Naptha Hydrotreating Unit

Hydrotreating

Most products of crude and vacuum distillation in refineries contain a significant amount of sulpur
that must be removed prior to further processing or use. Hydrotreating or hydrodesulfurization
refers to a set of operations that remove sulphur and other impurities. During hydrotreating, crude
oil cuts are selectively reacted with hydrogen in the presence of a catalyst at relatively high
temperatures and moderate pressures. The process converts undesirable aromatics, olefins,
nitrogen, metals, and organosulfur compounds into stabilized products. Some hydrotreated cuts may
require additional processing to meet final product specifications.

Basic Outline of a Petroleum Refinery with Hydrotreating Units

Why is Hydrotreatment required?

Hydrotreatment processes reduce the impurity content of petroleum products, which increases the
efficiency of the fuels and reduces the production of harmful combustion byproducts such as NOx
and SOx. Hydrotreatment also helps to satisfy final product specifications. Contaminants can affect
the performance of downstream unit operations, catalysts, or even engines.

Compounds removed by Hydrotreating

 Sulphur is the most critical compound to remove. It is present in nearly all crude oil
feedstocks as sulphur mercaptans, sulphides, disulfides, polysulfides, and thiophenes.
  Nitrogen is typically treated with hydrogen gas and transformed into ammonia gas.
 Oxygen is reacted with hydrogen and eliminated as water. Most oxygen in distillation cuts is
not present as oxygen gas, but bonded to hydrocarbons.
 Olefins are volatile and unstable, and they are not desirable in fuels. Olefins are transformed
into stable paraffinic hydrocarbons.
 Metals are removed because they can deposit on catalysts and in engines.

Basics of Hydrotreating Operation

It is common to assume that the hydrotreating process is a single unit operation that converts all of
the raw feed into a final desulfurized product. However, this is not the case; most hydrotreatment
processes require many unit operations, including a reactor, gas separators, separation columns, and
heat exchangers. The process can be divided into three main processing blocks:

 heat exchange network

 reactor in which the actual hydrotreating takes place

 stripping where the desulfurized product stream is separated from the volatiles, gases, and
impurities.

Each hydrotreating unit is tailored to the feedstock and end product. For instance, the process to
hydrotreat naphtha is not the same as the process for diesel fuels. The most common cuts that are
hydrotreated in a refinery include: light naphtha, heavy naphtha, jet fuel or kerosene, and diesel oils
(e.g., light and heavy coker diesel oil). This article focuses on the two main cuts: naphtha and diesel
oil.

Process Description

The feed is first pressurized and mixed with the recycle and makeup hydrogen streams. The mixture
is heated to about 290–430°C before entering the fixed-bed reactor, which operates at about 7–180
bar. Higher temperatures and pressures are used for processing heavier feedstocks, such as diesel
oils. Overall, however, hydrotreater temperatures are relatively moderate, which avoids thermal
cracking of molecules while being high enough to enable reaction of the feedstock.

Inside the fixed-bed reactor, hydrogenolysis and mild hydrocracking reactions take place to convert
sulfur, nitrogen, oxygen, and other contaminants to hydrogen sulphide, ammonia, water vapor, and
other stabilized byproducts (Figure 3). The catalyst used in the reactor is a crucial design
consideration that greatly affects the final products. If sulphur removal is the primary goal, cobalt-
molybdenum catalysts are favored. If the crude oil is relatively low in sulphur, nitrogen removal
becomes the priority and nickel-molybdenum catalysts are chosen. Depending on the conditions and
composition of the outlet streams, the byproducts are either discarded, recycled, or sent for further
treatment.

Most outlet streams undergo further treatment to lessen their environmental impact and/or recover
the material for use. Sour gas (which contains hydrocarbons, carbon dioxide, and a significant
amount of hydrogen sulfide) is commonly sent to an amine gas treating unit that separates the
hydrocarbon gases from the hydrogen sulfide and carbon dioxide.
Hydrotreating of Naptha

Naphtha is a valuable product of petroleum refining, as it is one of the main constituents of the
gasoline blending pool. While there is no formal definition of naphtha, it is commonly considered the
C5–C12 cut, which is divided into light and heavy naphtha. Light naphtha has an initial boiling point
(IBP) of about 30°C and a final boiling point (FBP) of about 145°C. It contains most of the
hydrocarbons between C4 and C6. Heavy naphtha has an IBP and FBP of about 140°C and 205°C,
respectively. It contains most of the hydrocarbons in the C6–C12 range.

High sulphur content is associated with cuts that are heavier than naphtha. However, removing the
relatively small amount of sulphur in naphtha is beneficial for engine performance and operational
longevity.

Schematic of Naptha Hydrotreating Unit

Processing of Naptha

Heating

The naphtha feed enters the hydrotreatment unit through a charge pump. It is first mixed with
hydrogen gas from either the catalytic reforming unit (CRU) or refinery hydrogen plant. The mixture
is then heated to 340°C while being contacted with the reactor’s effluent.

