Distillate/Diesel Hydrotreating

Introduction
Distillate or Diesel Hydrotreaters, also referred to as Hydro-desulfurization Units, remove organic
sulfur, nitrogen, halide, oxygenate, and metals compounds from diesel boiling range feed.
Hydrotreaters achieve this by passing feed over a bed of hydrotreating catalyst in the presence
of hydrogen and at high temperatures and relatively high pressures. Organic Sulfur and Nitrogen
Compounds must be removed from diesel product to reduce SOX and NOX emissions from
diesel engines during combustion. In the diesel hydrotreating process, organic sulfur, nitrogen,
and oxygen compounds are converted to H2S, Ammonia, and Water, respectively. C4H9SH +
H2 → C4H10 + H2S C5H5N + 5H2 → C5H12 + NH3 C6OH +H2 → C6H12+ H2O

Metal contaminants are trapped on the reactor catalyst surface, which in addition to coking,
deactivates the catalyst overtime and necessitating catalyst change-out. Because these
reactions take place in the presence of hydrogen, hydrotreating also saturates olefin and
aromatic compounds in the feed.

Feed and Feed Pre-Heat

Diesel from numerous units in the refinery e.g. Crude/Vac, FCC, Coker, etc. are combined with
makeup and recycle hydrogen. The combined feed is directed to the feed preheat section of the
plant where it is exchanged with hot reactor effluent to raise the mixture to optimum feed heater
inlet temperature. This decreases the duty (energy) requirement of the fired feed heater-saving
on natural gas or fuel oil which fires the heater. In the fired heater, the feed passes through the
fired heater’s tubes where it is raised to the required reactor inlet temperature to promote the
hydrotreating reactions, 300 to 400C in the unit depicted above.

Reactor
The hydrotreating reactions are exothermic. As a result, a temperature rise is observed across
the reactor catalyst bed. To prevent a runaway, or uncontrolled, extremely high temperature
reactions in the catalyst bed, reactor bed temperatures are closely monitored. A runaway results
in extremely high temperatures that could potentially result in a serious safety hazard for refinery
personnel as well as catalyst and equipment damage as temperatures exceed the specifications
of the metallurgy of the reactor vessel. The refiner has several handles to control the rate of
reaction: Feed Quality, H2/HC Ratio or H2 Makeup, Reactor Temperature, Recycle, Quench,
LHSV, and Catalyst.

Feed Quality
Feed quality to the diesel hydrotreater, DHT, varies with the refinery’s current crude mix, the type
of upstream unit feeding the diesel hydrotreater, and the operating mode of the upstream units.
Refinery process units do not operate in a vacuum-they are dependent on the operating mode of
the entire refinery. If the refinery is running sweet crudes, less that .5% sulfur, the amount of
sulfur in the feed to a DHT will be much lower than when the refinery is running sour crude.
Another concern is the amount of crack stock in the feed to the unit. Cracked stock is product
from a thermal or catalytic cracking unit like a delayed coker or FCC. These units process the
heavier cuts from the crude unit like gas oil and residue which contain more difficult to process
sulfur, nitrogen organic compounds as well as a higher amount of metals. Diesel direct from the
crude unit, referred to as straight run diesel, results in a much lower exothermal reaction
(temperature rise) across the reactor bed because 1) it is derived direct from the lower sulfur
portion of the crude mix and 2) it contains fewer olefinic , or unsaturated, straight-chain
compounds. Olefins react rapidly with hydrogen (to saturate), an exothermic reaction that results
in a large heat release. Another consideration is operation of the fractionation sections of the
upstream units. If the end point of the light cycle oil, LCO, from the FCC’s Main Column
increases (meaning heavier material is drawn from the diesel/LCO draw from the column and
sent to the DHT), a higher amount of more difficult to hydro treat material will be sent to the DHT.

