazardous Chemical Processes
U.S. refineries use very large quantities of Hydrofluoric Acid (HF) in
alkylation and Sulfuric Acid (SA) for both alkylation and
polymerization
Some have >1/2 million pounds on site of chemical catalyst
HF readily vaporizes in the atmosphere. A large release can form a
vapor cloud that can travel great distances
SA is a highly corrosive acid and exist in liquid form at atmospheric
pressure. Can cause chemical and thermal burn if in contact
33
Alkylation and Polymerization
Catalyst
HF and SA Extremely Toxic
OSHA & EPA regulate as highly toxic a Toxic Inhalation
Hazard (TIH)
Damages eyes, skin, nose, throat, respiratory system and
bones
Fast acting, can cause deep, severe burns and can cause
permanent damage
High concentrations are immediately dangerous to life and
health (IDLH 30 ppm)
Serious exposures require a knowledgeable health
practitioner to administer antidote calcium gluconate as
soon as possible after exposure
34
Recent Releases
HF Related Oil Industry Incidents

Marathon Canton, OH (February 23, 2011) release of 145
pounds of HF
CITGO Corpus Christi, TX (July 19, 2009) explosion, fire, HF
release critically injured one
Sunoco Philadelphia, PA (March 2009) HF release sends
13 workers to hospital
Giant Industries, Ciniza, NM (April 4, 2004) 4 workers
seriously in fire on HF unit
35
CITGO Incident
Citgo, Corpus Christi, TX. July 2009 explosion and fire in the HF alkylation unit
severely injured one worker and burned for two days. According to the CSB
investigators, about 10% of the estimated 42,000 pound release traveled
beyond the refinery fenceline.
36
Most Recent

37
HF release in South Korea, Gumi National Industrial Complex in
the southern city of Gumi. Five workers killed, 18 injured, 3,000
treated for exposure. Numerous cattle and crops were affected.
Aftermath
Health and Safety Considerations
for Alkylation


Fire Potential
Alkylation units are closed processes
However, the potential exists for fire should a leak or release occur
that allows product or vapor to reach a source of ignition.

Safety
For chemical:
Sulfuric acid and hydrofluoric acid are potentially hazardous
chemicals
Loss of coolant water, which is needed to maintain process
temperatures, could result in disaster
Precautions are necessary to ensure that equipment and materials
that have been in contact with acid are handled carefully and are
thoroughly cleaned before they leave the process area or refinery
Immersion wash vats are often provided for neutralization of
equipment that has come into contact with hydrofluoric acid.
Hydrofluoric acid units should be thoroughly drained and chemically
cleaned to remove all traces of iron fluoride and hydrofluoric acid.
Following shutdown, where water has been used the unit should be
thoroughly dried before hydrofluoric acid is introduced.

For piping and tank:
Leaks, spills, or releases involving hydrofluoric acid or hydrocarbons
containing hydrofluoric acid can be extremely hazardous
Care during delivery and unloading of acid is essential
Process unit containment by curbs, drainage, and isolation so that
effluent can be neutralized before release to the sewer system is
considered
Vents can be routed to soda-ash scrubbers to neutralize hydrogen
fluoride gas or hydrofluoric acid vapors before release
Pressure on the cooling water and steam side of exchangers should
be kept below the minimum pressure on the acid service side to
prevent water contamination
For process units:
Some corrosion and fouling in sulfuric acid units may occur from the
breakdown of sulfuric acid esters or where caustic is added for
neutralization
These esters can be removed by fresh acid treating and hot-water
washing
To prevent corrosion from hydrofluoric acid, the acid concentration
inside the process unit should be maintained above 65% and
moisture below 4%
Health
This is a closed process, exposures are expected to be minimal during
normal operations.
There is a potential for exposure should leaks, spills, or releases occur.
Sulfuric acid and hydrofluoric acid are potentially hazardous chemicals
so special precautionary emergency preparedness measures and
protection appropriate to the potential hazard and areas possibly
affected need to be provided.
Safe work practices and appropriate skin and respiratory personal
protective equipment are needed for potential exposures to
hydrofluoric and sulfuric acids during normal operations such as reading
gauges, inspecting, and process sampling, as well as during emergency
response, and maintenance.
Procedures should be in place to ensure that protective equipment
and clothing worn in hydrofluoric acid activities are decontaminated
and inspected before reissue.
Appropriate personal protection for exposure to heat and noise also
may be required.
Health and Safety Considerations
for Polymerization
Fire potential
Polymerization is a closed process where the potential for a fire exists
due to leaks or releases reaching a source of ignition
Safety
The potential for an uncontrolled exothermic reaction exists should
loss of cooling water occur
Severe corrosion leading to equipment failure will occur should
water make contact with the sulfuric acid, such as during water
washing at shutdowns
Corrosion may also occur in piping manifolds, reboilers, exchangers,
and other locations where acid may settle out
Health
This is a closed system, exposures are expected to be minimal under
normal operating conditions.
There is a potential for exposure to caustic wash (sodium hydroxide),
to sulfuric acids used in the process or washed out during shutdown
Safe work practices and/or appropriate personal protective
equipment may be needed for exposures to chemicals and other
hazards such as noise and heat, and during process sampling,
inspection, maintenance, and turnaround activities
The collection, transportation,
and disposal of garbage,
sewage, and other waste
products.

