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For an FCC unit, conversion refers to the volume percent of the feed
converted to gasoline, light hydrocarbons, and coke. The conversion is
calculated as 100 minus the volume percent of light cycle oil plus slurry
oil products.
Hydrotreating the FCC feed can result in substantial benefits including
improvedconversionof the heavy gas oil feed, less severe or no hydrotreating
requirements for FCC gasoline, reduced severity hydrotreating for the FCC
distillate product, and reduced emissions from the FCC regenerator.
FCC hydrotreating projects can be very costly because the capacity is
relatively large compared with other refinery hydrotreating units. For
example, a 100,000-b/sd refinery may have 50,000-b/sd of FCC feed
material to hydrotreat but only 20,000-30,000 b/sd of naphtha or distillate.
Typically this unit will operate at substantially higher pressure than other
hydrotreaters, thus increasing the cost for expensive alloys that are used
for piping and equipment.
Hydrotreating FCC feed also produces significant quantities of hydrogen
sulfide and ammonia that must be recovered and disposed of appropriately.
This step often requires new auxiliary facilities such as amine
treating K , sulfur recovery L , and sour-water stripping M .
Furthermore, because of the relatively large capacity, additional hydrogen is
needed, which might require more refinery hydrogen-generation capacity
or purchase from a third party.
Typical hydrotreated FCC product sulfur specifications are about 0.2 wt
% if the main processing objective is improved conversion and reduced
emissions. Some of the more recent feed hydrotreating projects have
reduced product sulfur to about 500 ppm (wt). This reduces FCC-gasoline
sulfur content to the extent that hydrotreating after the FCC is not required
to meet the US low-sulfur-gasoline requirements and similar standards
that have been adopted or are pending in other countries.
Nitrogen removal and reduction in aromatics via saturation with hydrogen
in the FCC feed are also important processing objectives that can improve
FCC conversion.
FCC gasoline hydrotreating N is a relatively new technology developed
to assist refiners in complying with US low-sulfur-gasoline requirements.
These rules require that a refiners total gasoline pool have an average
sulfur content no greater than 30 ppm (wt) in a given year.
Feed to an FCC gasoline hydrotreater can vary from full boiling-range
material (C5 to 430 F. boiling range) to heavy FCC gasoline with a 325-
430 F. boiling range.
Steps
Heating
In the first step in a hydrotreating process, a hydrocarbon stream(naphtha,
diesel fuel, gasoline, gas oil) mixes with hydrogen and is heated via exchange
with hot reactor products in heat exchangers 1 and then in a charge heater
2 at moderate temperatures (600-800 F.) and pressures (300-1,500 psig).
The charge heater controls the temperature of the feed to the reactor.
Reactor
In the next step, the heated oil-hydrogen mixture from the charge heater
enters the reactor 3 , which is filled with catalyst in one or more fixed beds.
Uniform feed distribution over the catalyst bed is important for maximum
catalyst utilization. Proprietary reactor internals can provide almost 100%
catalyst utilization while ensuring almost uniform distribution of feed across
the catalyst bed.
Hydrotreating catalysts typically consist of a base material containing
small quantities of cobalt and molybdenum, nickel and molybdenum, or
a combination of both. The exact catalyst formulation varies according to
a variety of criteria including feed composition, contaminant levels, and
operating pressure. The top and intermediate catalyst beds are supported
by a metal screen affixed to the reactor walls. The bottom bed rests on inert
support material in the bottom of the reactor. Each catalyst bed can be up
to 35 ft long.
The temperature rise through any one bed is typically limited to about
50 F. At temperature increases greater than 50 F., a quench stream is
added between the beds. This requires special reactor internals to ensure
that the quench medium, usually hydrogen, is completely mixed with the
material from the catalyst bed.
Contaminants
Hydrogen reacts with organic sulfur in the feed oil to formH2S, and reacts
with the nitrogen in the oil to form ammonia. These contaminants are then
removed fromthe final product stream. Hydrogen also reacts with the olefins
and diolefins to form paraffins and isoparaffins.
Contaminants in naphtha hydrotreating are:
Silicon. Normally found in naphthas from delayed cokers, silicon
deactivates hydrotreating catalysts but can be abated with extra catalyst
and specialized catalysts with high silica retention capacity.
