Producing Naphtha And Kerosene

1. Naphtha
The first unit process in a petroleum refinery is the crude oil distillation unit. The
overhead liquid distillate from that unit is called virgin or straight-run naphtha and that
distillate is the largest source of naphtha in most petroleum refineries. The naphtha is a
mixture of many different hydrocarbon compounds.
Naphtha (/np/ or /nf/) is a flammable liquid hydrocarbon mixture. Mixtures
labelled naphtha have been produced from natural gas condensates, petroleum
distillates, and the distillation of coal tar and peat. In different industries and regions
naptha may also be crude oil or refined products such as kerosene.Hydrotreated Naphtha
is combined with recycled Hydrogen and Catalyst and Heat exchanged against reactor
Effluent. The combined feed is then raised to reaction temperature in the Reformer Fired
Heater and sent to Catalytic Reforming Reactor. The Hydrogen Rich gas is
compressed to Separators to recovery system and Stabilizer Column. Over the
reaction coke is built-up on catalyst. This partially deactivated catalyst is sent to CCR
Regenerator so that by burning the coke re-activate the catalyst. The heat generated is
the effluent heat used for heating of the reactor mix too.
From Destillation process was gotten 2 kind of Naphtha :
1. Light Naphtha
2. Heavy Naphtha

1.1 Light Naphtha

The Light naphtha balances include : light naphtha, natural gasoline, full range (open
spec) naphtha and also heavy paraffinic naphtha that is not suitable feed for catalytic
reforming.
a. Light Naphtha Hydroteater Unit
Hydrotreating processes aim at the removal of impurities such
as sulfur and nitrogen from distillate fuelsnaphtha, kerosene, and
dieselby treating the feed with hydrogen at elevated temperature
and pressure in the presence of a catalyst. Hydrotreating has been
extended in recent years to atmospheric resids to reduce the sulfur and
metal content of resids for producing low-sulfur fuel oils. The operating
conditions of treatment are a function of type of feed and the desulfurization
levels desired in the treated product. The feed types considered
here are :
Naphtha.
Kerosene.
Gas oils.
Atmospheric resids or reduced crudes.

The principal impurities to be removed are

Sulfur.
Nitrogen.
Oxygen.
Olefins.
Metals.
Sulfur
The sulfur-containing compounds are mainly mercaptans, sulfides,disulfides,
polysulfides, and thiophenes. The thiophenes are more difficult to eliminate than most
other types of sulfur.
Nitrogen
The nitrogen compounds inhibit the acidic function of the catalyst considerably.These
are transformed into ammonia by reaction with hydrogen.
Oxygen
The oxygen dissolved or present in the form of compounds such as phenols or
peroxides are eliminated in the form of water after reacting with hydrogen.
Olefins
The olefinic hydrocarbons at high temperature can cause formation of coke deposits
on the catalyst or in the furnaces. These are easily transformed into stable paraffinic
hydrocarbons. Such reactions are highly exothermic. Straight run feeds from the crude
unit usually contain no olefins. If, however, the feed contains a significant amount of
olefins, a liquid quench stream is used in the reactor to control the reactor outlet
temperature within the design operating range.
Metals
The metals contained in the naphtha feed are arsenic, lead, and to a lesser degree
copper and nickel, which damage the reforming catalyst permanently. Vacuum gas oils
and resid feeds can contain a significant amount of vanadium and nickel. During the
hydrotreating process, the compounds that contain these metals are destroyed and the
metals get deposited on the hydrotreating catalyst.
The basic reactions involved are outlined in Figure :
Process Diagram :