The charge heater has four passes with four gas burners. Heater tubes are constructed of Type 321
stainless steel, which is the grade of choice for applications with temperatures up to around 900°C,
because it combines high strength and resistance to scaling with resistance to aqueous corrosion.

Reaction

After preheating, the mixture is fed to a reactor with two catalyst beds. The desulfurization reactions
take place over the cobalt-molybdenum bed and the nitrogen reactions take place over the alumina
bed. The reactor temperature is held at a constant 315°C and a pressure of 370 psig.

The reactor effluent contains mostly the desulfurized naphtha, excess hydrogen, hydrogen sulphide,
ammonia, and light hydrocarbons (C1–C4) due to mild cracking. The reactor effluent is cooled and
partially condensed through a feed/effluent heat exchanger and then cooled with air.
Separation

The separation process, or stripping section, uses a series of separators and columns to stabilize the
naphtha.

The cooled stream from the reactor is sent to a pressurized flash separator at 290 psig. The light
ends, mainly hydrogen sulphide, ammonia, excess hydrogen gas, and light hydrocarbons, are
separated from the bulk of the desulfurized naphtha.

The liquid naphtha stream from the separator is then sent to the stripping unit. The stripping column
is heated to 340°C by a reboiler and held at a pressure of 205 psig. High temperature and pressure
enable removal of volatile material (light hydrocarbons), which would vaporize at final storage and
use conditions. Inlets to the stripping column include desulfurized raw naphtha, recycled
desulfurized stripped naphtha, and the bottoms of the column. The outlet streams include mostly
light gases (C1–C5 hydrocarbons) that are sent for amine treatment to recover them as fuels.

The resulting liquid naphtha is then cooled by air and sent out of the unit’s battery limits as stabilized
hydrotreated naphtha product.

Process Route Description(for Simulation)

The feed from the refinery mainly raw Naphtha (NHTFEED) at a temperature of 63 °C and pressure of
3.5 kg/cm2 entered into a Surge Drum 151-W-1001.and the bottom entered into Pump 151-PA-1001
A/B. The fluid was charged using the pump to a mixer 151-MX where it mixed with a fresh Hydrogen-
Feed, gas stream at high pressure and temperature of 67°C. This was pumped into an Exchanger of
Combined Feed (151EE-1001A-N) to be preheated by the products of the reactor from a temperature
of 65 °C to 292°C. The preheated stream temperature was increased by heating it to the desired
reaction temperature of 334 °C by Heater (151-FE-1001) and then entered into the Reactor 151-
RB1001 in which the following reactions; hydrodesulphurization, hydro-denitrogenation,
hydrodeoxidation and olefin saturation occurred with respective following products of Hydrogen
Sulfide (H2S), Ammonia (NH3), Steam (H2O) and Cyclohexane (C6H12) obtained. The products of the
exothermic reactions at a temperature of 343°C were passed through the tube side of the Exchanger
of combined Feed (151EE-1001A-N) to pre-cool the product stream simultaneously preheating the
reactant incoming fluid stream. The product from the Exchanger of combined feed was left at a
temperature of 235 °C and was allowed to cool to a temperature of 75 °C in Products Condensers
151-EA1001A-P. The condensed product was channeled to a Separator 151-W-1003. In which the
sour H2 gas (vapour phase) moves from the top of the separator and entered the Recycle
Compressors 151-KA-1001 A/B, from where a part of this gas is sent to CFE in which part of it is used
as makeuphydrogen for the reactions. On the other hand, the liquid obtained from the bottom of
Separator 151-W-1003 was channeled to the Stripper 151- CC-1001 at a temperature of 49 °C,
through a Pump (151- PA-1006 A/B). Off gas and unstabilized LPG respectively from the top and
bottom of the Stripper receiver were sent to the SGC unit. The treated naphtha from the bottom of
Stripper 151-CC-1001 was sent to Splitter 151-CC-1002 to divide the bottom product from the
Stripper to give two products; Light Naphtha and Heavy Naphtha[1], [2].

Operating Data

Operating Data consist of Temperatures, Pressures, Stream Compositions, and Flows. The data for
the Piping and Instrumentation Diagram of the Naphtha Hydrotreating (NHT) Unit was obtained from
the case model [10]-[12]. The process simulation using Aspen HYSYS version 8.6 [16] was done using
data extracted from the laboratory model manual[10]-[12] of the model. The data comprises
compositions for the feed, stream pressures, temperatures, mass flow rates and those required for
piping and instrumentation of Naphtha Hydrotreating unit.

Process Simulation and Modelling

The processes taking place in the Naphtha Hydrotreating plant as shown in the flow sheet (PFD)
include the following standard unit operation blocks and logical units (e.g. Heaters, Reactor, Heat-
exchanger, Coolers, Separators, Columns etc.). These were modelled and simulated using a
sequential process software - Aspen HYSYS Version 8.6.

