Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 10.6
KEROSENE ISOSIV PROCESS
FOR PRODUCTION OF
NORMAL PARAFFINS
Stephen W. Sohn
UOP LLC
Des Plaines, Illinois

The straight-chain normal paraffins in the kerosene range (C10 to C18) have their principal
uses in detergent manufacture, chlorinated fire retardants, plasticizers, alcohols, fatty
acids, and synthetic proteins. The separation of these straight-chain normal paraffins from
other classes of hydrocarbons, such as branched-chain isoparaffins, naphthenes, and aro-
matics, was a virtual impossibility prior to the advent of the synthetic zeolites known as
molecular sieves. These uniform, molecular-pore-sized adsorbents, developed by Union
Carbide in the early 1950s, opened the way for refiners and petrochemical producers to
add adsorption as a means of separating hydrocarbon classes to those already known, such
as distillation and liquid-liquid extraction. To date, eight kerosene IsoSiv systems have
been started up (Table 10.6.1). The IsoSiv* process is licensed by UOP* subsequent to the
joint venture ownership of UOP by Union Carbide and Allied Signal in 1988. Currently as
a result of the merger of UCC with Dow, and Allied Signal with Honeywell, UOP is now
owned jointly by Dow and Honeywell.

GENERAL PROCESS DESCRIPTION

The IsoSiv process separates normal paraffins from a hydrocarbon mixture, such as
kerosene or gas oil, by selective adsorption on a molecular-sieve adsorbent material. This
material is a crystalline zeolite having uniform pore dimensions of the same order of mag-
nitude as the size of individual hydrocarbon molecules. The molecular sieve used for nor-
mal paraffin separation has openings in the crystalline structure that are sized to allow
normal paraffin molecules to pass through the pore openings into the internal crystal cav-
ity, where they are retained. Nonnormal hydrocarbons, such as isoparaffins, naphthenes,
and aromatics, have larger molecular diameters and are therefore excluded from entering
the crystal cavity through the pore opening.

*Trademark and/or service mark of UOP.

10.69
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 KEROSENE ISOSIV PROCESS FOR PRODUCTION OF NORMAL PARAFFINS

10.70 SEPARATION PROCESSES

TABLE 10.6.1 Kerosene IsoSiv Commercial Applications

Normal paraffin
Unit Feed type Start-up Location capacity, BPSD
1 Kerosene 1964 United States 2300
2 Kerosene 1971 West Germany 650
3 Kerosene-gas oil 1972 Italy 2600
4 Kerosene 1973 Italy 2600
5 Kerosene-gas oil 1974 Italy 5800
6 Kerosene-gas oil 1976 Italy 5800
7 Kerosene 1983 Brazil 2600
8 Kerosene 1992 People’s Republic of China 950

Note: BPSD ⫽ barrels per stream-day.

The heart of the IsoSiv process is the adsorber section, consisting of vessels filled with
molecular-sieve adsorbent. The kerosene or gas oil feedstock is fed into one end of an
adsorber vessel, the normal paraffins in the feedstock remain in the vessel by being
adsorbed in the molecular sieve, and the remainder of the feedstock passes out the other
end of the vessel as a denormalized kerosene gas oil. The normal paraffins are recovered
from the adsorber vessel as a separate product by using a purged material. All process
hardware in an IsoSiv unit is conventional refinery equipment, such as pumps, furnaces,
heat exchangers, and compressors, designed to deliver the feedstock and the purge mate-
rial to the adsorber section and to remove the products from the adsorber section. The
kerosene IsoSiv process typically recovers 95 wt % of the normal paraffins in the feedstock
and produces a normal paraffin product of 98.5 wt % purity.

