Hydrotreating - UOP - A Honeywell Company

Handbook of Petroleum Processing
DOI 10.1007/978-3-319-05545-9_4-1
# Springer International Publishing Switzerland 2014
Hydrotreating in Petroleum Processing

Peter Kokayeff*, Steven Zink and Pamela Roxas
UOP – A Honeywell Company, Des Plaines, IL, USA
Abstract
Hydrotreating or catalytic hydrogen treating removes objectionable materials from petroleum
fractions by selectively reacting these materials with hydrogen in a reactor at relatively high
temperatures and at moderate pressures. These objectionable materials include, but are not solely
limited to, sulfur, nitrogen, olefins, and aromatics. The lighter distillates, such as naphtha, are
generally treated for subsequent processing in catalytic reforming units, and the heavier distillates,
ranging from jet fuels to heavy vacuum gas oils, are treated to meet strict product quality specifi-
cations or for use as feedstocks elsewhere in the refinery. Hydrotreating is also used for upgrading
the quality of atmospheric and vacuum resids by reducing their sulfur and organometallic levels.
Hydrotreaters are designed for and run at a variety of conditions depending on many factors such as
feed type, desired cycle length, and expected quality of the products. Until about 1980, hydrotreating
was a licensed technology being offered by a fairly large number of companies. From 1980 until the
end of the last century, hydrotreating catalysts were becoming more commoditized as the formula-
tions were less differentiated among the various suppliers. Many of the product quality specifica-
tions are driven by environmental regulations, and these regulations are becoming more stringent
every year. With the advent of ultra-low-sulfur fuel regulations ushering in the first decade of the
twenty-first century, however, it was required for hydrotreating research and development to deliver
quantum improvements in catalyst performance and process technology. This was accomplished in
the form of so-called Type II supported transition metal sulfide (TMS) catalysts, unsupported/bulk
TMS catalysts, improved bed grading catalysts and stacking strategies, advanced catalyst loading
techniques, improved trickle-flow reactor internals designs, and more effective catalyst activation
methodologies.
Keywords
Hydrotreating; Hydrodesulfurization; Hydrodenitrogenation; Resid; Gasoline; Distillate;
Upgrading; Desulfurization; Denitrogenation
Introduction
Hydrotreating or catalytic hydrogen treating removes objectionable materials from petroleum
fractions by selectively reacting these materials with hydrogen in a reactor at relatively high
temperatures at moderate pressures. These objectionable materials include, but are not solely limited
to, sulfur, nitrogen, olefins, and aromatics. The lighter materials such as naphtha are generally treated
for subsequent processing in catalytic reforming units, and the heavier distillates, ranging from jet
*Email: [email protected]
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fuels to heavy vacuum gas oils, are treated to meet strict product quality specifications or for use as
feedstocks elsewhere in the refinery. Hydrotreating is also used for upgrading the quality of
atmospheric and vacuum resids by reducing their sulfur and organometallic levels. Many of the
product quality specifications are driven by environmental regulations that are becoming more
stringent every year. Hydrotreaters are designed for and run at a variety of conditions depending on
many factors such as feed type, desired cycle length, and expected quality of the products; in general,
they will operate at the following ranges of conditions: LHSV, 0.2–8.0; H2 circulation, 300–4,000
SCFB (50–675 Nm3/m3); H2 partial pressure, 200–2,000 psia (14–138 bara); and typical SOR
temperatures ranging between 500 F and 740 F (260–393 C), with the lower limits representing
minimum operating conditions for naphtha hydrotreating and the higher values showing operating
conditions used for hydrotreating atmospheric resids. Until about 1980, hydrotreating was a licensed
technology being offered by a fairly large number of companies. From 1980 until the end of the last
century, hydrotreating catalysts were becoming more commoditized as the formulations were less
differentiated among the various suppliers. With the advent of ultra-low-sulfur fuel regulations
ushering in the first decade of the twenty-first century, however, it was required for hydrotreating
research and development to deliver quantum improvements in catalyst performance and process
technology. This was accomplished in the form of so-called Type II supported transition metal
sulfide (TMS) catalysts, unsupported/bulk TMS catalysts, improved bed grading catalysts and
stacking strategies, advanced catalyst loading techniques, improved trickle-flow reactor internals
designs, and more effective catalyst activation methodologies.
The common objectives and applications of hydrotreating are listed below:
• Straight-run and coker naphtha (catalytic reformer feed pretreatment) – to remove sulfur, nitro-
gen, and contaminants (e.g., Si) that otherwise would poison downstream, noble metal reforming
catalysts
• Pyrolysis gasoline and coke-oven light oil – to remove sulfur and nitrogen and to hydrogenate
di-unsaturates that would otherwise deactivate/foul downstream equipment and/or catalysts in the
aromatics complex
• LPG – to remove sulfur and nitrogen and to hydrogenate di-unsaturates that would otherwise
deactivate downstream, noble metal dehydrogenation catalysts
• Kerosene and diesel – to remove sulfur and to hydrogenate unsaturates, resulting in improved
properties of the streams (kerosene smoke point, diesel cetane, specific gravity) as well as storage
stability
• Shale oil – to remove sulfur, nitrogen, arsenic, and oxygen, resulting in improved properties of the
streams as above
• Lube oil – to improve the viscosity index, color, and stability as well as storage stability
• Used lube oil – to remove contaminants and blending package additives, which, for example, may
contain zinc and phosphorus, and to at least restore the quality to that of the original base oil
• Vegetable oils and animal tallows – to remove contaminants and to complete one step in the
