Catalytic Polymerisation

CHAPTER 20
CATALYTIC
POLYMERIZATION
The technology to be discussed here is the catalyzed reaction of

propylene and/or butylenes to produce gasoline- and/or distillate-
boiling-range materials. This became of interest to the refiner as a
means of utilizing the olefins resulting from thermal cracking to
produce more gasoline. Later, it was supplanted largely by the
charging of these olefins to alkylation. The cat cracker is the
primary source of olefins today. A second source is the byproduct
C4 stream from the thermal crackers producing ethylene (and
propylene) as primary product for polymerization into much larger
polymer molecules. The quantities available from this source are
much more variable than those from the cat cracker.
The polymerization of butylenes for the above purposes is
highly unlikely because of increasing demand for isobutylene for
the production of MTBE and the increasing value of alkylate in
future gasolines.
Though there has been much interest shown in dimerization of
propylene to blend into gasoline, the future of this outlet is very
uncertain. An examination of the following tabulation can be
instructive in this regard:
Dimer as produced after saturation

Bromine No. 131 1.3
RON 94.5 63.7
299
PETROLEUM REFINERY P ROCESS ECONOMICS
Dimer as produced after saturation

MON 80.9 70.6
Average Octane 87.7 67.3
The dimer as produced is still an olefin as shown by the high bromine

number and high sensitivity (RON–MON). On saturation, the bromine
number drops dramatically, but so does the octane. With pressure on reduc-
tion of olefins in gasoline, the future for poly gas doesn't look bright.
Isobutylene can be selectively converted to dimer and trimer in the pres-
ence of other butanes.1 These polymers can be hydrogenated to saturation
without loss of RON, but with dramatic increase in MON making the prod-
uct more or less equivalent to butylene alkylate. However, it is doubtful that
units will be constructed for this purpose in the face of competition for
isobutylene in existing alkylation units, and present and future MTBE units.
This technology can be, and has been, used to produce intermediates
for the manufacture of synthetic detergents, alcohols, plasticizers, etc.
A lingering interest in this technology is for the production of distil-
late–boiling–range material. It has been demonstrated that propylene poly-
mer (specifically the tetramer) has a better cetane number (20–21) than
does the polymer from butylenes with similar boiling range. On hydro-
genation, the cetane is 34–35. This material is still an inferior diesel, but
could be blended into premium diesel fuel to some extent. In fact, one oper-
ator has 60 cetane number material into which he can blend 35% of the
polymer and still produce a 45 minimum cetane diesel.2
Perhaps a more interesting use, is as a premium jet fuel blending stock
as shown by the following tabulation:3
Untreated Specification
Polymer Hydrogenated Polymer
Bromine No. — 77.9 0.019
Smoke Point, mm 42 — 25 minimum
Freeze Point, ˚C -70 -68 -40 max
A study of these possibilities (jet fuel from LPG) was made for a client
with very special circumstances. It involved the production of the olefin
300
CHAPTER 20 • CATALYTIC POLYMERIZATION
from paraffin by dehydrogenation. Even in the face of this very expensive

requirement, the scheme proved attractive. Where the olefin (preferably
propylene) is already a commodity (as in the U.S.), this technology should
be considered.
Catalytic polymerization process description

Two processes will be described. The older process (still practiced
today in modified form) uses a solid phosphoric acid catalyst on silica. The
feed to the process needs to be treated to remove basic nitrogen and sulfur.
The first is a poison to the catalyst and the second is not desired in the prod-
ucts. Moisture content needs to be controlled as well.
The treated feed is combined with recycle, exchanges heat with reactor
effluent, and enters the reactor. Early reactors usually consisted of tubes
filled with catalyst and surrounded by a boiling water bath to absorb the
heat of reaction and maintain the desired temperature in the reactor. In a
flash drum, recycle is separated from the polymer that is stabilized to
remove remaining C3 and C4 hydrocarbons. The polymer is then separated
by fractionation into the different products with dimer and trimer going to
gasoline if desired or recycled to increase production of heavier materials,
such as the tetramer and pentamer.
Reactors today are more likely to have the catalyst disposed in hori-
zontal beds in a vertical vessel with the temperature controlled by the intro-
duction of propane and/or butane between the beds as a quench. Figure
20–1 illustrates this scheme.
The other process uses a homogeneous catalyst system that is more or
less miscible with the hydrocarbon phase. The catalyst complex includes an
aluminum–alkyl and a nickel coordination complex. According to Andrews
and Bonnifay,4 “The reaction rate for propylene dimerization is high enough
to obtain conversion rates above 90% in a single reaction.” The catalyst is
injected continuously in very low concentrations into the reactor. The cata-
lyst is separated from the reaction product(s) by the addition of ammonia
into the stream followed by a water wash. From the separator, the aqueous
phase goes to waste water treatment and the hydrocarbon phase is stabi-
lized and fractionated into LPG and dimer as shown in Figure 20–2.
301
Fig. 20–1 Typical Catalytic Condensation Unit Flow (© UOP; reprinted with permission)
Fig. 20–2 IFP Dimersol for Hexenes
302
Catalytic polymerization yield correlations