PROCESS PERSPECTIVE

During the early 1960s, the appeal of molecular-sieve adsorption led to widespread efforts
at innovating new adsorption technology. Many of these efforts were successful, in that
they resulted in molecular-sieve processes capable of separating long-chain normal paraf-
fins from kerosene-range feedstocks at just the time when the detergent industry decided
to switch to linear alkylbenzene sulfonates as a basis for its formulations of “soft” deter-
gents. The consequent demand for long-chain normal paraffins led to a worldwide wave of
construction: at least 12 adsorption plants were built to process kerosene-range feedstocks
and use processes developed by Union Carbide, UOP, Esso, British Petroleum, Shell, and
Texaco. Among the first units was the South Hampton Company’s naphtha IsoSiv unit,
which was converted to the kerosene range in 1961. In 1964 Union Carbide Corporation
installed at its Texas City, Texas, petrochemical complex an IsoSiv unit producing 100,000
metric tons/year (MTA) (220,000 lb/yr) of normal paraffins from kerosene. This unit was
to remain the world’s largest normal paraffin-producing plant for almost 10 years.
At the beginning of the 1970s, a further extension of adsorption technology was
required. The normal paraffins used as substrates for protein production extend into the gas
oil feedstock range. Suitable modifications can and have been made to existing adsorption
technology to allow successful application to the new requirements. In 1972, Liquichimica
S.p.A., now Condea Augusta S.p.A. but then a subsidiary of the Liquigas Group of Italy,
installed and started up in Augusta, Sicily, a modified IsoSiv unit to produce 110,000 MTA
(242,000 lb/yr) of normal paraffins from both kerosene and gas oil feedstocks. Plant
expansions put on-stream in 1973 brought normal paraffin production capacity at Augusta

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 KEROSENE ISOSIV PROCESS FOR PRODUCTION OF NORMAL PARAFFINS

KEROSENE ISOSIV PROCESS 10.71

up to approximately 250,000 MTA (551,000 lb/yr), making it by a wide margin the largest
single normal paraffin-producing installation in the world. A second unit that came on-
stream in December 1974 almost doubled previous capacity. A third IsoSiv unit of more
than 200,000 MTA (440,000 lb/yr) came on-stream in 1976. Total installed capacity is
more than 650,000 MTA (4,862,000 lb/yr) of normal paraffin production. These units have
used feedstocks ranging from kerosene to gas oil and intermediate mixtures of both.
A seventh kerosene IsoSiv unit came on-line in Brazil in 1983. An eighth came on-line
in China in 1992.

DETAILED PROCESS DESCRIPTION

The kerosene IsoSiv process employs the highly selective adsorption capability of molec-
ular sieves. The simplified process flow scheme is shown in Fig. 10.6.1. The basic cycle
consists of three steps: adsorption, copurge, and desorption. This section describes each in
detail.

Adsorption Step

Hydrocarbon feed at elevated temperature and slightly above atmospheric pressure is

passed upward through an adsorber vessel, where the normal paraffins are selectively
adsorbed in the bed. In processing gas oil feedstock, hexane is added to the gas oil feed to
dilute it and prevent capillary condensation from occurring on the adsorbent bed. As the
normal paraffins are adsorbed, the liberated heat of adsorption creates a temperature front
that travels through the bed. This front closely coincides with the mass-transfer front and
gives an indication of when the adsorption step should be terminated to prevent the nor-
mal paraffins from breaking through the effluent end of the bed. The temperature front is

FIGURE 10.6.1 Kerosene IsoSiv process.

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 KEROSENE ISOSIV PROCESS FOR PRODUCTION OF NORMAL PARAFFINS

10.72 SEPARATION PROCESSES

used in pilot-plant work to determine optimum design conditions and can be employed in
commercial units to set the cycle timer to prevent the front from reaching the bed exit. The
unadsorbed isomer and cyclic hydrocarbons and some purge hexane that pass through the
beds combine with the copurge effluent and are heat-exchanged against the feed stream to
recover heat. This stream is then sent to a distillation system, where the hexane purge
material is recovered as a distillate product and the heavier isomers are taken as bottoms
products.

Copurge Step

After the adsorption step, the normal paraffin-loaded beds are purged in the cocurrent
direction with just enough vaporized hexane to displace the nonadsorbed feed and isomeric
hydrocarbons from the void spaces in the adsorber vessel. This step is important especial-
ly in the production of protein substrates because it ensures that a high-purity product will
be recovered from the desorption step. The effluent from the cocurrent purge step is com-
bined with the adsorption effluent stream, as mentioned previously.