conversion of triglycerides to jet, kerosene, and diesel fuels
• FCC feed – to improve FCC yields especially of gasoline and propylene, to improve the quality of
the gasoline and the diesel/light cycle oil, and to reduce catalyst usage and stack emissions
• Hydrocracking – to maximize the yield of ultra-low-sulfur diesel (ULSD) and to improve the
properties of hydrocracked fuels (naphtha sulfur and nitrogen, kerosene smoke point, diesel
cetane, specific gravity)
• Atmospheric and vacuum residua – to provide low-sulfur, low-metal fuel oils to effect conversion
and/or pretreatment for further conversion downstream
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Brief History
Hydrotreating has its origin in the hydrogenation of finely powdered, bituminous coal to liquid
hydrocarbons, accomplished by Berthelot in 1869 with a nascent hydrogen source, hydriodic acid
(Berthelot 1869). In 1897, Sabatier and Senderens published their discovery that unsaturated
hydrocarbons could be hydrogenated in the vapor phase over a finely powdered, reduced nickel
catalyst (Sabatier and Senderens 1897). Shortly after the turn of the century, Ipatieff extended the
range of feasible hydrogenation reactions by the introduction of elevated hydrogen pressures
(Ipatieff et al. 1900). At the time, the progress of the automobile industry was expected to entail a
considerable increase in the consumption of gasoline. This led to the experimental work by Bergius,
started in 1910 in Hanover, Germany, who sought to produce gasoline by cracking heavy oils and oil
residues as well as converting coal to liquid fuels. He realized that to remedy the inferior quality of
the unsaturated gasoline so produced, the hydrogen removed mostly in the form of methane during
the cracking operation has to be replaced by addition of fresh hydrogen. Thus, formation of coke was
avoided and the gasoline produced was of a more saturated character. Bergius also noted that the
sulfur contained in the oils was eliminated for the most part as hydrogen sulfide. Ferric oxide was
used in the Bergius process to remove the sulfur. Actually, the ferric oxide and sulfides formed in the
process acted as catalysts, though the activity was very poor. The first plant for hydrogenation of
brown coal was put on stream in Leuna, Germany, in 1927 (Stranges 1984). The plant utilized
unsupported molybdenum and tungsten sulfides (TMSs) to hydrogenate brown coal. The first TMS
catalysts supported on activated g-alumina were developed and in use during the early 1940s by
I.G. Farbenindustrie AG/Badische Anilin- und Soda-Fabrik (BASF) in Ludwigshafen, Germany.
Metal shortages while in wartime motivated the idea to disperse a relatively smaller quantity of
metals on an activated alumina support (Wu and Storch 1968). Among the first such catalysts
utilized industrially were catalysts 7,846 (NiMo) and 8,376 (NiW) (Weisser and Landa 1973; Pier
1949). The past large-scale industrial development of hydrogenation in Europe, particularly in
Germany, was due entirely to military considerations. Germany used hydrogenation extensively
during World War II to produce gasoline: 3.5 million tons were produced in 1944. The first
commercial hydrorefining installation in the United States was at the Standard Oil Company of
Louisiana in Baton Rouge in the 1930s. WWII plants were developed by Humble Oil and Refining
Company and Shell Development Company, though there was considerably less dependence on
hydrogenation as a source of gasoline. Even though hydrogenation has been of interest to the
petroleum industry for many years, hydrogen-consuming processes were seldom used industrially
due to the lack of low-cost hydrogen. This limitation was relieved in the early 1950s upon the advent
of catalytic reforming, making by-product hydrogen more readily available, thus motivating an
extensive and increased interest in processes that utilized such hydrogen to upgrade petroleum
stocks. As a result of the enormous growth of hydrotreating, as of the beginning of 2001, there were
more than 1,600 hydrotreaters operating in the world with a total capacity in excess of 39,000,000
B/D (4,800,000 MT/D).
Flow Schemes
Although the “hydrotreating process” has several different applications (e.g., hydrogenation,
hydrodesulfurization, hydrodenitrogenation, hydrodemetallation, etc.) and is used to process a
variety of petroleum fractions from LPG all the way to atmospheric residue, practically all units
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Feed H2
•F
Fig. 1 Schematic flow diagram of a hydrotreater
have the same flow scheme. It consists of a higher-pressure reactor section “R” and a lower-pressure
fractionation section “F.” This is shown schematically in Fig. 1 and is described below in general
terms.
Reactor Section
The reactor section consists of the following major pieces of equipment: feed pump, feed/effluent
exchangers, reactor charge heater, reactor(s), reactor effluent condenser, product separator, recycle
gas compressor, and makeup gas compressors. Additional equipment may be specified in some
hydrotreating units: fresh feed filters, reactor effluent hot separator, and recycle gas scrubber.
Figure 2 features a typical flow diagram of the UOP Unionfining™ Process, which includes a reactor
section and all the equipment described in the preceding section.
Feed Filters
It is preferable to route the feed directly from an upstream unit, bypassing intermediate storage.
When storage facilities are used, however, feed filters should be used. The purpose of the filters is to
trap corrosion products and other particulate matter entrained by the feed while passing through
intermediate storage. The feed filters are either automatic backwash filters operating on a pressure
drop setting or manual cartridge (disposable) filters.
Feed/Effluent Exchangers
Via a series of feed/effluent shell-and-tube exchangers, the reactor effluent preheats the reactor
charge before entering the reactor charge heater. This recovers as much heat as possible from the heat
of reaction and the sensible and latent heats of the reactor effluent. Liquid feed may be preheated
separately with reactor effluent exchange before combining with the recycle (treat) gas, depending
on the heat integration scheme.
Reactor Charge Heater