H2/HC Ratio
The desulfurization, denitrogenation, and deoxygenation reactions consume hydrogen.
Hydrogen, H2, also saturates olefins and aromatics and prevents coking or condensation of
hydrocarbon on hydrotreating catalyst. Think of coking essentially as hydrocarbons burning and
leaving carbon residue on the active sites of the catalyst preventing catalyst from carrying out the
required hydrotreating reactions or catalyst deactivation. H2/HC ratio is the amount of Makeup+
Recycle Hydrogen divided by barrels of feed. Hydrogen is a feed source for several units in the
refinery. Refineries are often H2 limited or do not have enough hydrogen to meet the needs of all
H2 consumers. Hydrogen is generated in the refinery’s Catalytic Reforming or Steam Methane
Reforming Units or purchased from an outside provider. Hydrogen is costly for the refinery to
produce or purchase. As such, the H2 to HC ratio must be optimized to not only meet the needs
of the hydrotreating reactions and to maintain catalyst life but also to ensure profitability for the
refinery. To prevent waste of Hydrogen, Separator Hydrogen is recycled back to the feed of the
hydrotreater in addition to normal H2 make-up. Some refineries also cascade hydrogen purge
from one hydrotreater to another if the hydrogen content is high enough to meet the units needs.

Reactor Temperature
Reactor Temperature is a variable in daily unit operation as well as long term catalyst activity
monitoring. Operations can control the heater coil outlet temperature of the furnace and quench,
described below. Several thermocouples are inserted throughout the catalyst bed to monitor
catalyst activity and look for hot spots due to channeling and poor catalyst loading. Poor
distribution of hydrocarbon through the bed results from channeling which leads to reactor
internals damage or temperature runaway. The Weight Average Bed Temperature is used by unit
engineers to monitor catalyst deactivation. WABT increases SOR to EOR (Start of Run to End of
Run) due to coking or metals deposition on catalyst. Operators should not operate the unit to
WABT in daily operation. Temperatures from individual thermocouples throughout the catalyst
bed should be considered and monitored for hot spots. Still, because of the distance between
thermocouples, it is still possible to have undetected hot spots.

Recycle
Recycling hydrotreated product from the fractionation section back to the feed can also be used
to control the severity of hydrotreating operation. Recycling back the product reduces the amount
of highly contaminated and thus highly reactive feed to the unit. However, this also limits the
capacity or the amount of feed that can be processed in the unit.

Quench
Some Distillate Hydrotreaters have the option of directing hydrogen directly in between beds in
multiple catalyst bed reactors. This hydrogen serves as a means of cooling to the reactors in high
severity operations as well as additional hydrogen for the treating reactions.

LHSV
Liquid Hourly Space Velocity is the volumetric feed rate divided by catalyst volume. Higher LHSV
means a higher feed rate to the unit, means a greater amount of reactive material to the catalyst,
leading to a greater temperature rise across the catalyst. This also leads to earlier catalyst
deactivation.

