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Isomerization is an intermediate, feed preparation-type of process.

Two isomerization processes are of interest. For some time, the iso-
merization of normal butane to isobutane has been practiced as a
means of supplementing that normally available to the refiner from
refinery gases or field butanes. Isobutane is an essential ingredient
in alkylation and is chronically short in most refineries, limiting
alkylate output. Recently a demand has developed for isobutylene
for the production of methyl tertiary butyl ether (MTBE). Iso-
butylene can be produced from isobutane by dehydrogenation.
Hence, the butane isomerization unit can be a supplier directly to
alkylation and/or indirectly to MTBE.
The other kind of isomerization is for the conversion of C5 and
C6 normal paraffins into branched-chain hydrocarbons with much
higher octanes.

Butane Isomerization
This is stuctural isomerization, wherein the carbon skeleton of
the molecule is rearranged with no change in the molecular formula:

n–butane isobutane


This is an equilibrium reaction. The composition of the equilibrium

mixture is a function of temperature, with lower temperature favoring
isobutane as shown in Figure 18–1, which was calculated from data in
Chemetron's Physical and Thermodynamic Properties of Elements and

Fig. 18–1 Isobutane/Normal Butane Equilibrium

The rate at which equilibrium is attained is also determined by the

temperature, the rate increasing with temperature. Therefore, the tempera-
ture at which the process operates is a compromise that gives a satisfactory
conversion to isobutane at a reasonable rate.

Butane isomerization process description

While the actual isomerization unit itself is quite simple (Fig. 18–2),
there are several ways it can be integrated into a refinery. A deisobutanizer
tower (DIB) may be included in the scheme. The relative position of the
DIB depends on the concentration of isobutane in the feed. If the concen-


Fig. 18–2 Hot Butamer Flow Scheme (© UOP; reprinted with persmission)

tration is 30% or more,2 it is advantageous to charge both fresh feed and

recycle to the DIB. Then by taking a sidecut below the feed zone, a higher
concentration of normal butane is available to feed the reactor.
If the DIB in the alkylation unit is not loaded, fresh feed could be sent to
this tower, saving the expense of another DIB in case the isomerization unit
is an add–on. A new refinery could be designed with a single, common DIB.
The usual catalyst is a platinum–bearing alumina–chloride type that
must be protected from water, sulfur, and fluorides. Leaving the dryer, the
feed is joined by a recycle gas stream to which hydrogen has been added to
minimize deposition of coke on the catalyst. This combined stream is heat-
ed to reaction temperature and passed through a fixed catalyst bed to a sep-
arator. Separator gas is recycled. Separator liquid is stabilized to remove
small quantities of light hydrocarbons resulting from side reactions. Since
an organic chloride is introduced with the feed to replace the chloride
removed from the catalyst as HCl, stabilizer light ends are scrubbed with
caustic before going into the fuel system.

Butane isomerization yields

The volumetric yield of isobutane formed will be greater than the vol-
ume of butane converted due to the high selectivity of the catalyst and the


specific gravity ratio of normal to iso of 1.038. With a reasonable DIB

design, at least 95% of the isobutane can be recovered in an overhead
stream containing at least 95% isobutane.

Butane isomerization operating requirements

For the isomerization unit alone, the requirements per barrel of feed are
approximately 1 kWh of electric power, 12,000 Btu of fuel and 36 pounds
of steam. With a DIB included, the total requirements become 3.5 kWh and
420,000 Btu with a fired reboiler on the DIB.

Butane isomerization capital cost

From the limited data found in the literature, it appears that a 10,000
BPD butane isomerization unit at the first of 1991 would have cost about
$5 million. The addition of a DIB tower to the unit would have brought the
cost to almost $20 million.