In most units, the fresh feed and recycle gas are heated together as “combined feed” to the desired
reactor inlet temperature in a combined feed charge heater. In units processing heavy feed, especially
the atmospheric residue units, the liquid feed is preheated separately in the reactor feed/reactor
effluent exchange, and only the recycle gas is heated in the heater upstream of the reactor.
Makeup Hydrogen System

Makeup hydrogen is typically obtained from hydrogen manufacturing plants, naphtha cracking
complexes, and/or naphtha catalytic reforming units. Depending on the pressure of the hydrotreating
unit, the makeup hydrogen might have to be compressed before introduction into the unit.
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Vgo unionfining unit

(Reactor section)
schematic flow diagram
Recycle gas
Feed Feed Reactor Reactor Hot Hot flash Recycle gas scrubber
filter surge charge separator drum compressor
drum heater
Gas
makeup
Fresh To off gas

Cold
feed scrubber
Cold flash
separator drum
Reactor Sour
To Sour
charge water
stripper water
pump
column
Water
To stripper injection
column
Fig. 2 Schematic flow diagram of a reactor section
Reciprocating compressors are typically used for this service. The makeup gas is introduced into the
recycle gas system.
Recycle Hydrogen System

After the reactor effluent’s gas and liquid phases are separated, the gas flows to the recycle gas
compressor. In some cases, the recycle gas will be sent first to an amine scrubber to remove most of
the hydrogen sulfide. Most often, the recycle gas compressor is a separate centrifugal machine, but it
could also be a part of the makeup gas compressors, as additional cylinders in a reciprocating
compressor. The recycle gas compressor is designed to pump a large volume of gas at a relatively
low compression ratio.
Recycle Gas Scrubbing

The recycle gas stream will typically contain hydrogen sulfide. The hydrogen sulfide reduces the
reactor hydrogen partial pressure and thus suppresses the catalyst activity. This effect is more
pronounced with a high-sulfur feed stream, and for the same feedstock, the heavier the cut, the
higher the sulfur content. Recycle gas scrubbing is typically included in the design of selective FCC
naphtha hydrotreaters to minimize the temperature severity of hydrotreating, which directly impacts
monoolefin hydrogenation and octane retention.
Reactor(s)
Once the feed and recycle gas have been heated to the desired temperature, the reactants enter the
reactor inlet. As the reactants flow downward through the catalyst bed, various exothermic reactions
generate heat, and the temperature increases. Multiple catalyst beds with interbed quenching may be
required, depending mostly upon the feedstock quality and the product specifications. Specific
reactor designs will depend upon several variables. Reactor diameter is typically set by the cross-
sectional liquid flux. As the unit capacity increases, the reactor diameter increases to the point where
two parallel trains would be considered. Reactor height is a function of the amount of catalyst and
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number of beds required. Depending on the expected heat of reaction, cold recycle gas or cold
product separator liquid is brought into the reactor at the interbed quench points in order to cool the
reactants and thus control the reaction rate. Good distribution of reactants at the reactor inlet and at
the top of each subsequent catalyst bed is essential for optimum catalyst performance. There are
many companies that design proprietary internals: reactor inlet diffuser, top liquid distribution tray,
quench section which includes quench inlet assembly, quench and reactant mixing device and
redistribution tray, as well as the reactor outlet device, or collector. Not all reactors are specified
with all the internals described above.
Reactor Effluent Water Wash

Cooling of the reactor effluent is accomplished in the feed/effluent exchangers, which are typically
the shell-and-tube design. Final cooling of the reactor effluent is obtained in air fin coolers and/or
water trim coolers. Water is injected directly into the stream before it enters the coolers to prevent the
deposition of salts. The salts would tend to corrode and foul the coolers. The sulfur and nitrogen
contained in the feed are converted to hydrogen sulfide and ammonia in the reactor. These two
reaction products combine to form ammonium salts that can solidify and precipitate as the reactor
effluent is cooled. Likewise, ammonium chloride may be formed if there is any chloride in the
system. The purpose of the water is to keep the salts of hydrogen sulfide and ammonia in solution
and not allow them to precipitate. Various companies have slightly different guidelines for the
quality of the water injection; in general, boiler feedwater is preferred.
Vapor/Liquid Separation
The exact method of separating vapor and liquid will vary depending on the optimum heat
integration scheme. Up to four separate vessels may be used to disengage and individually remove
vapor, water, and hydrocarbon liquid. A hot high-pressure separator is sometimes installed after the
feed/effluent exchangers to collect the heavier hydrocarbon material from the reactor effluent and
send it to fractionation via a hot low-pressure flash drum. The overhead vapor from the hot high-
pressure separator continues through an air cooler into a cold high-pressure separator. The
two-separator system is depicted in Fig. 2.
Hydrogen Purification
Increasing the recycle gas hydrogen partial pressure will decrease the catalyst deactivation rate.
Depending upon the feedstock and type of unit, additional measures may be taken to increase the
hydrogen purity. These measures may include hydrogen enrichment and/or membrane separation.
Fractionation Section
A schematic flow diagram of a typical fractionation section is shown in Fig. 3.
The function of the fractionation section is to separate the net reactor effluent into the desired
products. This can be accomplished with either a one- or a two-column fractionation scheme,
depending on the type of hydrotreating unit.
In the two-column scheme, the flash drum liquids combine and flow to a stripper column. Steam
and/or a fired heater reboiler is used to strip naphtha (if desired) and lighter material overhead. The
stripper bottoms stream flows to a fractionator where it is further separated into naphtha (if desired)
and heavier products. The fractionator feed is typically preheated with fractionator bottoms and a
fired heater before entering the column. Stripping steam is used to drive lighter material up the
column, and various product strippers are used to pull side-cut products to the desired specifications.
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Vgo unionfining unit

(Fractionation section)
schematic flow diagram
Product
Stripper Off-Gas Product fractionator Diesel
column Scrubber fractionator column stripper
feed heater
C3/C4
product
Boot
water
Sour Cold flash Naphtha
water drum vapor product
Hot flash
drum liquid
Stripping
stream Stripping
steam
Stripping
steam
Unconverted Diesel
Cold flash
oil product
drum liquid
Fig. 3 Schematic flow diagram of a fractionation section
Chemistry
The following chemical steps and/or reactions occur during the hydrotreating process (depending on
the impurities present):
• Sulfur removal, also referred to as desulfurization or hydrodesulfurization (HDS) in which the