Desorption-Purge Step

After the copurge step, the beds are purged countercurrently with hexane. This counter-
current purging desorbs the normal paraffins and sweeps these desorbed vapors from the
bed, thus maintaining the average desorbate partial pressure below the value in equilibri-
um with the loading on the bed. The continuous removal of the desorbate vapor and the
simultaneous transfer of the adsorbed phase to the purge gas in an attempt to establish
equilibrium drive the desorption toward completion. In addition to this stripping effect, the
normal hexane itself becomes adsorbed on the bed and helps displace the heavier normal
paraffin desorbate. A complete removal of the heavy normal paraffin adsorbate is not
achieved on each desorption. An economic balance between the bed size, as determined by
the fraction of heavy normal adsorbate removed (or delta loading), and the hexane purge
required determines the degree of removal of the heavy normals obtained. As the purge
quantity is decreased, the delta loading is decreased; and larger adsorbers are required for
a given hydrocarbon feed throughput and cycle time. This decreased delta loading increas-
es the rate of adsorbent deactivation and consequently the required burn-off frequency
because the higher residual loading increases the rate of coke formation. Conversely,
increasing the purge quantity increases delta loading until the hexane-handling equipment
and operating costs become significant factors.
The desorption effluent containing heavy normal paraffins and hexane is partially con-
densed by heat exchange with the cold hexane purge. The vapor fraction and the conden-
sate are transferred to the normal dehexanizer system, where the normal paraffins are
separated from the hexane by standard fractionating techniques. The normal paraffin prod-
uct from the bottom of the column is cooled and removed from the process. This separa-
tion is relatively easy because of the wide difference in boiling point between hexane and
the lightest heavy normal paraffin. The recovered hexane from this column is also con-
densed and circulated back to the hexane accumulator without fractionation. Small addi-
tions of fresh hexane are required to make up losses of hexane carried out in both product
streams.
The foregoing operation sequence is integrated into continuous processing by the
cyclic use of several adsorber vessels. Automatic valves are operated by a sequencing con-
trol system. The flow of both feed and products is uninterrupted. Suitable interlocks and
alarms are provided so that the plant can operate with a minimum of operator attendance.

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 KEROSENE ISOSIV PROCESS FOR PRODUCTION OF NORMAL PARAFFINS

KEROSENE ISOSIV PROCESS 10.73

Oxidative-Regeneration Description

As the adsorber beds are cycled at the elevated operating temperatures, a carbonaceous
deposit gradually accumulates. This deposit reduces the capacity of the adsorbent, and this
reduction ultimately results in a breakthrough of normal paraffins into the isomer product
stream and decreased normal paraffin recovery. The rate at which this deposit accumulates
depends on factors such as temperature, feed impurities, feed properties, cycle time, and
residual paraffin loadings. This type of adsorbent deactivation is not permanent, and the orig-
inal bed capacity can be restored by burning off this deposit under controlled conditions. For
a kerosene-type feedstock, a bed can be cycled for 15 to 30 days before oxidative regenera-
tion is necessary. For a gas oil feedstock, the period is reduced to about 6 to 10 days.
When a bed has been cycled to the point at which oxidative regeneration is required, it
is removed from the processing operation, and another adsorber vessel is put into opera-
tion. This change is made without any interruption in the cycling sequence. The coked bed
is removed from cycling after the desorption step and is given an additional long desorp-
tion purge to remove as much of the residual normal paraffins as possible. The bed is then
completely isolated from the cycling system, and a downflow circulation of nitrogen is
pumped by means of a compressor or blower and then passed through a heater to the adsor-
ber vessel. The circulation of hot nitrogen has two purposes: to purge the hexane from the
bed and to raise the temperature of the bed to above the coke ignition point prior to the
introduction of oxygen into the system. The effluent gas from the bed is cooled to con-
dense the hydrocarbons and water that desorb.
When the bed is up to temperature, air is introduced into the circulating stream at a con-
trolled rate. The oxygen in the gas combusts with coke in the top of the bed. The heat
released from combustion is carried out of the burning zone as a preheat front traveling
ahead of the burning front. This preheat front raises the bed temperature even further. This
temperature is controlled by regulating the amount of oxygen in the entering gas. Because
excessive internal adsorbent temperatures permanently destroy the molecular-sieve crys-
tal, the gas-phase temperature is critical. As the burning front passes through the bed, the
temperature drops back to the gas inlet temperature. Because the coke deposit contains
hydrogen, water is formed during combustion in addition to carbon oxides. This water
must be removed from the system because the molecular-sieve crystal is permanently dam-
aged by repeated exposure to water at high temperatures. To minimize this damage, a dry-
er is used to prevent the water from accumulating. The proper design of the regeneration
process and the rugged nature of the molecular sieve ensure that the adsorbent has a long
operating life.
After the regeneration is complete, the bed is cooled down to the process operating
temperature and purged of any remaining oxygen by circulating nitrogen. The bed is now
ready to go on-stream to replace one of the adsorbers in use so that it, in turn, can be reac-
tivated.