Olefins. The saturation of olefins in the feed will lead to the formation
of mercaptans that will not be removed from the treated product. The
result is a product with excessive sulfur. This reaction normally occurs
with coker naphtha and FCC gasoline and can be mitigated by adding a
second-stage reactor with cooling between the stages.
Diolefins. Normally associated with cracked naphthas, diolefins form
polymerization products, which are heavy materials resulting from the
combination of many single molecules. These polymers normally form at
temperatures found in the feed exchangers and can cause plugging that
will restrict the flow through the unit.
Although not contaminants, light ends (methane, ethane, propane, and
butanes) are usually formed to some degree in hydrotreating and must
be removed from the final product. Light-end formation is usually minimal
(less than 1%) at naphtha-hydrotreater process conditions.
Contaminants in distillate hydrotreating are:
Nitrogen. Feed nitrogen levels can vary depending on the feed source.
Product nitrogen content depends on the severity of hydrotreating. For
ULSD, the product nitrogen content will be about equal to product sulfur.
Olefins. The high heat of reaction can require an inter-reactor-bed quench
stream.
Aromatics. Depending on the type of catalyst used, aromatics in the feed
can react (saturate) with the hydrogen, and these reactions increase
hydrogen consumption and heat release. Some European countries
and California require product aromatics levels as low as 10 vol %.
Heat release in the reactor is not necessarily undesirable. In fact, it results
in a reduction in overall fuel consumption. Hydrogen, however, is generally
used for quench, which adds to compression requirements. Also this
decreases the amount of hydrogen available for the desirable hydrotreating
reactions.
Light ends. In distillate hydrocracking,
side reactions convert about 2 wt % of the
feed into light ends, depending on process
conditions.
In FCC feed hydrotreating, metals in
the feed can poison the catalyst. FCC feed
hydrotreaters use feed filters to remove
solids. Also in these units, a guard bed
reactor 4 is normally installed upstream
of the main reactor. It contains a special
catalyst that will capture metals and prevent
them from poisoning the main catalyst.
As noted previously, the reactor has
specially designed internals to ensure
uniform distribution of the hydrogen and
hydrocarbons over the catalyst.
The accompanying table shows typical
reactor conditions for hydrotreaters.
Separators
In the next step, several arrangements
are available for separating liquids and
vapor that exist in the reactor effluent. In
general, the decision is whether to use a
hot, high-pressure separator (HHPS) in
addition to a cold, high-pressure separator
(CHPS), or to use a CHPS only.
The HHPS 5 separates vapor, liquid
hydrocarbons, and water and usually
operates at about 500-550 F. The hot
vapors from the separator can be used
to heat recycle gas and liquids from the
cold separator. The HHPS improves the
efficiency of heat use in the hydrotreating
unit, which results in a smaller product
stripper and auxiliary equipment. Using
an HHPS will also improve the oil-water
separation in the CHPS.
For heavy gas oil hydrotreating, a hot separator is practically mandatory
to achieve adequate oil-water separation. This is less of a concern for
diesel hydrotreating unless there are significant quantities of cracked
material in the unit feed, which decreases the API gravity.
Disadvantages of this design are a 5-10% lower recycle gas purity,
which requires more recycle hydrogen compressor 6 horsepower. Using
an HHPS can be a viable option for increasing the capacity of an existing
hydrotreater that is limited by the flow of oil in the reactor loop. This revamp
would require, however, a modest increase in inlet flow capacity and power
for the recycle compressor.
Other options include using hot and cold low-pressure separators. These
designs marginally decrease the amount of materials in the upper part of
the stripper 7 and result in improved LPG recovery.
Compressors
The recycle compressor 6 , in the next step, circulates hydrogen and
light ends in the reactor loop. The objective of the compressor is to provide
excess hydrogen in the reactor, which promotes reactions and minimizes the
amount coke produced.
Typically at the reactor inlet, at least four to five volumes of circulating
hydrogen to one volume of hydrogen actually consumed in the various
reactions are desired to obtain a reasonable cycle length before the catalyst
has to be replaced. A hydrotreater should typically run at least 2 years before
needing to have its catalyst replaced.
The hydrogen compressor that handles the initial (makeup) hydrogen
stream compresses the makeup hydrogen, 8 which is typically from
a reformer or hydrogen plant, from the supply pressure to the reactor-
loop pressure.