organic sulfur compounds are converted to hydrogen sulfide
• Nitrogen removal, also referred to as denitrogenation or hydrodenitrogenation (HDN) in which
the organic nitrogen compounds are converted to ammonia
• Metal (organometallics) removal, also referred to as demetallation or hydrodemetallation (HDM),
in which the organometallics are converted to the respective metal sulfides
• Oxygen removal, also referred to as hydrodeoxygenation, in which the organic oxygen com-
pounds are converted to water
• Olefin saturation, in which organic compounds containing double bonds are converted to their
saturated homologues
• Aromatic saturation, also referred to as hydrodearomatization, in which some of the aromatic
compounds are converted to naphthenes
• Halides removal, also referred to as hydrodehalogenation, in which the organic halides are
converted to hydrogen halides
The first three types of compounds are always present, though in varying amounts, depending on
the source of feedstock. For example, naphtha will typically contain extremely low amounts of
organometallic compounds, while atmospheric residues may contain levels in excess of 100 wppm.
Some crudes contain much more sulfur in all the fractions when compared with other crudes. For
example, most middle eastern crudes contain much more sulfur than some crudes from Indonesia or
North Africa. The same is true for nitrogen levels. The other impurities are not always present. In
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general, the hydrotreating reactions proceed in the following descending order of ease:
(organometallic) metals removal, olefin saturation, sulfur removal, nitrogen removal, oxygen
removal, and halide removal. The contaminant removal in residue hydrotreating involves controlled
breaking of the hydrocarbon molecule at the point where the sulfur, nitrogen, or oxygen atom is
joined to carbon atoms. Some aromatic saturation also occurs. The chemistry of residue
hydrotreating is essentially that of contaminant removal. Some cracking occurs in residue
hydrotreating, but it is normally less than 30 vol% of the fresh feed charge.
In general, the hydrodesulfurization reaction consumes 100–150 SCFB/wt% change
(17–25 Nm3/m3/wt% change), and the hydrodenitrogenation reaction consumes 200–350 SCFB/
wt% change (34–59 Nm3/m3/wt% change). Typically, the heat released in hydrotreating is about
0.1–0.2 F/SCFB H2 consumed (0.35–0.70 C/Nm3/m3H2).
In general, the “general principles” concerning hydrotreating reaction rates, heats of reaction, and
hydrogen consumption are:
• Hydrodesulfurization and olefin hydrogenation are the most rapid reactions.

• Olefin hydrogenation liberates the most heat per unit of hydrogen consumed.
• Hydrodenitrogenation and hydrodearomatization are the most difficult reactions.
• Hydrogen consumption and heat of reaction are related.
Sulfur Removal
From the end of the last century until now, ultra-low-sulfur fuel specifications continue to tighten. By
2020, it is anticipated that most of the industrialized world will have legislated no more than
10 wppm sulfur in both motor gasoline and diesel products, consistent with the desire to improve
fuel economy and reduce vehicle emissions. Timelines for these changes are summarized in Fig. 4
(TransportPolicy.Net 2014).
Sulfur removal occurs via the conversion to H2S of the organic sulfur compounds present in the
feedstock. This conversion is sometimes referred to as desulfurization or hydrodesulfurization
(HDS). Sulfur is found throughout the boiling range of petroleum fractions in the form of many
hundreds of different organic sulfur compounds which, in the naphtha-to-atmospheric residue range,
can all be classified as belonging to one of the following six sulfur types: mercaptans, sulfides,
disulfides, thiophenes, benzothiophenes, and dibenzothiophenes. Typical reactions for each kind of
sulfur compound are shown below.
Mercaptans
R-SH þ H2 ! R-H þ H2 S
Sulfides
R1-S-R2 þ 2H2 ! R1-H þ R2-H þ H2 S
Disulfides
R1-S-S-R2 þ 3H2 ! R1-H þ R2-H þ 2H2 S
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Fig. 4 Selected timelines for introduction of new sulfur limits for motor fuels
Thiophene
Step (1)
+ 2H2 H2C = CH – CH = CH2 + H2S
S
Step (2)
H2 C ¼ CH-CH ¼ CH2 þ 2H2 ! H3 C-CH2 -CH2 -CH3
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Benzothiophenes
R
CH2-CH3
+ 3H2 + H2S
S
Dibenzothiophenes
S
+ 3H2 (1) (2) + H2
+ H2S
S S
+ H2
+ H2S
Most of the reactions are straightforward, with the exception of the hydrodesulfurization of
aromatic sulfur species. This reaction is more complex, since several routes are possible: direct
desulfurization, or hydrogenolysis to a biphenyl species, hydrogenation of one aromatic ring
followed by hydrogenolysis, and isomerization of sterically hindering alkyl groups in the
4- and/or 6- positions followed by the preceding pair of reactions. The latter of the three mechanisms
is not depicted. The relative rate of hydrogenolysis in the second step is much faster than the
hydrogenation in the first step (Dugulan et al. 2008).
Shown below is a ranking of the six sulfur types ranked on the basis of ease of removal:
Easiest to remove ! hardest to remove

Mercaptans ! sulfides ! disulfides ! thiophenes ! benzothiophenes ! dibenzothiophenes
The relative ease of removing sulfur from a particular hydrocarbon fraction depends greatly on the
sulfur types present. In naphtha fractions, much of the sulfur is present as mercaptans and sulfides,
which makes for relatively easy sulfur removal. In gas oil fractions, the majority of the sulfur is
present as benzothiophenes, naphthobenzothiophenes, and dibenzothiophenes. Hence, the sulfur is
much more difficult to remove from gas oils than from naphtha fractions. And the more difficult
sulfur species are found in the heavier fractions, which means that heavy gas oils are more difficult to
treat than light gas oils (Fig. 5).
Nitrogen Removal
Nitrogen is mostly found in the heaviest end of petroleum fractions in five- and six- membered
aromatic ring structures. Both the molecular complexity and quantity of nitrogen-containing
molecules increase with increasing boiling range, making them more difficult to convert. The
hydrodenitrogenation reaction proceeds through a different path from that of desulfurization. In
hydrodesulfurization, the sulfur is removed first and the resulting intermediate olefin is saturated; in
hydrodenitrogenation, the aromatic ring is saturated first and then the nitrogen is removed. This is
shown below.
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Relative Reaction Rates of Selected Sulfur Species

