Increasing Hydro

Treated Naphtha Yield

via Variable Changes
Conventionally, in refineries, hydro treated naphtha is recovered as a product
of naphtha hydro treating unit (NHU); its feed, straight-run naphtha (SRN),
is routed from the atmospheric crude distillation tower. As demand and
severity to produce cleaner hydro treated naphtha increases, refiners must
adjust and optimize their process variables in other to meet these demands.
Optimizing naphtha hydro treating plants requires the evaluation of several
key process variables that affect unit capabilities. Process engineers and
technologists must identify those variables in other to improve final results.

T
he purpose of Naphtha hydro treating is to actor, where all the chemical reactions take place.
hydro de-sulphurize straight-run naphtha The reactions are related to sulphur, nitrogen, oxy-
from the splitter bottom to produce a suitable gen, and metals removal, and to olefin saturation.
feed stock for the catalytic reforming for a
high octane gasoline blend. This is obtained by Sulphur removal/Hydro desulphurization
catalytically treating the naphtha with hydrogen Mercaptan
supplied by the reforming unit. This reaction is car- C-Sulphide
ried out at high temperature and moderate pressure.
SRN enters the hydro treating unit at about 38 de- Disulphide
T gree Celsius and
13kg/cm 2, and Thiophere
E is preheated to-
gether with the
C hydrogen rich
recycle gas in the NITROGEN REMOVAL
H combined feed
PYRIDINE
N heat exchanger.
And then routed
O to the feed
h e ater where it
L is heated up to
QUINOLINE
the reaction tem-
O perature.
The heated
G feed is routed to
Y the naphtha hy-
dro treating re- Fig. 1 Naphtha Hydro Treating Plant