Catalyst
Hydrotreating Catalyst is typically made of Nickel-Molybdenum. Catalyst is selected by the
refinery to meet a variety of feed, product, and operating goals e.g. typical feed quality and
desired operating severity, medium or Ultra Low Sulfur Diesel operating mode, and length of
catalyst life.
Gas Separation
Effluent from the reactor passes through the feed effluent exchanger and enters a fin fan
exchanger where the effluent is cooled to separator temperature, 35C per the above diagram.
Organic Chlorides combined with Ammonia from the denitrogenation reactions to for ammonium
salts which could deposit on the tubes of the fin fan exchanger and, in addition to reduced
cooling/heat transfer, cause lead to corrosion. To prevent this, water is combined with the reactor
effluent which washes the salts away. Once the material is cooled, it enters the separator where
the gas phase hydrogen and light end material (typically C1-C4) is separated or flashes off from
the now liquid phase product. This light end C1-C4 material comes from the small amount of
hydrocracking that also occurs in addition to the hydrotreating reactions. This number is small
typically .4-.6 wt% of feed in most operations. The separator sets the pressure for the unit.
Typically two pressure control schemes are used: 1) the Makeup hydrogen rate is maintained to
set unit pressure while the HPS vent to the sour gas system floats or the HPS vent to the sour
gas system is used to control pressure while make-up hydrogen floats. Remember Hydrogen
Partial pressure and pressure of a DHT is essentially synonymous as it makes the greatest
contribution to the pressure of the unit. Products from the Separator are typically Recycle
Hydrogen (Unless Once Through), Vent Gas to the Sour H2 System or Fuel Gas, Water if there
is a water boot, and Liquid Hydrocarbon. The Recycle Hydrogen in the diagram above is directed
to an amine contactor to scrub for H2S and Ammonia before directing it to the recycle
compressor suction to pressure the gas back to the feed or the reactor as quench. Fractionation
The liquid from the separator is directed to the unit’s fractionation section where products are
prepared for downstream units or product blending. The stripping column depicted above is total
condensing meaning that no overhead product is drawn from the top of the tower other than light
ends which are sent to the refinery’s gas plant. This light end material is removed not only to rid
diesel product from any dissolved H2S and ammonia but also to allow the diesel to meet other
specifications like flash for blending. There may also be a naphtha overhead product that is
drawn from the overhead in partial condensing towers (reflux plus product draw). In the drawing
above, the stripping column is heated or reboiled by exchanging a portion of the bottoms material
with hot oil or steam and returning that material to the bottom of the tower. When feed enters the
tower, lighter material vaporizes and rises through the trays of the column while the heavier
material flows down the column. Some valuable diesel product material is also vaporized and
entrained with lighter material which exits the top of the column. This vapor is cooled to liquid
phase in a condenser, collected the overhead receiver. Uncondensed light ends are vented to
sour gas treatment and the heavier liquid is refluxed back to the column to improve separation.
Cooled refluxed higher distillate concentrated liquid flows down over the upper column trays and
comes in contact with rising vapors. Due to vapor liquid equilibrium discussed in earlier posts,
heavy material flows back down the column leading to product purification. Light end material
leaves the overhead drum and is directed to the refinery’s sour gas plant. Product diesel is drawn
from the tower bottoms and sent to tankage or blending.
Pitting corrosion

Pitting corrosion results when dust particles get deposited on a metal surface.
The portion covered by the dust will be less aerated compared to the exposed
surface
The covered portion thus becomes anodic with respect to the exposed surface
The presence of electrolytes and moisture corrosion starts beneath the dust resulting
in a pit
Once a pit is formed,the corrosion progress rapidly.This is because of the formation
of small anodic area(pit) compared to a large cathodic area(surface)

Pitting Corrosion

Pitting corrosion is a localized form of corrosion by which cavities or "holes" are

produced in the material.A small, narrow pit with minimal overall metal loss can lead
to the failure of an entire engineering system. Pitting corrosion, which, for example,
is almost a common denominator of all types of localized corrosion attack, may
assume different shapes.
Suppose . . . that a small cavity exists in the surface of the metal into which oxygen
cannot diffuse quickly. A current will be produced between the unaerated area within
the cavity, which will become anodic, and the aerated part of the surface outside,
which will be the cathode; soluble salt will be formed at the anodic surface within the
cavity, but this will not, of course, interfere with further anodic attack. At the mouth of
the cavity where the soluble metallic salt from the interior mixes with the alkali from
the cathodic part outside, hydroxide may be precipitated, but it will not put a stop to
the anodic attack proceeding within. Since the rate of attack is determined by the
supply of oxygen to the whole surface outside the pit, and since it is all concentrated
on the small area within the pit, the rate at which the corrosion bores into the metal
will be very great; . . . U.R. Evans, 1924
Pitting corrosion can produce pits with their mouth open (uncovered) or covered with
a semi-permeable membrane of corrosion products. Pits can be either hemispherical
or cup-shaped
Pitting is initiated by:
a.Localized chemical or mechanical damage to the protective oxide film; water
chemistry factors which can cause breakdown of a passive film are acidity, low
dissolved oxygen concentrations (which tend to render a protective oxide film less
stable) and high concentrations of chloride (as in seawater)
b.Localized damage to, or poor application of, a protective coating
c.The presence of non-uniformities in the metal structure of the component, e.g.
nonmetallic inclusions.
Theoretically, a local cell that leads to the initiation of a pit can be caused by an
abnormal anodic site surrounded by normal surface which acts as a cathode, or by
the presence of an abnormal cathodic site surrounded by a normal surface in which
a pit will have disappeared due to corrosion.