3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
Thiophene Benzothiophenes
Dibenzothiophenes 4, 6-Dimethyldibenzothiophene
Fig. 5 Relative reaction rates of selected sulfur species
Denitrogenation Mechanism
(a) Aromatic hydrogenation
+ 3H2
N
N
(b) Hydrogenolysis
+ H2 H3C–CH2–CH2–CH2–CH2–NH2
N
(c) Hydrodenitrogenation
H3 C-CH2 -CH2 -CH2 -CH2 -NH2 þ H2 ! H3 C-CH2 -CH2 -CH2 -CH3 þ NH3
Some typical examples of denitrogenation reactions are shown below:
(a) Amine
H3 C-CH2 -CH2 -CH2 -NH2 þ H2 ! H3 C-CH2 -CH2 -CH3 þ NH3
(b) Pyrrole
+ 4H2 H3C-CH2-CH2-CH3 and H3C-CH-(CH3)-CH3 + NH3

N
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(c) Pyridine
+ 5H2 H3C-CH2-CH2-CH2-CH3 and H3C-CH-(CH3)-CH2-CH3 + NH3

N
(d) Quinoline
-CH2-CH2-CH3
+ 4H2 + NH3
Nitrogen is more difficult to remove and consumes more hydrogen than sulfur removal because
the reaction mechanism often requires aromatic ring saturation prior to nitrogen removal. Hydro-
genation of associated aromatic ring structures is very dependent on hydrogen partial pressure and is
the rate-limiting reaction step in nitrogen removal. Nitrogen removal is therefore strongly dependent
on hydrogen partial pressure.
Oxygen Removal
Most petroleum crudes contain low levels of oxygen. The oxygen-containing compounds are
converted, by hydrodeoxygenation, to the corresponding hydrocarbon and water. The lower-
molecular-weight compounds are easily hydrodeoxygenated; however, the higher-molecular-weight
compounds – e.g., furans – are more difficult to convert. Shown below are typical examples of
hydrodeoxygenation:
Phenols
-OH
+ H2 + H2O
-R -R
Oxygenates
ðCH3 Þ3 -C-O-CH3 þ 2H2 ! ðCH3 Þ3 -CH þ H2 O þ CH4
Naphthenic acids
O
R C + 3H2 R-CH3 + 2H2O
OH
Olefin Saturation
Olefins are not found in petroleum, but are formed when processed in thermal or catalytic units. In
general, fractions containing olefins are unstable and thus must be protected from contact with
oxygen prior to hydrotreating to prevent the formation of polymer gums. That is especially true of
feedstocks derived from thermal cracking operations such as coking and ethylene manufacturing, or
naphtha cracking. Typical olefin saturation reactions are shown below:
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Hexene
C6 H12 þ H2 ! C6 H14
Cyclohexene
+ H2
Olefin saturation reactions are very rapid and highly exothermic. While the hydrodenitrogenation
reaction shows a heat of reaction of 1 Btu/lb of feed for each 100 ft3 of hydrogen consumed and the
hydrodesulfurization reaction generates 1 Btu/lb of feed for each 10 ft3 hydrogen consumed, the
olefin saturation generates 1 Btu/lb of feed for each 2 ft3 of hydrogen consumed. If proper care is not
exercised during operations, it can result in flow obstructions, such as excessive coking that can lead
to pressure drop buildup and/or poor liquid flow distribution through the catalyst bed(s). Diolefins
are readily hydrogenated to olefins at low temperatures, e.g., <375 F.
Aromatic Saturation
Saturation of aromatics is desirable for improvement of the properties of petroleum products, e.g.,
smoke point, diesel index, etc. The aromatics found in the naphtha to gas oil boiling range are
present as one-, two-, and three-ring aromatics – often referred to as mono-, di-, and tri-aromatics.
Typical reactions are shown below:
One ring – toluene
-CH3 -CH3
+ 3H2
Two rings – naphthalene
+ 3H2
Three rings – phenanthrene
+ 3H2
+ 3H2
The reactions shown above provide the mechanism by which polyaromatic compounds saturate,
via a stepwise mechanism: from tri-aromatics, to di-aromatics, to mono-aromatics. The end products
are naphthenic. Ring opening does not occur in hydrotreating (it does in hydrocracking) because a
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hydrotreating catalyst’s support is not designed with significant acidity, unlike a hydrocracking
catalyst. The aromatic saturation reaction is strongly favored by high hydrogen partial pressure.
Unlike all the other hydrotreating reactions, the amount of conversion of aromatics becomes
equilibrium limited at higher operating temperatures within the commercial operating range, since
the naphthene dehydrogenation reverse reaction becomes favored when temperature is increased.
The optimum temperature for maximum aromatic saturation depends on LHSV, hydrogen partial
pressure, and catalyst type but typically lies in the range of 670–730 F.
Mono-aromatic rings are much more difficult to saturate than the di- and tri-aromatic rings
because the saturation of the last aromatic ring requires the most energy. This means that as aromatic
saturation proceeds, there is little progress in total aromatics reduction until most, if not all, of the di-
and tri-aromatics have been saturated. The complete saturation of aromatics requires the application
of noble metal catalysts in a sulfur- and H2S-free environment and is generally not possible in
conventional hydrotreating with base metal sulfide catalysts.
Metals and Nonmetal Removal