WASTE AND EMISSIONS

During normal operation of the kerosene IsoSiv unit, the vent gas is not expected to con-
tain more than 5000 vol ppm of total sulfur on the average. The maximum peak sulfur lev-
el in the vent gas stream is not expected to exceed 5 vol % when the unit is operating with
feedstocks containing up to 500 wt ppm total sulfur. A second vent stream contains
approximately 1000 vol ppm of sulfur during the burn-off of an adsorber bed. The peak
concentration is not expected to exceed 5 percent. This vent will also contain approxi-
mately 2 vol % carbon monoxide.

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 KEROSENE ISOSIV PROCESS FOR PRODUCTION OF NORMAL PARAFFINS

10.74 SEPARATION PROCESSES

Proper handling of these vent gas streams depends on many factors. One suggested
method of handling these streams is to feed them to the hexane-heater firebox, provided
acceptable stack sulfur levels can still be maintained.

ECONOMICS

Many factors affect the cost of extracting normal paraffins. They include the nature of
the feedstock from which the normal paraffins are to be extracted, the specifications of the
product normal paraffins, the production capacity or size of the plant, and the location.
The last factor includes such items as climatic conditions and availability and cost of labor,
utilities, storage, and transportation.
The feedstock is of primary importance. The normal paraffin content of gas oils ranges
from 10 to 40 percent, depending on the crude oil source. The higher the normal paraffin
content, the more amenable it is for normal paraffin processing. Refiners also find this feed
the least attractive for fuel oil or diesel fuel because of its high pour or freeze points.
Extracting the normal paraffins reduces the freeze point considerably, thus making the iso-
mer product more salable. Impurities such as the amount of sulfur must also be considered.
Normal paraffin specifications as required by the selected fermentation process are also
important. The hydrocarbon range, normal paraffin content, and types of impurities bear
directly on whether prefractionation of the feedstock before normal paraffin extraction or
postfractionation after extraction is required and on whether and to what degree some form
of posttreatment is required to remove trace sulfur and aromatic compounds. The IsoSiv
process produces normal paraffins at 98.5 wt % purity.
Plant size is important because large plants tend to be more economical. For normal
paraffin extraction, plants producing less than 100,000 MTA (220,000 lb/yr) are consid-
ered to be relatively small from an economic point of view. However, plants with capaci-
ties larger than 500,000 MTA (1,102,000 lb/yr) offer little economic incentive. Location is
also important.
All these economic considerations, plus an uncertain and rapidly changing economic
climate, make estimates of capital investment and operating costs for extracting normal
paraffins extremely tenuous. However, the estimated erected cost of a kerosene IsoSiv unit
for the recovery of 100,000 MTA (220 million lb/yr) of normal paraffins is about $30 mil-
lion.
In summary, commercially proven large-scale production technology is available for
the economic production of high-quality normal paraffins in the kerosene range. The util-
ity requirements for such a unit per metric ton of product are as follows:

Electric power, kWh 79.5

Hot oil heat, 103 J/h (Btu/h) 205 (195)
Cooling water circulated [15°C (27°F) rise], m3 (gal) 8.3 (293)

BIBLIOGRAPHY

LaPlante, L. J., and M. F. Symoniak: “Here’s One Way of Economically Producing Long-Chain
Paraffins,” NPRA Meeting, San Antonio, Tex., 1970.
Reber, R. A., and M. F. Symoniak: “IsoSiv: A Separation Process to Product n-Paraffins for Single
Cell Protein,” American Chemical Society meeting, Philadelphia, April 1975.

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