In the second case, post-examination should reveal the local cathode, since it will
remain impervious to the corrosion attack as in the picture of an aluminum specimen
shown on the right. Most cases of pitting are believed to be caused by local cathodic
sites in an otherwise normal surface.
Apart from the localized loss of thickness, corrosion pits can also be harmful by
acting as stress risers. Fatigue and stress corrosion cracking (SCC) may initiate at
the base of corrosion pits.
One pit in a large system can be enough to produce the catastrophic failure of that
system. An extreme example of such catastrophic failure happened recently in
Mexico, where a single pit in a gasoline line running over a sewer line was enough to
create great havoc to a city, killing 215 people in Guadalajara.

Corrosion Pit Shapes

Pitting corrosion can produce pits with their mouth open (uncovered) or covered with
a semi-permeable membrane of corrosion products.
In this micrograph of an aluminum specimen exposed to a 3,5% NaCl solution for
seven days one can clearly (?) see different types of attack on the same surface.
The width of the picture is approximately 1 mm.
Can you see at least three regions of attack in this picture? ('click here' if you want to
see our answer)

Localized Corrosion of Aluminum

The corrosion attack of aluminum of the 2000 family is mixed. While most of the
surface is uniformly pitted (yellow arrow), as A92024 would do in similar conditions,
we can see the formation of deeper pits (red arrow) that are surrounded by
unattacked regions (blue arrow).

Pits can be either hemispherical or cup-shaped.In some cases they are flat-walled,
revealing the crystal structure of the metal, or they may have a completely irregular
shape. Pitting corrosion occurs when discrete areas of a material undergo rapid
attack while most of the adjacent surface remains virtually unaffected. The following
are common pit shapes divided in two groups:
Trough Pits
Sideway Pits

Narrow, deep
Subsurface

Shallow, wide
Undercutting

Elliptical
Horizontal grain attack

Vertical grain attack

Pit Depth Measurement

Pit depth measurement has been a requirement of corrosion inspectors for many
years. Many different tools for the measurement of corrosion damage have been
developed. The most successful of the pit depth tools was a lever type pit gauge
used by Mr. William R. Thorpe, a former Chevron inspector in the Tulsa area. Mr.
Thorpe had company craftsmen fashion a variety of configurations during his tenure
there. As a retirement present, his coworkers presented him with a new copy of his
latest configuration. (adapted from Pit Gauges – History and Development by: Mark
Palynchuk, General Manager Western Instruments Inc.)
Unfortunately Mr. Thorpe passed on soon after his retirement, but his pit gauge lived
on, through an accounting firm. Any further development ceased, but this incredibly
simple product became an industry standard for 40 years. As a result, of corrosion
inspectors complaining about the limitations of the Thorpe, the development of
Western Instruments bridging pit gauge™ resulted.