Most metallic contaminants are present as organometallic compounds. Once deposited, these metals
contribute to catalyst deactivation; unlike coke, they cannot be removed by regeneration. In naphtha
hydrotreating, the most commonly occurring contaminants are arsenic from certain crude sources,
alkali metals (e.g., Ca, Na), mercury from certain condensates, and silica from
polydimethylsiloxane-based antifoam agents used in visbreakers, delayed cokers, and deepwater
drilling for crude oil. Gas oil streams may contain traces of nickel and vanadium in the heavier
fractions. These too are deposited on the catalyst and contribute to deactivation. Atmospheric
residua can contain metals, almost exclusively Ni and V, in the 20–500 ppm range. Hydrodeme-
tallation of that type of feedstock is an important goal of processing and special hydrodemetallation
catalysts are applied for that purpose. Hydrodemetallation of nickel and vanadium occurs before any
substantial hydrodesulfurization and conversion of the feedstock take place:
R-Me þ H2 S ! R-H2 þ MeS
Arsenic trapping catalysts, necessary for trapping organo-arsine contaminants such as triethylarsine,
are typically NiS based. These trapping catalysts rely on arsenic binding with NiS to form nickel
arsenides. Higher operating temperatures lead to greater arsenic pickup. In the case where arsenic
and silica are both present, it is advantageous to utilize a moderate concentration of Ni, as in
10–15 wt%, so that the trapping catalyst will still have sufficient surface area to trap silica.
Alkali metals can originate from various crudes, from mis-operation of the crude desalter, and
from various operations which utilize caustic soda. Alkali metals adsorb to the acid sites of the
catalyst support, reducing activity. Their presence may also be indicated by a rapid increase in
pressure drop, especially in the layers above the primary hydrotreating catalyst(s). During catalyst
regeneration, the presence of alkali metals tends to sinter the catalyst surface, resulting in surface
area loss beyond what is typically observed.
Mercury contaminants can generally be classified as hydrocarbon soluble, water soluble, and
asphaltenic. These can be found, in various proportions, within those crudes extracted near tectonic
plate boundaries. Elemental mercury and alkyl-mercury compounds will exit a crude column with
the product streams according to their relative volatility, from the LPG through to the heavy diesel.
Water-soluble mercury would be found in the heels of crude storage vessels and in the aqueous
drawoff from desalters. Asphaltenic mercury can be found in the atmospheric resid and vacuum
resid refinery streams. Asphaltenic mercury can be converted to the lighter, hydrocarbon-soluble
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forms of mercury through hydroprocessing, which can be problematic for an equipment that
processes finished product streams, since elemental mercury will form amalgams with
Cu-containing alloys and with equipment constructed at least in part of aluminum, leading to
embrittlement failures. In general, mercury is not substantially trapped by typical hydrotreating
catalysts, so installation of a posttreat bed of mercury-trapping adsorbent may be needed to prolong
downstream equipment life and to otherwise satisfy market requirements (Hadden et al. 2010).
Silica guard catalysts, loaded above the primary HDS catalysts in naphtha hydrotreaters, are
designed with high surface area. These catalysts are often designed with a modest hydrogenation
function via the NiMoS active phase. The heat release of hydrogenation in this reactor drives the
silica capacity higher than an equivalent silica guard support without a NiMoS active phase. The
adsorption mechanism is directed by the available surface area and the operating temperature, such
that higher temperatures and surface areas result in greater silica capacities. Silica adsorption can be
tracked by proxy via the regular monitoring of the hydrodenitrogenation performance, rather than
the hydrodesulfurization performance. Several products of polydimethylsiloxane decomposition
have been identified. It has been proposed that the decomposition products’ silanol groups react with
the alumina support hydroxyl groups (Chainet 2012).
Halide Removal
Organic halides, such as chlorides or bromides, can be present in petroleum fractions at trace levels.
Under hydrotreating conditions, organic halides are largely converted to the corresponding hydro-
carbon and hydrogen halide. The typical reaction is shown below:
-CH2-CH2-CH2-Cl -CH2-CH2-CH3
+ 4H2 + HCll
With the above to serve as an introduction and overview, a number of important hydrotreating
applications are presented below in greater detail.
Distillate Hydrotreating
As specifications for diesel fuels became ever more stringent, especially with regard to sulfur but
also with regard to aromatics and density, improved hydrotreating technology is needed to satisfy the
new specifications. This has led to the development of ever more active catalysts, e.g., Type II
hydrotreating catalysts, and an intensification of research and development efforts aimed at improv-
ing hydrotreating fundamentals understanding.
Catalytic Chemistry of Diesel Desulfurization

Full-range diesel has a rather broad boiling range, from 300 F to 700 F, and contains a very
broad range of sulfur compounds ranging from lower-molecular-weight alkyl sulfides and
benzothiophenes through dibenzothiophene, substituted dibenzothiophenes, and higher-molecular-
weight naphthobenzothiophenes. Generally, all sulfur compounds boiling lower than 4-
methyldibenzothiophene undergo rapid desulfurization at conditions required for production of
10 wppm sulfur diesel (ULSD).
Examples of typical sulfur compounds found in diesel fuels are presented below, ranging from the
easiest sulfur compounds to convert to the most difficult:
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Ethylhexyl sulfide:
Benzothiophene:
Dibenzothiophene:
4-methyldibenzothiophene:
4,6-dimethyl dibenzothiophene:
4-ethyl, 6-methyl-dibenzothiophene:
The most difficult sulfur compounds to desulfurize are the substituted dibenzothiophenes,
especially those where the substituent is adjacent to the sulfur atom, in the 4- position or in the 4-
and 6- positions for the case of double substitution. These compounds, such as 4-
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Fig. 6 Comprehensive GC 3D image of hydrocarbon content of distillate
methyldibenzothiophene and 4,6-dimethyldibenzothiophene and similar structures, present the most

difficult compounds to desulfurize.
Analytical Characterization
Approximately 10 years ago saw the introduction of a powerful new analytical technique applied
to the characterization of petroleum fractions, comprehensive gas chromatography (GC), or
“two-dimensional” GC, commonly referred to as GCxGC. While the description of the method
may be found elsewhere, the results offer much greater insights into the chemical composition of
petroleum fractions than was possible previously. A comprehensive GC 3D representation of the
hydrocarbon structures present in a distillate is shown in Fig. 6.
The paraffinic structures appear as spikes along the x-axis with increasing molecular weight.
Single-ring aromatics appear as families of spikes angling at a 45o angle to the right, again with
increasing molecular weight as one progresses to the right from one family to the next, e.g., from C3
benzenes to C4 benzenes. The larger spikes, beyond the indane “range,” are the di-aromatics
(naphthalenes) again arranged in “families” of increasing molecular weight. The next, smaller,
series of spikes are three-ring aromatics, followed by traces of multi-ring aromatics. All compounds
may be identified and quantified to fully characterize the composition of the distillate.
A similar GCxGC analysis focusing on sulfur compounds is shown in Fig. 7.
The type of compound is shown, e.g., thiophene, benzothiophene, or dibenzothiophene, as well as
the extent of substitution on the ring.
The same can be accomplished for nitrogen species (Fig. 8).
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Fig. 7 Comprehensive GC 3D image of sulfur compounds in distillate
Catalysts and Reactions

