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 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
Oxygen Removal quantity and quality of feedstock the unit is de-
signed to process. While minor changes in feed
Phenols 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
This involves the liberation of oxygen molecule as faster rate of coke formation which will reduce the
water (steam). period between regenerations. A reduced feed rate
may lead to bad flow distributions through the cata-
Olefin Saturation lyst, so that higher temperatures will be required to
Linear Olefin obtain good product quality. In order to minimize
(and Isomers) the effect of variations in charge ratio, it should be
made a common practice to reduce the reactor tem-
Cycle Olefins 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-
The Olefins or alkenes (double bonds) are satu- sition is also decelerated by the fact that a heavier
rated. feed contains more of the precursors that favors coke
formation. In addition to the above, high boiling
The reactor effluent, after exchanging heat with fractions also contain increased quantities of metals
the incoming feed is separated of the hydrogen which lead not only to higher reactor pressure drop,
rich recycle gas. The hydrogen rich free reactor but to rapid catalyst deactivation as well. It must be
effluent is routed to the stripper where light ends remembered that regeneration will not restore the
and sour water leave over head at about 45 degree activity of a catalyst that has been poisoned by exces-
Celsius and 3.5 kg/cm2 to the over head condenser, sive quantities of metals.
while the desulphurised naphtha is withdrawn Thus, it is seen that processing higher than design
from the stripper bottoms at about 120 degree end point feeds will at best reduce the length of the
Celsius and 15 kg/cm2. operating cycle, and under extreme conditions, may
lead to an irrevocable loss of catalyst activity. There-
Operating Variables fore, every effort must be made to maintain the end
Proper operation of the naphtha hydro treating point of the feed within the design limits. Storage
unit will depend on the judicious selection and con- 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- The hydrogen partial pressure required for the
mize the formation of coke producing materials. A operation of the unit is based on the degree of sul-
reduction in the API gravity of the feed for the same phur and nitrogen removal that must be achieved,
boiling range is an indication of higher unsaturates and is an economic optimum that balances initial
content. This type of feed will result in increased investment and operating costs against catalyst life.
hydrogen consumption and higher temperature The operating pressure (ie. the high pressure separa-
rises across the catalyst bed. It also contains more of tor pressure) must be held constant at the design
the materials that easily condense to form coke in value; in fact, while higher then design operating
the reactor and associated equipment. pressure favor catalyst life and may result in some-
what better catalyst activity, such operation would
2. Reactor Temperature be detrimental since the equipment (heaters, reac-
The reactor inlet temperature is controlled in or- tors, exchangers, compressors, safety values, etc)
der to adjust the amount of sulphur removed from have been designed based on a fixed separator pres-
the feed. The reactor outlet temperature is a func- sure. An increase in the separator pressure will lead
tion of the feed quality and cannot be easily varied, to accelerated wear on the equipment, and in ex-
except by changing the reactor inlet temperature. treme case could result in costly and dangerous
The inlet temperature must always be controlled at equipment failovers. A reduction of the operating
the minimum required to achieve the desired sul- pressure below the design level will have a negative
phur and/or nitrogen removal. Temperatures above effect on the activity of the catalyst and will acceler-
this minimum will only lead to higher rates of coke ate catalyst deactivation due to coke formation.
formation, reduced processing periods, and ex-
cessive fuel consumption. During the course of an 4. Hydrogen to Hydrocarbon Ratio
operating cycle the temperature required to obtain The H2/Hc rate is an important variable in the
the desired product quality will increase as a result of satisfactory performance of the unit, which should
catalyst deactivation. The gradual loss in catalyst not be operated at less than design since rapid cata-
activity can be compensated for by increasing re- lyst deactivation will result.
actor temperature up to a limited about 400 c
maximum bed temperature, above which coke for- Then H2/Hc ratio is calculated as follows:
mation becomes very rapid and little improve-
ment in performance is obtained. Note that this H2/Hc = (Total gas at standard conditions per unit time
temperature is the highest temperature in the cata- To reactors x H2 purity) / Raw oil charge per unit time
lyst bed and is not necessarily the outlet tempera-
ture of heater or reactor. The temperature rise As the amount of gas that can be circulated is a
across the reactors must be monitored continu- function of the compression ratio, a gradual reduc-
ously in order to ensure that the design limitations tion in recycle gas rate will be observed during the
of the unit are not exceeded. This can be especially course of an operating period as a result of higher
important when changing feed stock since olefin reactor system pressure drop. Such a reduction in the
saturation results in reactions generating consid- recycle gas rate is acceptable as long as the calculated
erably higher levels of heat. H2/Hc ratio does not fall below the design value.
When it is no longer possible to maintain the mini-
3. Reactor Pressure mum hydrocarbon ratio, the catalyst must be regen-
The reactor section operating pressure is control- erated and screened in order to reduce the reactor
led by the pressure maintained at the high pressure pressure drop. In all cases that result in less than
separator. This pressure, multiplied by the hydrogen design H2/Hc ratio, due to pressure drop or me-
purity of the recycle gas, determines the partial pres- chanical difficulties, the raw oil charge rate must be
sure of hydrogen in the reactor. lowered in order to obtain the required H2/Hc ratio.

H2 PARTIAL PRESSURE = TOTAL REACTOR 5. Recycle Gas Purity

PRESSURE * H2 PURITY The effective completion of the hydrogenation

Performance
Optimization 36 HYDROCARBON ASIA, OCT-DEC 2009 Visit our website at: http://www.safan.com
reactions occurring over the catalyst requires that be well understood and controlled within accept-
a certain quantity of hydrogen be present at a able limits. HA Enquiry Number 10/12-01
minimum partial pressure. As noted previously,
both the quantity (H2/Hc) and partial pressure are This publication thanks Mr. Nwaoha Chikezie
dependent upon the hydrogen content, i.e. purity for providing this paper, which was first pub-
of the recycle gas. Partial considerations such as lished in the May 2009 issue of Flow Control
the cost of compression, catalyst life, etc, limit the Magazine. He possesses a Bachelor’s Degree in
purity of the recycle gas to a minimum value Petroleum Engineering from the Federal Univer-
usually in the range of 70-80 mol%. sity of Technology, Owerri, Nigeria. He has com-
Lower hydrogen purities are detrimental to the pleted a term as an operator (student trainee)
performance of the unit since higher temperatures with Port Harcourt Refining Company in Ni-
must be used to achieve the desired product qual- geria, and is currently working on several re-
ity. The light hydrocarbons present in the recycle search projects involving flow systems design,
gas enter the system with the make-up gas in addi- including an initiative with the Caribbean Afri-
tion to these being formed in the reactor, and must can Student Exchange Initiative (CASEI). As part
be vented from the high pressure separator to pre- of his research, Mr. Chikezie Nwaoha has
vent their accumulation in the recycle gas. The H2S authored a number of engineering articles in
formed in the reactors can reach equilibrium values leading international journals. Mr. Chikezie
higher than 5 mol% in the recycle gas. Nwaoha is a member of SPE, ASME, AIChe,
This concentration of H2S has a depressing effect IMechE, ICE, IGEM and Nigerian Gas Associa-
on the activity of the catalyst, and on the equilibrium: 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