Heavy Naphtha cut from the atmospheric crude oil distillation column
in a refinery is sent to a Naphtha Hydrotreating Unit. After the naphtha
hydrotreating unit, naphtha is sent to an isomerisation unit or a catalytic
reformer unit, which often use reforming catalysts. Most reforming catalysts
contain platinum as the active material. Sulfur and nitrogen compounds
present in naphtha cut from atmospheric distillation column can deactivate
the catalyst and must be removed prior to catalytic reforming.
Purpose of the naphtha hydrotreating unit is to remove sulphur and
nitrogen compounds. The naphthahydrotreating unit uses a cobalt-
molybdenum catalyst to remove sulfur by converting it to hydrogen sulfide
that is removed along with unreacted hydrogen. Some of the hydrogen
sulphide-hydrogen mixture is recycled back to the reactor to utilize the
unreacted hydrogen, using a compressor.
Reactor conditions for naphthahydrotreating unit are around 400-
500F (205-260C) and pressure of 350-650 psi (25-45 bar). As coke deposits
on the catalyst, reactor temperature must be raised. Once the reactor
temperature reaches ~750F (400C), the unit is scheduled for shutdown and
catalyst replacement.
 If required, the boiling range of the catalytic reforming charge
stock can be changed by redistilling in the naphtha hydrotreater in a stripper
as shown in Figure-2. Often light naphtha containing pentanes, hexanes and
light naphtha are stripped off and sent directly to gasoline blending or
pretreated in an isomerization unit prior to gasoline blending. The heavy
naphtha from the bottom of the stripper column goes back to the catalytic
reformer unit before blending with gasoline.
b. Isomerization Plant
A component of refinery gasoline pools that frequently offers the best
opportunity for quality improvement is the pentane-Hexane fraction, or light
straight-run (LSR) naphtha. The LSR is characterized by a low octane number,
ordinarily 60 to 70 research octane number (RON). Isomerization converts linear
molecules such as normal pentane into higher-octane branched molecules for
blending into the end-product gasoline. This Process also removes Benzene from
the feed. The isomerization unit is comprised of three sections, Feed Preparation,
Penex and Molex and increases the octane from 65 to 90.
1.2. Heavy Naphtha
Heavy Naphtha balance include : Heavy Naphtha with high naphthenic and
aromatic content that are suitable feed to reforming.
a. Heavy Naphtha Hydroteater Unit
Heavy Naphtha cut from the atmospheric crude oil distillation column in a
refinery is sent to a Naphtha Hydrotreating Unit. After the naphtha
hydrotreating unit, naphtha is sent to an isomerisation unit or a catalytic
reformer unit, which often use reforming catalysts. Most reforming catalysts
contain platinum as the active material. Sulfur and nitrogen compounds
present in naphtha cut from atmospheric distillation column can deactivate
the catalyst and must be removed prior to catalytic reforming.
Purpose of the naphtha hydrotreating unit is to remove sulphur and
nitrogen compounds. The naphthahydrotreating unit uses a cobalt-
molybdenum catalyst to remove sulfur by converting it to hydrogen sulfide
that is removed along with unreacted hydrogen. Some of the hydrogen
sulphide-hydrogen mixture is recycled back to the reactor to utilize the
unreacted hydrogen, using a compressor.
Reactor conditions for naphthahydrotreating unit are around 400-
500F (205-260C) and pressure of 350-650 psi (25-45 bar). As coke deposits
 on the catalyst, reactor temperature must be raised. Once the reactor
temperature reaches ~750F (400C), the unit is scheduled for shutdown and
catalyst replacement.
b. Catalytic Reformer
Process Objective:
To convert low-octane naphtha into a high-octane reformate for gasoline
blending and/or to provide aromatics (benzene, toluene, and xylene) for
petrochemical plants.Reforming also produces high purity hydrogen for
hydrotreating processes.
Primary Process Technique:
Reforming reactions occur in chloride promoted fixed catalyst beds; or
continuous catalyst regeneration (CCR) beds where the catalyst is transferred
from one stage to another, through a catalyst regenerator and back again.
Desired reactions include:
dehydrogenation of naphthenes to form aromatics; isomerization of
naphthenes;
dehydrocyclization of paraffins to form aromatics; and isomerization of
paraffins.
Hydrocracking of paraffins is undesirable due to increased light-ends
make.
Process steps:
Naphtha feed and recycle hydrogen are mixed, heated and sent through
successive
reactor beds
Each pass requires heat input to drive the reactions
Final pass effluent is separated with the hydrogen being recycled or
purged for hydrotreating
Reformate product can be further processed to separate aromatic
components or be used for gasoline blending
2. Kerosene
Kerosene is an oil distillate commonly used as a fuel or solvent. It is a thin, clear
liquid consisting of a mixture of hydrocarbons that boil between 302F and 527F (150C
and 275C). While kerosene can be extracted from coal, oil shale, and wood, it is
primarily derived from refined petroleum. Before electric lights became popular,
kerosene was widely used in oil lamps and was one of the most important refinery
products. Today kerosene is primarily used as a heating oil, as fuel in jet engines, and as a
solvent for insecticide sprays.
Kerosene is extracted from a mixture of petroleum chemicals found deep within
the earth. This mixture consists of oil, rocks, water, and other contaminates in
subterranean reservoirs made of porous layers of sandstone and carbonate rock. The oil
itself is derived from decayed organisms that were buried along with the sediments of
early geological eras. Over tens of millions of years, this organic residue was converted
to petroleum by a pair of complex chemical processes known as diagenesis and
catagensis. Diagenesis, which occurs below 122F (50C), involves both microbial
activity and chemical reactions such as dehydration, condensation, cyclization, and
polymerization. Catagenesis occurs between 122F and 392F (50C and 200C) and
involves thermocatalytic cracking, decarboxylation, and hydrogen disproportionation.
The combination of these complex reactions creates the hydrocarbon mixture known as
petroleum.
2.1. Merox Treater
The Merox process was initially introduced to the refining industry more
than 40 years ago. In the intervening years, on-going process and catalyst
innovations have enabled the Merox process to become one of UOPs most
successful processes with more than 1,700 units licensed. Even as processing
objectives changed to meet impending sulfur content regulations, the Merox
process has been one of the key refining technologies with more than 300 Merox
units licensed since 1990.
All versions of the Merox process are characterized by the catalytic
oxidation of mercaptans (RSH) to disulfides (RSSR) in an alkaline (basic)
environment.
The overall reaction is:

In a liquid-liquid extraction Merox process application, mercaptans in

lighter feeds such as gases, C3s, C4s, LPG, and naphtha are extracted with a
caustic solution, which is regenerated by oxidation with air in the presence of
Merox catalyst. The resultant disulfides are separated and the caustic reused for
extraction. The sulfur content of the extracted hydrocarbon is reduced.
 Heavier hydrocarbon fractions such as naphthas, kerosene, jet fuel and
diesel contain types of mercaptan which cannot be readily extracted from the
hydrocarbon. Hence, in a fixed-bed sweetening Merox process application, the
mercaptan oxidation reaction takes place in the presence of air, Merox catalyst
and a basic environment, such as caustic. The mercaptans are converted to
disulfides which remain in the sweetened hydrocarbon product. The overall sulfur
content, therefore, remains the same. Mercaptan sweetening in a fixed bed of
Merox catalyst have replaced the older liquid-liquid catalyst sweetening units.
Figure down shows the Merox process applications for various types of
hydrocarbon.