SECTION D:

LIGHT DISTILLATE
PROCESSING
 CHAPTER 16

NAPHTHA DESULFURIZATION

Naphtha hydrotreating is generally practiced to prepare feedstock

for a catalytic reformer and many refiners treat the two processes
as one unit.
All the stocks normally reformed except hydrocrackate con-
tain sulfur, which is a poison to the noble metals present in
reformer catalysts. The primary purpose of hydrotreating these
naphthas is to reduce the sulfur content to a tolerable level.
An appreciation of the task facing the hydrotreater can be
gained by reviewing data presented by J. T. Pistorius of American
Cyanamid Co.:1

Maximum acceptable contaminant

levels for reformer feeds:
Sulfur 1 wt ppm
Nitrogen 0.5 wt ppm
Lead 10 wt ppb
Arsenic 2 wt ppb
Water 10 wt ppm
Chloride 1 wt ppm

Sulfur is readily removed from naphthas. Naphthas from some

crudes will require more severe treatment to meet the nitrogen
requirement. Where metals are expected to be a problem, one

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licensor advises the addition of an amount of sacrificial catalyst as a trap.

Certain crudes contain sufficient levels of arsenic, for example, to require
some such precaution.

Naphtha hydrotreater process description

The naphtha hydrotreater is essentially the same as the hydrotreater
described in the previous chapter. It consists of a feed heater, a reactor,
high– and low–pressure separators, a recycle compressor, and a treated
naphtha splitter. In addition, when a highly unsaturated stock such as coker
naphtha is being fed, a separate additional reactor may precede the main
reactor (Fig. 16–1). This is to selectively saturate (under milder conditions
than those in the main reactor) acetylenes and dienes in order to prevent
runaway temperature increases due to the highly exothermic reactions
when they are present.

Fig. 16–1 Naphtha Hydrotreater

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 CHAPTER 16 • NAPHTHA DESULFURIZATION

A hydrogen sulfide stripper is sometimes placed between the separa-

tors. If naphtha is being received from storage where there is no inert gas
blanket, a reboiled stripper would be needed ahead of the heater to remove
oxygen.

Naphtha hydrotreating correlations

Table 16–1 is a tabulation of data on naphtha hydrotreating assembled
from the literature references listed. The data were segregated by type of
stock for individual study. As in the case of hydrotreating the heavy distil-
lates, some of the stocks did not correlate well (at least within the data pop-
ulations at hand). In the case of hydrogen required, coker naphtha showed
a decreasing hydrogen requirement as the sulfur content of the feed

Table 16–1a Naphtha Hydrodesulfurization Database

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Table 16–1b Naphtha Hydrodesulfurization Database cont’d

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 CHAPTER 16 • NAPHTHA DESULFURIZATION

increased. In the case of the increase in API gravity of naphtha resulting

from hydrotreating, it was the catalytic cracked naphtha that did not give a
satisfactory correlation.
Good results were obtained when data for all the naphthas were com-
bined. It was necessary to disregard some obvious “outliers” in the process.
The results are shown in Table 16–2 and Figures 16–2 and 16–3. The API
is needed only to permit weight balance(s) around the hydrotreater and/or
the reformer. The hydrogen requirement is needed in making a hydrogen
balance, with due allowance for solution losses, etc.
One matter that is of importance to the reformer is the composition of
the feed with respect to hydrocarbon types. This does change in the course
of hydrotreating, notably in the case of the cracked materials.
Consequently, Table 16–3 was prepared to illustrate some of these changes
and give the reader some guidance. As we shall see, the yield of reformate
is strongly dependent on the PONA analysis of the reformer feed.

Table 16–2 Some Results of Naphtha Hydrotreating Correlations

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PETROLEUM REFINERY P ROCESS ECONOMICS

Fig. 16–2 Hydrogen Required in Naphtha Desulfurization

Fig. 16–3 API Increase in Naphtha Hydrotreating (API Gravity of Feed as Parameter)

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 CHAPTER 16 • NAPHTHA DESULFURIZATION

Table 16–3 Effect of Hydrotreating on Naphtha Properties

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PETROLEUM REFINERY P ROCESS ECONOMICS

As we would expect, the properties shown in Table 16–3 for straight

run naphthas are little affected by hydrodesulfurization. We see some slight
increases in API gravity and octane, but little change in PONAs. A very dif-
ferent picture is seen for thermal naphthas. The API increases are still small,
but the decrease in octane is very dramatic. This is due to saturation of
olefins that generally have higher octane than the corresponding paraffin.
The value shown as olefin includes cyclic olefins as well as alkenes. So we
see an increase in naphthenes as well as paraffins. These same generaliza-
tions apply to the other cracked stocks.
Some of the PONAs are denoted as Ave. and can be used as represen-
tative where specific data are lacking. Data are included for heavy hydroc-
rackates. Even though they would not go through the hydrotreater, they are
generally reformed to increase their octane.

Naphtha hydrotreating operating requirements

Operating requirements for naphtha hydrotreating are modest and con-
sist of approximately the following:

Electric power, kW/b 2

Fuel, kBtu/b 30
Steam, #/b 15

Naphtha hydrotreating capital cost

An average cost of $16 million was estimated for a 30,000 BPD plant
at the beginning of 1991.

Notes
1. Pistorius, J.T., Oil & Gas Journal, June 10, 1985, pp. 146–151

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