Also encompasses management
of all processes and resources
for proper handling of waste
materials, from maintenance of
waste transport trucks and
dumping facilities to compliance
with health codes and
environmental regulations


OBJECTIVES
Ensure
environmental
protection
Encourage
waste into
energy option
Ensure an
efficient and
effective waste
management
To design
manufacturing
process that
can avoid and
minimize waste
Increase in
reuse and
recycling rates
and product
Waste Water
Any kind of water that has been
adversely affected in quality by
anthropogenic influence
Source of
wastewater in
refinery
Process Water Boiler feed water Cooling water
Fire water Utility water
Contaminant P
r
o
bl
e
m
Removal
methods
Turbidity Makes water cloudy and deposits in water
lines and process equipment
Coagulation, settling and filtration
Hardness Primary source of scale formation in heat
exchangers and pipe lines
Softening, distillation, surfactants
Alkalinity Causes foaming in steam systems and
attacks boiler steel. Bicarbonate and
carbonate produce carbon dioxide in steam
which is highly corrosive
Lime and lime-soda softening, Zeolite
softening, Dealkalization by anion
exchange
Sulphate Adds to the solids content of water and
combines with calcium to form calcium sulfate
scale
Demineralization, distillation
Chloride Adds to solids content and increases the
corrosive properties of water
Demineralization, distillation, desalination
(if sea water is being used)
Silica Scaling on heating and cooling
equipment and pipelines
Anion exchange resins, distillation

Iron and
magnesium

Discolors the water and precipitates in
water lines and process equipment

Aeration, coagulation and filtration, lime
softening, cation exchange
Oil

Source of scale, sludge and foaming in
boilers. Impedes heat exchange.
Undesirable in most processes

Oil/water separators strainers.
coagulation and filtration. Diatomaceous
earth filtration
Oxygen Corrosion of water lines heat exchange
equipment, boilers, return lines, etc.
Deaeration, sodium sulphite, corrosion inhibitors

Hydrogen sulphide

Cause of rotten egg odor. Corrosion, toxicity

Aeration, chlorination, highly basic anion
exchange
Conductivity Conductivity is the result of ionizable solids in
solution. High conductivity can increase the
corrosive characteristics of a water
Processes which decrease dissolved solids
content will decrease conductivity. Examples are
demineralization, lime softening
Dissolved solids

Dissolved solids is the measure of total
amount of dissolved material. High
concentrations of dissolved solids are
objectionable because of process
interference and as a cause of foaming in
boilers

Various softening process, such as lime
softening and cation exchange by zeolite, will
reduce dissolved solids. Demineralization,
distillation
Suspended solids

Suspended solids is the measure of
undissolved matter. Suspended solid plug
lines, cause deposits in heat exchange
equipment, boilers, etc.

Sedimentation. Filtration, usually
preceded by coagulation and settling

WHY WE NEED TO TREAT
Contaminant Concentration (mg/l)
BOD 150-205
COD 300-600
Phenol 20-200
Benzene 1-100
Heavy Metal 0.1-100
Pyrene 1-100
WASTEWATER TREATMENT
Physical Treatment method consists of:
Screening
Sedimentation
Flotation
Filtration
Chemical treatment:
Precipitation
Ion Exchange
Chemisorption
Biological Treatment Method:
Aerobic degradation
Anaerobic degradation
microorganism
Environmental Issues
Environmental Issues
Air Issues
Under the Clean Air legislation 1978 states have the primary
responsibility to address air-related impacts from energy
development. States are required under the Act to maintain - or
come into attainment with -National Ambient Air Quality Standards
(NAAQS)
Criteria air pollutants (ozone, CO, SO
2
, PM, and their precursors,
including No
x
and VOCs)
Hazardous Air pollutants (HAPs, primarily fugitive VOC emissions
from oil and gas production)
Haze precursors (which include ozone, No
x
SO
2
, and particulates)
greenhouse gases (GHGs, which include CO
2
and CH
4
)

Environmental Issues
Water Issues
Water Enactment 1920 (Act 418)
produced water
drilling fluids, cuttings and well treatment chemicals
process, wash and drainage water
sewerage, sanitary and domestic wastes
spills and leakage

Act
Environmental Quality Act 1974
OSHA 1994
Petroleum (Safety Measure) Act 1984
Petroleum Development Act 1974
Gas Supply Act 1993
International Act
1963 Clean Air Act:
Establishes levels for chemicals and particulates.
Can regulate hazardous chemicals.
1972 Noise Control Act
1974 Safe Drinking Water Act
Gives EPA authority to formulate and enforce drinking water
standards.
Covers flushing chemicals down the drain.