No correlations were made in this area, since the results are very
straightforward for the several processes and product objectives as illus-
trated in the following tabulations:
5 6 7
Reference
Olefin in Feed, wt % 78 59 71.6
Products, Wt%
LPG 22 41.3 32
Gasoline 10 10.5 68
Distillate 67.5 47.0 ––
Heavy Polymer 0.5 1.2 ––
Product Properties Gaso Dist Gaso Dist Gaso

API 58 52.2 65 49.9 73.5
RVP — — 3 — 6.5
RON — 94.5 94 97 —
MON — 80.9 82 82 —
Cetane No. — — — — 18
Freeze Point, ˚C — -70 — — —
Catalytic polymerization operating requirements

The requirements tabulated below are representative of these opera-
tions:
Phosphoric Homogeneous
Acid Catalyst Catalyst
Operation Gasoline Distillate Gasoline
Electric, kWh/b 1.5 8 2
Fuel, kBtu/b –– 250 ––
Steam, lb/b 250 350 60
CW, gal/b –– –– 20
303
Catalytic polymerization capital cost

Based on the meager data in the literature, the capital cost of a unit pro-
ducing 3,000 BPD of product at the start of 1991 would be about as
follows:
Homogeneous catalyst process $3.6 million

Phosphoric acid process
Gasoline production $14 million
Distillate production $33.5 million
However, it is doubtful that units will be constructed for this purpose in the
face of competition for olefin in existing alkylation units and present and
future MTBE units.
Notes
1. Scharfe, G., Hydrocarbon Processing, April, 1973, pp. 171–173
2. Maples R.E., and Jones, J.R., Chemical Engineering Progress,

February, 1983, pp. 55–59
3. Anon., “Chevron Bulk Acid Polymerization Process,” Chevron

Research Company, San Francisco, 1972
4. Andrews, J.W., and Bonnifay, P.L., “The IFP Dimersol Process

for Dimerization and Codimerization,” 1973 NPRA Annual
Meeting, San Antonio
5. Swart, J.S., Czajkowski, G.J., and Conser, R.E., Oil & Gas
Journal, August 31, 1981, p. 86
6. Tajbl, D.G., in Meyer's Handbook of Petroleum Refining

Processes, McGraw–Hill Book Company, New York, 1986, pp.
1–43 to 1–53
7. Benedek, W.J., and Mauleon, J.L., Hydrocarbon Processing, May,

1990, pp. 143–149
304
References
Andrews, J.W., and Bonnifay, P.L., Hydrocarbon Processing, April,
1977
Chauvin, Y., Gaillard, J., Leonard, J, Bonnifay, P., and Andrews, J.W.,
“New Processing Techniques as an Outgrowth of IFP Dimersol
Technology,” 1982 NPRA Annual Meeting, San Antonio
Kohn, P.M., Chemical Engineering, May 23, 1977, pp. 114–116
Weismantel, G.E., Chemical Engineering, June 16, 1980, pp. 77–80
305

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CHAPTER 20

The technology to be discussed here is the catalyzed reaction of

Dimer as produced after saturation

Dimer as produced after saturation

The dimer as produced is still an olefin as shown by the high bromine

from paraffin by dehydrogenation. Even in the face of this very expensive

Catalytic polymerization process description

Fig. 20–2 IFP Dimersol for Hexenes

Catalytic polymerization yield correlations

Product Properties Gaso Dist Gaso Dist Gaso

Catalytic polymerization operating requirements

Catalytic polymerization capital cost

Homogeneous catalyst process $3.6 million

2. Maples R.E., and Jones, J.R., Chemical Engineering Progress,

3. Anon., “Chevron Bulk Acid Polymerization Process,” Chevron

4. Andrews, J.W., and Bonnifay, P.L., “The IFP Dimersol Process

6. Tajbl, D.G., in Meyer's Handbook of Petroleum Refining

7. Benedek, W.J., and Mauleon, J.L., Hydrocarbon Processing, May,

Kohn, P.M., Chemical Engineering, May 23, 1977, pp. 114–116

Weismantel, G.E., Chemical Engineering, June 16, 1980, pp. 77–80

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