Both Co/Mo and Ni/Mo catalysts have been employed in the hydrotreatment of distillate fuels.
While, in the early stages of development, the Ni/Mo catalysts were judged to be slightly more active
in hydrodesulfurizing diesel fuels to ULSD (<10 wppm Sulfur) specifications, more recent devel-
opments have provided Co/Mo catalysts with equivalent activity to ULSD. The observations that
Ni/Mo catalysts may be more active for ULSD is in accord with the theory that for the desulfuri-
zation of the most difficult sulfur molecules, dimethyldibenzothiophenes with substituent groups in
the 4- and 6- positions, such as 4,6-dimethyldibenzothiophene, one of the rings needed to undergo
saturation of one of the rings, allowing the sulfur atom to be more accessible due to the greater
flexibility of the saturated ring. This pathway for desulfurization was termed the “hydrogenation”
pathway and was most pronounced over Ni/Mo catalysts with their higher activity for saturation.
The other pathway involved direct abstraction of the sulfur atom, and formation of H2S was termed
the “direct abstraction” route and was the dominant route on Co/Mo catalysts.
The direct abstraction reaction is depicted below:
+ 2H2 + H2S
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Fig. 8 Comprehensive GC 3D image of nitrogen compounds in distillate
The “hydrogenation” pathway, in simplified form, is
+ 2H2
S S
followed by
+ 3H2 + H2S
There has been considerable debate as to which pathway is dominant; it is likely that both are
active, although to differing degrees, on modern Type II catalysts. For the case of the “hydrogena-
tion” pathway, it may be inferred that the reversible saturation of one ring may be limiting at low
pressures. This issue was addressed by Jones and Kokayeff (Jones et al. 2005) as well as Ho
(Ho 2003, 2004).
While these sulfur compounds are the most difficult to desulfurize and present the greatest challenge
to achieving ULSD (<10 wppm S diesel), an additional complication is the inhibition by nitrogen
compounds. While inhibition by nitrogen has been known for some time, the magnitude of the
inhibitory effect can only been appreciated when deep desulfurization to ULSD levels is required.
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Nitrogen Compounds
The most difficult to convert nitrogen compounds present in diesel are the carbazoles.
Carbazole
Methyl Carbazole
1,2-Dimethyl Carbazole
1,8-Dimethyl Carbazole
The carbazole compounds boil within the same boiling range as the substituted
dibenzothiophenes, 620–660 F. At conditions that desulfurize the feed to <10 wppm S,
hydrodenitrogenation is very extensive and is essentially complete.
Aromatics
Aromatic compounds are another class of compounds that are of importance in the hydrotreating of
distillate fuels. Aromatic compounds may be classified in three main classes – multi-aromatics (3+
condensed rings), di-aromatics, and mono-aromatics.
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2-Ethyl-7-methylanthracene
C
H2
1,7-Dimethylanthracene
7-Ethyl-2-methyl-1,2,3,4,4a,9a-hexahydroanthracene
C
H2
7-Ethyl-2-methyl-1,2,3,4,4a,9,9a,10-octahydroanthracene
H2
C
Saturation reactions of aromatic compounds proceed sequentially
The saturation reactions are exothermic and reversible. These reactions consume hydrogen (not
shown) but also improve the quality of the diesel fuel by increasing the cetane number; therefore,
they are not necessarily undesirable, and distillate hydrotreater pressures and catalyst choices are
sometimes dictated by the desire to achieve a given cetane number. Additionally, there is evidence
that aromatics may inhibit the desulfurization of the most difficult, sterically hindered
dibenzothiophenes, sulfur species (Jones et al. 2004).
Feedstocks
Feed to a distillate hydrotreating unit may be any blend or combination of straight-run distillate
(SRD), coker distillate (LCGO), and light cycle oil (LCO).
Straight-run distillate is, as the name implies, derived from the distillation of crude oil and is the
cut obtained crude column, boiling in the range of 300 F to 730 F. Straight-run distillates are
characterized by high API gravities, in the range of 28–32 and sometimes higher and low levels of
sulfur (0.5–1.5 wt%), nitrogen (40–100 wppm), and aromatics (usually <20 wt% total).
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Coker distillates, while boiling in the same range as straight-run distillates, are derived from
coking operations and differ from straight-run distillates in that they contain greater amounts of
sulfur (up to 2.5–3.0 wt are possible), higher levels of nitrogen (500–1,500 wppm), and somewhat
higher aromatics content. The additional feature that sets them apart is the presence of olefins
(typically measured as a bromine number) with a bromine number of 10–30. Due to the olefin
content and the higher aromatics content of coker distillates, their processing in a hydrotreater is
accompanied by a significant temperature rise due to the exothermic saturation reactions of olefins
and aromatics. Finally, the presence of fragments of the Si-based antifoam agent used in cokers will
deactivate the hydrotreating catalysts processing the coker streams.
Light cycle oils are characterized by low gravities (API gravities in the range of 12–22) and high
levels of aromatics. Aromatics levels in LCOs may be as high as 70 wt% with the di-aromatics being
the most prevalent. A typical aromatics distribution of an LCO containing 70 wt% aromatics may be
10 wt% mono-aromatics, 45 wt% di-aromatics, and 15 wt% tri-aromatics. The concentration of
sulfur in an LCO may range from 500 wppm (for an LCO derived from an FCC with an FCC feed
pretreater) to 2 wt% for FCC units processing high-sulfur feeds without a FCC feed pretreater.
Nitrogen levels are not usually very high, reaching into several hundred wppm. Processing LCO in a
hydrotreater is accompanied by high hydrogen consumption due to the saturation of the aromatic
compounds and high heat release and temperature rise due to the exothermic nature of the saturation
reactions. Temperature control is important due to the rapid saturation rate of the multi-ring
aromatics.
Process Configuration
A simplified process flow diagram of a distillate hydrotreater is shown in Fig. 9.
The feed enters the feed surge drum from which it is pumped through a bank of feed/effluent
exchangers, is mixed with recycle gas, is heated to reaction temperature, and enters the reactor.
Reactor effluent is passed through a bank of feed/effluent exchangers and a fin fan cooler and then
enters the separator. The gas is recovered and sent to an amine scrubber to remove hydrogen sulfide
and ammonia and then routed to a recycle gas compressor and recycled to the reactor. The liquid
product is then directed to a flash drum, where any light gases are recovered overhead while the
hydrocarbon is routed to a stripper to remove any dissolved hydrogen sulfide and ammonia in the
product as well as any wild naphtha formed. The stabilized product is then sent to blending or
storage. Wash water is added to the reactor effluent just upstream of the air fin cooler to absorb the
ammonia produced in order to avoid precipitation of ammonium hydrosulfide salts in the colder
sections for the plant.
The process flow diagram shows one quench location between two catalyst beds. The number of
beds and quenches will depend on the type of feed being processed with SR distillates requiring only
one point while LCGOs and LCOs requiring three or more beds with interbed quenches to control
temperature rise.
Process Conditions
Process conditions applied in distillate hydrotreating today are much more severe than they were in
the past. This is due primarily to the requirement to produce ULSD (ultra-low-sulfur diesel, i.e., with
a sulfur level <10 wppm). Typical process conditions are shown in Table 1.
The variation in process conditions is due to a number of factors including feedstock character-
istics, such as sulfur content and nitrogen content, feedstock type, and process objective:
hydrodesulfurization to ULSD levels and/or cetane improvement. Note that conditions to effect
significant improvements in cetane are usually sufficient to produce ULSD sulfur specifications.
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Simplified Process Flow Diagram