The number of compression stages depends on the source pressure and
the reactor-loop pressure.
Towers
If a unit produces a single product, such as with naphtha hydrotreaters,
kerosine hydrotreaters, and some ULSD units, a stripper tower 7 in the final
step distills light ends, including hydrogen sulfide from the bottom product.
This tower can use heat from a fired reboiler or steam. Strippers have only
two product streams, a top and bottom.
With a steam stripper, downstream processing is required to remove
water from the hydrotreated product. This is typically a salt dryer which is
preceded by a coalescer or vacuum dryer.
If multiple products are produced (diesel and kerosine, or FCC feed
and diesel, for example), then a fractionator 9 with a fired reboiler 10 is
also used. The charge heater and fired reboiler share a common stack 11 .
Fractionators have multiple product streams.
Product strippers for FCC feed hydrotreaters cannot be reboiled because
temperatures of more than 700 F. are required to remove the light ends
and hydrogen sulfide. These high temperatures can lead to thermal cracking
some of the product oil to light ends and accelerated coke formation, which
is undesirable. Typically these strippers use a combination of feed heating
via a furnace and steam.
Bistillation
Bistillation
Bottoms
vacuum
tower
bottoms
vacuum qas oil
0ll qas
LF
Liqht coker qas oil
Coker nahtha
heavy coker
qas oil
Belayed
coker
FCC leed
hydrotreater
Crude oil
Liqht ends
hahtha
hydroqen
hydroqen
0ll qas
0ll qas
0ll qas 0ll qases
Liqht qasoline
Treated qasoline
Treated qasoline
Straiqhtrun qasoline
Relormates
Alkylate
heavy qasoline
hydroqen
asoline
hydrotreater
Alkylation unit
FCC qasoline
LF
hahtha
Bistillate
hydrotreater
Sourwater
strier
Sullur
recovery
unit
Coke
Biesel
Jet luel/kerosine
Cutter stock/
carbon black
manulacturinq
hydroqen
FCC qasoline
slitter
Amine
treatinq
Treatinq
Relinery luel qas
asolines
asoline
blendinq
hydroqen
hahtha
hydrotreater
Liqht nahtha
Relormer leed Catalytic
relormer
someri/ation
unit
Kerosine
Biesel
as oil
hydroqen
Fluidi/ed
catalytic
crackinq (FCC)
unit
FCC clarilied oil
Liqht cycle oil
0ll qas
Refiners worldwide face new regulations that
require them to reduce sulfur in transportation
fuels and, indirectly, intermediate products. Such
regulations have recently taken effect in some regions;
others will take effect in coming years.
In the US, sulfur content has been reduced to an average
30 ppm (wt) in motor gasoline and to 15-ppm (wt) maximum
for on-road diesel (ultralow-sulfur diesel; ULSD). This requirement
for on-road diesel practically always requires hydrotreating. Similar
regulations are pending or have been implemented in Europe, South
America, and Asia.
Hydrotreating is a process that employs hydrogen to remove sulfur and other
contaminants from refinery intermediate products and finished transportation
fuels (called hydrotreating feed). It is, therefore, the primary process refiners are
using to comply with the new regulations.
Processes
Several hydrotreating processes are typically found in a refinery and are similar in concept
but have different operating conditions and costs.
Naphtha hydrotreating A removes sulfur and nitrogen fromnaphtha that is typically fed to catalytic
reforming (reformer B ) and isomerization C units to increase the octane number so that this material
can be blended into gasoline D . Sulfur and nitrogen in the feed to the reformer are catalyst poisons, and
the hydrotreater must convert them to very low levels (0.5 ppm wt).
Naphtha hydrotreating feed comes from crude-oil distillation E or from thermal processes such as delayed
coking F and visbreaking. Distillate and gas-oil hydroprocessing units can also yield a small naphtha stream that
is usually processed in the naphtha hydrotreater.
Distillate hydrotreating G processes any of several refinery fuel products including jet fuel, on-road diesel, marine
diesel, railroad diesel, and home heating oil. Diesel hydrotreating, a form of distillate hydrotreating, removes organic sulfur
from diesel. The feed to distillate hydrotreating also comes from crude oil distillation, thermal processes, and fluid catalytic
cracking H units.