As the operational envelopes of pressure equipment (pipelines, boilers, vessels,

piping, and storage tanks), oil country tubular goods (tubing/casing, drill pipe, bottom
hole assemblies), bridges/structures, concrete, and aircraft components were
pushed, so were their corrosion allowances. Unfortunately tools were slow to evolve,
simply due to cost, but as the cost of equipment (and failures) increased, so did the
perceived need of equipment to measure corrosion increased. Inspectors were
constantly required to perform more accurate pit depth measurements even if their
tools were inadequate. Other tools were “adapted” for pit measurement, such as
machinist’s depth gauges. While the dial indicators (and micrometer barrels) used in
depth gauges were an improvement in accuracy, they were cumbersome to use for
field inspection. Furthermore, dial indicators were expensive and any modification to
them was cost prohibitive. With the advent of automatic machining, and computer
aided designs, manufacturers of dial indicators were more readily able to perform
short runs, with very specific modifications. This lead to the development of dial
Indicator pit gauges.
Today we see the use of highly specialized computer controlled coordinate
measuring machines mapping entire areas of weight-loss corrosion. A modern
ultimate pit gauge costing over $50,000. While such specialized tools fulfill a niche in
industry, they require a skilled technician to operate, a specialist to interpret, and
skilled maintenance and repair personnel. When an inspector is not familiar with
specialized measurement tools, such as dial or digital indicators, a dial indicator pit
gauge can be an intimidating piece of equipment. It was not recognized until recently
that the greatest demand for pit gauges was not for these specialized tools but still
for the the simple lever type pit gauge, a tool that had not changed in 40 years.
Simple lever pit gauges have not evolved to meet modern industry requirements. For
example, no gauge could be found with both metric and imperial scales. A
development program was undertaken to test and identify the benefits and
shortcomings, of lever type pit gauges, correct them, and manufacture them
economically. The result of this program is a simple to use pit gauge, with a metric
and two imperial scales, a unique pointer that aids the inspector to eliminate
alignment errors. Since then the cost of the ‘task specific’ dial indicators has been
coming down. Furthermore, with an aging infrastructure the demand for corrosion
measurement and monitoring has increased substantially. Over the last 20 years we
have seen this industry evolve, with companies specializing in Corrosion
Measurement and Monitoring. Specialized manufactures have evolved, such as
ourselves, manufacturing industry specific tools. As Business 101 has taught us,
when there is a demand, a supply will soon follow. Today we see digital indicators,
and specialized fixtures, with their increased cost, being offered and used. This
same gauge has applications for weld Inspection, with such capability as measuring;
undercut depth, weld crown height, a porosity comparitor, with metric and imperial
units.
Pit Propagation Mechanisms
The formulation of the mechanism of pitting corrosion of aluminium is very complex.
Although, it is generally accepted that there are two steps to the mechanism:
Pit initiation
The initiation of pitting corrosion is often linked to the presence of local defects at the
metal surface such as flaws in the oxide or segregates of alloy elements, and the
presence of aggressive anions such as chlorides in the environment. The chlorides
are believed to locally disrupt the oxide, preferably at pre-existing weak spots,
resulting in microfissures of several nm in diameter.
Pit propagation
Amongst the many initiated pits only a few will propagate. The proposed mechanism
shown here supports recent studies indicating that pitting corrosion of aluminium is a
discontinuous process.
The overall reaction equation can be described as follows:
2Al + 3H2O + 3/2·O2 → 2Al(OH)3
The pit propagation process is built up of different intermediate steps:
1.In the initiated pit, aluminium is dissolved : 2Al + 2Al3+ + 3e−, and the Al3+ cations
react with Cl− anions to form a complex intermediate species AlCl4−. Hydrolysis of
this species results in acidification of the bottom of the pit to a pH < 3 (due to
formation of H+). This highly aggressive environment results in autopropagation of
the pit.
2.Al3+ cations concentrated at the bottom of the pit diffuse out of the pit, where they
encounter a more alkaline environment due to the cathodic process of hydrogen gas
evolution : 6H+ + 6e− → 3H2, or water reduction:
2/3·O2 + 3H2O + 6e → 6OH−
As a result aluminium hydroxide is formed and precipitates at the borders of the pit.
This deposit of white corrosion product grows to eventually block off the entrance to
the pit for further ionic exchange processes.
Many process streams in petroleum refineries contain enough H2 S to cause sulfide
stress cracking (SSC) in susceptible materials
This NACE standard establishes material requirements for resistance to sulfide
stress cracking (SSC) in sour refinery process environments, i.e., environments that
contain wet hydrogen sulfide (H2S). It is intended to be used by refineries,
equipment manufacturers, engineering contractors, and construction contractors.
The term “wet H2S cracking” as used in the refining industry covers a range of
damage mechanisms that can occur because of the effects of hydrogen charging in
wet H2S refinery or gas plant process environments. One of the types of material
damage that can occur as a result of hydrogen charging is SSC of hard weldments
and microstructures, which is addressed by this standard. Other types of material
damage include hydrogen blistering, hydrogen-induced cracking (HIC), and stress-
oriented hydrogen-induced cracking (SOHIC), which are not addressed by this
standard.