Exergy Calculation

Microsoft Excel of the Microsoft Office Suite 2013 package was used to calculate the exergy entering
and exiting, the irreversibility then the exergy efficiency of some selected components of the Naptha
Hydrotreating Unit. The Microsoft Excel of Microsoft Office was used for calculating the following
parameters: Inlet and Outlet streams temperatures, molar flow rate enthalpies and entropies, which
were extracted from the simulation of the streams entering and leaving the equipment. The
temperature 25 °C, enthalpy and entropy -28990KJ/Kg mole and 209.3KJ/Kg mole°C were used
respectively for the reference environment properties. Equations given by [17] were used to
calculate performance parameters for the following selected units Pumps (151-PA-1001AB and
151PA-1006AB), a Heat exchanger (151-EE-1001A-N), Reactor (151-RB-1001AB), Compressor (151-
KA-1001A/B), Separator (151-W-1003), Stripper and Splitter columns (151-CC-1001 and 151-EE1006),
Surge Knockout drum (151-W-1001), Heater (151- FE-1001A-N), Cooler (151-EA-1001A-P)[2]. The
obtained results were tabulated.

Heat Recovery

Major Exergy destruction and heat recovery through flue gas and the use of Nano fluids in
equipment were considered using expressions given by [18], [19]. In comparison with estimates by
[20]-[22] the cost-effectiveness was also obtained.

Process Flow Diagram

Efficiency of the Unit

The results of exergy calculations of the Naphtha Hydrotreating (NHT) Unit are presented in the
Tables below. The inlet and outlet exergies with the irreversibility for each piece of equipment are
shown in Table I. While Table II is the Exergy efficiency of the equipment. The Reactor has 82.4 %,
Heat Exchanger, 83.1 % and the Compressor 90.9 % exergy efficiencies respectively. It was noted that
a large amount of the energy that entered the heat exchanger was dissipated to heat within the
process [2], [23].

Similarly, high exergy efficiency of 84.7 % was found in the Separator while efficiencies of 73.9 % and
92.9 % were respectively observed for Pumps 151-PA-1006 and 151-PA1001. Interestingly, Heater
151-FE-101 had a low efficiency of 30.2 % and recorded a high value of irreversibility. The high loss of
heat in the furnace indicates its inefficiency. The effect of this is depletion of fossil fuel due to an
increase in the use of fuel for more energy resulting in an increase in carbon emission and
contributing to the environmental pollution problem. Process modifications of the temperature of
hot and cold stream in the Heater can be explored to reduce the heat losses and low efficiency of
this unit thereby improving the efficiency by increasing the heat recovery in the preheat train [2],
[23] The Splitter and Stripper columns had efficiencies of 85.0 % and 22.5 % respectively. Exergy
losses in columns could be associated with the separation process occurring in the column giving rise
to high entropy. The process involves loss of momentum as a result of mass transfer and thermal
losses respectively and pressure drop driving force due to mixing of fluids and temperature driving
force in the column [24].

Exergy Destruction(loss)

Exergy destruction (losses) occurred in the units mostly accrued from the resistance and friction
losses as a result of the fluid flowing unit and making contact with the wall. This effect is small in the
following units Reactor, Compressor, Pumps and low-Pressure separator [2], [19]. However high
exergy losses were observed in the following equipment Stripper and Heater having a High
irreversibility or destruction of 11724008.13 and 1771113225.5 KJ/h respectively, with the respective
contribution to irreversibility given as 32.7% and 51.9 % of the entire lost work as presented in Table
III. The entropy generation owing to temperature variations and drop in pressure resulted in exergy
losses which were attributed to high lost work in the stripper column. Low energy efficiencies are
reportedly associated with fractionators [2], [23]. C. Results Validation The validation of the results of
this model was done by comparing the observations of similar studies on the hydro treatment
process with another Refining and Petrochemical Company NHT unit at Kaduna; a refinery that has
been running for years.[2]. The comparison is presented in Table 3, showing a difference of 36.3 %
and 31.5 % exergy efficiency respectively in the Splitter and Heat exchanger, with that of the current
study being the better of the two. Similarly, differences of 26.5 % and 0.9 % were observed in the
efficiencies of the Compressor and Stripper column respectively, with those of the current study
found to be more efficient. Contrastingly, differences of 5.4 % and 1.9 % were observed in the
efficiency of the Reactor and Separator respectively with that of the KRPC model found to be more
efficient. The lesser efficiencies observed inmost of the equipment of the NHU of KRPC compared to
those of NHU in the present study can be attributed to the equipment age and inadequate
maintenance of the earlier. The current model observed 91.28 % conversion in the desulphurization
reaction, more than twice an observation of 44.35 % reported by a study that modelled the
Hydrodesulphurization Unit of KRPC [2].