To allow for some contamination in the distillate-product distribution system, and therefore not exceed 15 ppm (wt) at the
point of sale, US refiners typically manufacture a ULSD product with a maximum sulfur content of about 7 ppm (wt). Other
distillate streams may or may not require hydrotreating, depending on their sulfur contents and that of other intermediate
refinery diesel streams.
In the future, most off-road diesel in the US will have to meet the 15-ppm (wt) sulfur specification.
Fluid catalytic cracker (FCC) feed hydrotreating I is an optional refinery process. In the FCC unit H , heavy gas-oil feed is
catalytically converted to gas/LPG, FCC gasoline, light cycle oil (a distillate fraction), slurry oil, and coke.
For FCC feed hydrotreating, typical feed sources are heavy atmospheric gas oil, vacuumgas oil, heavy gas oils fromthermal
processes (coking and visbreaking, for example), and deasphalted oils from solvent deasphalting. Solvent deasphalting
extracts additional gas oil from the heavy bottoms product from vacuum distillation J .
Technical terms
LHSV = Liquid hourly space velocity:
the ratio of the volume of oil processed to
the volume of catalyst on an hourly basis.
WABT = Wei ght ed aver age bed
temperature: normally calculated as the
reactor inlet temperature plus two thirds
of the reactor temperature rise.
Treat gas/chemical ratio, also known as
hydrogen availability: The volume of pure
hydrogen at the reactor inlet divided by
the total pure hydrogen consumption from
reactions (desulfurization, denitrification,
aromatics saturation, hydrocracking).
Petroleum fractions derived from crude
oils are characterized as virgin stocks, i.e.
virgin naphtha, virgin distillate, etc. This
is in contrast to fractions that are derived
fromsuch conversion processes as coking,
visbreaking and fluid catalytic cracking.
Generally the non-virgin materials are
more difficult to hydrotreat.
Hydrotreater feed Naphtha Distillate FCC feed FCC gasoline
LHSV, hr-1 3.0-10.0 0.5-2.5 0.5-1.0 2.0-5.0
Total pressure, psig 400 for virgin feeds; 800 for virgin feeds, 1,500-2,500 250-300
800 with significant 1,500 with 25%+ FCC Light Cycle
(15%+) coker naphtha Oil/Coker Distillate and
in feed 1,000+ppm (wt) feed nitrogen
WABT, F. 550-700 600-700 700-800 500-650
Treat gas, scf 500-800 1,000-3,000 2,500-5,000 1,000-3,000
hydrogen/bbl of feed For new designs, hydrogen in treat For new designs
gas/chemical consumption ratio hydrogen in treat
(also know as the hydrogen availability) gas/chemical
should be about 5.0 consumption ratio
should be about 5.0.
Chemical hydrogen 20-200 200-600 200-1,000 20-200
consumption, scf
hydrogen/bbl of feed
Other comments Reboiled stripping
instead of steam to ensure
dry feed to reformer.
Reactor conditions
9
F
J
I
E
A
C
B
K
D
N
G
H
M L
4
2
3
7
1
5
6
8
8
11
10
Modern Refinery
Content by the Mustang technical team: Ed Palmer, Process Engineering Manager,
Stan Polcar, Process Manager, and John McWilliams, Sr. Piping Designer/3D Admin.
Distributed in partnership with National Petrochemical & Refiners Association (NPRA)
Artwork & rendering: Beau Brown, Industrial3d.com
Graphic coordination: Chris Jones, Xenon Group | xenongroupdesign.com
Back copies of this poster may be obtained from PennWell. To order: call 713/963-6210; fax 713/963-6228;
e-mail posters@pennwell.com; or submit request to 1700 West Loop South, Suite 1000, Houston, TX. 77027.
Reproduction of the contents of this poster, in any manner, is prohibited without the consent of PennWell Corp. 2007
OIL & GAS JOURNAL
1700 West Loop South, Suite 1000
Houston, TX 77027 USA
www.ogjonline.com
Editorial direction and coordination from
David Nakamura, Refining/Petrochemical Editor
Warren R. True, Chief Technology Editor
Modern Refinery:
Hydrotreating

www.npra.org
NPPA speaks for the petrochemical and
rening industries on issues important to
their business. we seek to inform policy-
makers and the public how these industries
help improve their lives, strengthen the
economy, protect the environment and
promote national security.
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