Performance
Optimization 34 HYDROCARBON ASIA, OCT-DEC 2009 Visit our website at: http://www.safan.com
PYRROLE
Oxygen Removal
Phenols
This involves the liberation of oxygen molecule as
water (steam).
Olefin Saturation
Linear Olefin
(and Isomers)
Cycle Olefins
The Olefins or alkenes (double bonds) are satu-
rated.
The reactor effluent, after exchanging heat with
the incoming feed is separated of the hydrogen
rich recycle gas. The hydrogen rich free reactor
effluent is routed to the stripper where light ends
and sour water leave over head at about 45 degree
Celsius and 3.5 kg/cm2 to the over head condenser,
while the desulphurised naphtha is withdrawn
from the stripper bottoms at about 120 degree
Celsius and 15 kg/cm2.
Operating Variables
Proper operation of the naphtha hydro treating
unit will depend on the judicious selection and con-
trol of the operating variables. The key ones are: feed
quality, reactor temperature, reactor pressure, hy-
drogen to hydrocarbon ratio, and recycle gas purity.
1. Feed Quality
The amount of catalyst loaded into the reactor, as
well as other design parameters are based on the
quantity and quality of feedstock the unit is de-
signed to process. While minor changes in feed
type and charge rate can be tolerated, wide varia-
tions should be avoided since they will tend to
reduce the useful life of the catalyst.
An increase in the charge rate will require
higher reactor temperature to achieve constant
desulphurization, as well as higher recycle gas
rate, to maintain a constant ratio of hydrogen
to hydrocarbons.
Increased reactor temperatures will also lead to a
faster rate of coke formation which will reduce the
period between regenerations. A reduced feed rate
may lead to bad flow distributions through the cata-
lyst, so that higher temperatures will be required to
obtain good product quality. In order to minimize
the effect of variations in charge ratio, it should be
made a common practice to reduce the reactor tem-
perature before lowering the feed rate, and con-
versely, to increase the feed rate before raising the
reactor temperature. The type of feed being proc-
essed is best indicated by its distillation range and
API gravity. An increase in the end point of the feed
will make sulphur and nitrogen removal more diffi-
cult, thus requiring higher reactor temperatures
which, in turn accelerates coke formation. Coke depo-
sition is also decelerated by the fact that a heavier
feed contains more of the precursors that favors coke
formation. In addition to the above, high boiling
fractions also contain increased quantities of metals
which lead not only to higher reactor pressure drop,
but to rapid catalyst deactivation as well. It must be
remembered that regeneration will not restore the
activity of a catalyst that has been poisoned by exces-
sive quantities of metals.
Thus, it is seen that processing higher than design
end point feeds will at best reduce the length of the
operating cycle, and under extreme conditions, may
lead to an irrevocable loss of catalyst activity. There-
fore, every effort must be made to maintain the end
point of the feed within the design limits. Storage
tanks used for the accumulation of feed to the unit
HYDROCARBON ASIA, OCT-DEC 2009 35
 should be gas (nitrogen) blanketed in order to mini-
mize the formation of coke producing materials. A
reduction in the API gravity of the feed for the same
boiling range is an indication of higher unsaturates
content. This type of feed will result in increased
hydrogen consumption and higher temperature
rises across the catalyst bed. It also contains more of
the materials that easily condense to form coke in
the reactor and associated equipment.
2. Reactor Temperature
The reactor inlet temperature is controlled in or-
der to adjust the amount of sulphur removed from
the feed. The reactor outlet temperature is a func-
tion of the feed quality and cannot be easily varied,
except by changing the reactor inlet temperature.
The inlet temperature must always be controlled at
the minimum required to achieve the desired sul-
phur and/or nitrogen removal. Temperatures above
this minimum will only lead to higher rates of coke
formation, reduced processing periods, and ex-
cessive fuel consumption. During the course of an
operating cycle the temperature required to obtain
the desired product quality will increase as a result of
catalyst deactivation. The gradual loss in catalyst
activity can be compensated for by increasing re-
actor temperature up to a limited about 400 c
maximum bed temperature, above which coke for-
mation becomes very rapid and little improve-
ment in performance is obtained. Note that this
temperature is the highest temperature in the cata-
lyst bed and is not necessarily the outlet tempera-
ture of heater or reactor. The temperature rise
across the reactors must be monitored continu-
ously in order to ensure that the design limitations
of the unit are not exceeded. This can be especially
important when changing feed stock since olefin
saturation results in reactions generating consid-
erably higher levels of heat.
3. Reactor Pressure
The reactor section operating pressure is control-
led by the pressure maintained at the high pressure
separator. This pressure, multiplied by the hydrogen
purity of the recycle gas, determines the partial pres-
sure of hydrogen in the reactor.
H2 PARTIAL PRESSURE = TOTAL REACTOR
PRESSURE * H2 PURITY
Performance
Optimization 36 HYDROCARBON ASIA, OCT-DEC 2009
The hydrogen partial pressure required for the
operation of the unit is based on the degree of sul-
phur and nitrogen removal that must be achieved,
and is an economic optimum that balances initial
investment and operating costs against catalyst life.
The operating pressure (ie. the high pressure separa-
tor pressure) must be held constant at the design
value; in fact, while higher then design operating
pressure favor catalyst life and may result in some-
what better catalyst activity, such operation would
be detrimental since the equipment (heaters, reac-
tors, exchangers, compressors, safety values, etc)
have been designed based on a fixed separator pres-
sure. An increase in the separator pressure will lead
to accelerated wear on the equipment, and in ex-
treme case could result in costly and dangerous
equipment failovers. A reduction of the operating
pressure below the design level will have a negative
effect on the activity of the catalyst and will acceler-
ate catalyst deactivation due to coke formation.
4. Hydrogen to Hydrocarbon Ratio
The H2/Hc rate is an important variable in the
satisfactory performance of the unit, which should
not be operated at less than design since rapid cata-
lyst deactivation will result.
Then H2/Hc ratio is calculated as follows:
H2/Hc = (Total gas at standard conditions per unit time
To reactors x H2 purity) / Raw oil charge per unit time
As the amount of gas that can be circulated is a
function of the compression ratio, a gradual reduc-
tion in recycle gas rate will be observed during the
course of an operating period as a result of higher
reactor system pressure drop. Such a reduction in the
recycle gas rate is acceptable as long as the calculated
H2/Hc ratio does not fall below the design value.
When it is no longer possible to maintain the mini-
mum hydrocarbon ratio, the catalyst must be regen-
erated and screened in order to reduce the reactor
pressure drop. In all cases that result in less than
design H2/Hc ratio, due to pressure drop or me-
chanical difficulties, the raw oil charge rate must be
lowered in order to obtain the required H2/Hc ratio.
5. Recycle Gas Purity
The effective completion of the hydrogenation
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reactions occurring over the catalyst requires that
a certain quantity of hydrogen be present at a
minimum partial pressure. As noted previously,
both the quantity (H2/Hc) and partial pressure are
dependent upon the hydrogen content, i.e. purity
of the recycle gas. Partial considerations such as
the cost of compression, catalyst life, etc, limit the
purity of the recycle gas to a minimum value
usually in the range of 70-80 mol%.
Lower hydrogen purities are detrimental to the
performance of the unit since higher temperatures
must be used to achieve the desired product qual-
ity. The light hydrocarbons present in the recycle
gas enter the system with the make-up gas in addi-
tion to these being formed in the reactor, and must
be vented from the high pressure separator to pre-
vent their accumulation in the recycle gas. The H2S
formed in the reactors can reach equilibrium values
higher than 5 mol% in the recycle gas.
This concentration of H2S has a depressing effect
on the activity of the catalyst, and on the equilibrium:
be well understood and controlled within accept-
able limits. HA Enquiry Number 10/12-01
This publication thanks Mr. Nwaoha Chikezie
for providing this paper, which was first pub-
lished in the May 2009 issue of Flow Control
Magazine. He possesses a Bachelor’s Degree in
Petroleum Engineering from the Federal Univer-
sity of Technology, Owerri, Nigeria. He has com-
pleted a term as an operator (student trainee)
with Port Harcourt Refining Company in Ni-
geria, and is currently working on several re-
search projects involving flow systems design,
including an initiative with the Caribbean Afri-
can Student Exchange Initiative (CASEI). As part
of his research, Mr. Chikezie Nwaoha has
authored a number of engineering articles in
leading international journals. Mr. Chikezie
Nwaoha is a member of SPE, ASME, AIChe,
IMechE, ICE, IGEM and Nigerian Gas Associa-
tion (NGA).

2R – SH + H2 ¤ 2H2S + 2R H

In some cases it is desirable to remove the H2S from

the recycle gas.
The stripper effluent that is de-sulphurised Naph-
tha is withdrawn from the bottom and split into two
streams through a flow valve and pumped by a
stripper reboiler pump. The first stream is pumped
to the stripper reboiler heater which is recycled
back to the stripper to improve the quality of Naph-
tha. This heater provides the necessary heating for
the stripper.
The second stream is pumped to the stripper
feed/bottoms exchanger for feed (Naphtha)
Preheating. After heating the feed, this second
stream is also spitted again into two streams, the
first (hydro reacted Naphtha) to the plat forming
unit and the second to the stripper net bottoms
cooler, which is cooled by a cooling supply.

Recommendation
Naphtha hydro treating should be run within
the operating conditions and design limits. This
is to improve hydro treated naphtha yield and
avoid side reactions, like coke formation. Thus
factors that affect the process reactions, influence
coke formation and deactivate the catalyst must

HYDROCARBON ASIA, OCT-DEC 2009 37