C5 /C6 Isomerization
As stated previously, the purpose of C5/C6 isomerization is to produce a
material with a significantly higher octane. Interest in C5/C6 isomerization
languished until it became apparent that lead was going to be phased out of
gasoline. This is because pentanes and hexanes have a high octane response
to TEL (high lead susceptibility). An appreciation of the interest in con-
verting normal paraffins to branched paraffins can be gained by examining
the following tabulation:

Component RON MON BP, ºF

Isopentane 93.5 89.5 82.14
Normal pentane 61.7 61.3 96.93
Cyclopentane 101.3 85.0 120.68
2, 2 DMB 93.0 93.5 121.54
2, 3 DMB 104.0 94.3 136.38
2 MP 73.4 72.9 140.49


Component RON MON BP, ºF

3 MP 74.5 74.0 145.91
Normal hexane 30.0 25.0 155.74
MCP 95.0 80.0 161.27
Cyclohexane 83.0 77.2 177.33
Benzene >100 >100 176.18

From the boiling points, it can be seen that most of the isopentane in a
feed could be removed ahead of the reactor in a deisopentanizer (DIP)
tower. Also, a split could be made between the two DMBs and 2 MP in a
deisohexanizer (DIH) tower. This would allow the MPs and normal hexane
to be recycled. A C5/C6 splitter could be inserted between the reactor and
the DIH to permit recycling C5’s back to the DIP. Another option would be
to send the reactor effluent to a molecular sieve to separate normal pentane
and normal hexane for recycle.
The stepwise addition of these towers into a complex could result in
increased production of isomerate with the same reactor.

C5 /C6 isomerization process description

The basic process is essentially the same as the butane isomerization
process. However, because of the large number of compounds involved,
there are a number of arrangements that might be employed as described
above. Figure 18–3 is an example of a once–through operation. Typical
results for the various process schemes are:

Case Arrangement RON Relative Capital Cost

I Once–through 83 1.0
II I plus DIP 84 1.2

Case Arrangement RON Relative Capital Cost

III II plus C5 /C6 Splitter 86.4 1.54
IV I plus Molecular Sieve 89 1.93
V III plus DIH 92.5 2.34


Fig. 18–3 UOP Hot Penex Process (© UOP; reprinted with persmission)

Figure 18–4 is a plot of the above data resulting from an earlier study
(1978) by the author for these five cases. It is thought that the same gener-
al relationships hold today.

C5 /C6 isomerization operating requirements

The operating requirements will, of course, vary with the scheme under
consideration. For the once–through situation:

1 kWh/b electric power, 10,000 Btu/b fuel, 36 lb/b steam

C5 /C6 isomerization capital cost

For a 10,000 BPD unit at the first of 1991, use $7 million for a
once–through unit (Type I); $17 million for a Type IV unit.


Fig. 18–4 Isomerization Cost vs. Octane

1. Anon., Physical and Thermodynamic Properties of Elements and
Compounds, Chemetron Corporation, Louisville, 1969

2. Rosati, D., Handbook of Petroleum Processes, R.A. Meyers, Ed.,

McGraw–Hill Book Company, New York, 1986, pp. 5–40 to 5–46

Anon., Hydrocarbon Processing, April, 1984, p. 111

Ibid., April, 1990, p. 73

Bour, G., Schwoerer, C.P., and Asselin, G.F., Oil & Gas Journal,
October 26, 1970, pp. 57–65


Chopey, N.P., Chemical Engineering, May 31, 1971, pp. 24–26

Cusher, N.A., in Meyer's Handbook of Petroleum Refining Processes,

pp. 5–3 to 5–13, and 5–15 to 5–24

Ewing, R.C., Oil & Gas Journal, August 16, 1971, pp. 61–66

Greenough, P., and Rolfe, J.R.K., in Meyer's Handbook of Petroleum

Refining Processes, pp. 5–25 to 5–37

Greenough, P., and Rolfe, J.R.K., Handbook of Petroleum Processes,

Ed. R.A. Meyers, McGraw–Hill Book Company, New York,
1986, pp. 5–25 to 5–37

Raghuram, S., Haizmann, R.S., Lowry, D.R., and Schiferli, W.J., Oil
& Gas Journal, December 3, 1990, pp. 66–69

Schmidt, R.J., Weiszmann, J.A., and Johnson, J.A., Oil & Gas
Journal, May 27, 1985, pp. 80–88

Symoniak, M.F., and Holcombe, T.C., Hydrocarbon Processing, May,

1983, pp. 62–64

Ware, K.J., and Richardson, Hydrocarbon Processing, November,

1972, pp. 161–162

Weiszmann, J.A., in Meyer's Handbook of Petroleum Refining

Processes, pp. 5–47 to 5–59