Distillate Hydrotreating Unit
Reactor Recycle Gas

Compressor
Reactor Charge
Heater Lean Amine
Makeup Amine
Wash Off Gas
Hydrogen Scrubber
Water to Refinery
Rich Amine
Wild Naphtha
Flash Drum to Refinery
Separator
Fresh Sour
Feed Water
Diesel
Product to MP Steam
Refinery Reactor
Stripper
Effluent
Fig. 9 Simplified process flow diagram of a distillate hydrotreater
Table 1 Distillate hydrotreater typical process conditions

Feed type SRD (straight run) LCGO (coker distillate) LCO (Light cycle oil)
LHSV, h1 1.5–2.0 1.0–2.0 0.75–1.5
SOR temperature, F ( C) 630–660 (330–350) 640–680 (340–360) 670–710 (355–375)
Pressure, psig (barg) 600–700 (41–48) 700–800 (48–55) 750–1,000 (50–70)
H2/Ol, SCF/B (Nm3/m3) 1,500 (250) 2,000 (340) 2,000 (340)
Naphtha Hydrotreating
Introduction
Naphtha is a general term that refers to the lightest liquid fraction of material in the refinery. A full
boiling range naphtha typically has an initial boiling point of 85 F (30 C) and a final boiling point
ranging from 380 F to 420 F (193–215 C), which roughly corresponds to C5 through C12
material. The back-end cut point of full boiling range naphtha ultimately depends on the individual
refinery’s configuration and whether the objective is to maximize gasoline, diesel, or petrochemical
feedstock production.
Straight-Run Versus Cracked Naphtha

Naphtha can be broadly categorized as either straight-run or cracked naphtha. Stabilized naphtha
from the crude column is referred to as straight-run material, since it has not been exposed to any
severe thermal or catalytic process conditions and therefore has a negligible olefins content. In
contrast, naphtha produced from a carbon rejection process, such as a coking or fluidized catalytic
cracking, is considered a cracked stock and will contain a significant olefins content. More
specifically, cracked naphtha will contain both monoolefins and diolefins; the reactivity of these
olefin species requires specific design considerations.
This section will primarily focus on straight-run and coker naphtha, since these two streams often
share the same disposition in the refinery. When producing gasoline, refiners tend to handle FCC
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Table 2 Properties of naphtha streams

Straight-run naphtha Coker naphtha
Sulfur, wppm 500 5,700
Nitrogen, wppm 10 150
Silicon, wppm 0 3–7
Diene, wt% Nil 3
Olefins, wt% 0 25
naphtha differently, since it has a relatively higher octane value and therefore it requires selective
desulfurization to meet final gasoline product sulfur specifications.
In addition to the difference in olefin content, straight-run naphtha contains less sulfur and
nitrogen than its coker naphtha counterpart from the same crude source. Furthermore, coker naphtha
also contains silicon due to the use of antifoaming agents in the upstream coking unit, which can
negatively affect hydrotreating catalyst as well as catalysts in downstream operating units, such as a
naphtha reforming process.
Table 2 provides an example of typical properties of straight-run naphtha compared to that of
coker naphtha.
Naphtha Disposition
For refineries that produce gasoline, the inherent octane values of the straight-run and coker naphtha
stream are too low to allow blending of the entire stream into the gasoline pool. To ensure that the
naphtha stream can be fully utilized for gasoline production, the refiner will send the naphtha stream to
a catalytic naphtha reforming unit to increase the stream’s octane value, primarily via dehydrogenation
of naphthenes to aromatics. Prior to being processed in the reforming unit, the naphtha stream needs to
be effectively hydrotreated to minimize the presence of organic sulfur, nitrogen, other trace contam-
inants, and olefins to avoid poisoning of the precious metals reforming catalyst and fouling its
continuous regenerator. The final liquid product from the reforming unit is often referred to as
reformate and can be used as a low-sulfur (sulfur-free), high-octane gasoline blend component.
Alternatively, some refiners choose to minimally hydrotreat their naphtha stream and sell the
lightly treated naphtha on the market as feedstock for petrochemicals production. In areas with high
bitumen crude production, naphtha can also be utilized as a diluent to improve the properties of
bitumen crude for transportation.
Processing Objectives and Considerations

Table 3 summarizes the recommended hydrotreated naphtha quality for feed to a naphtha reforming unit.
In order to achieve the reformer feed quality, the below contaminant removal reactions need to
take place in the presence of the appropriate grading material and hydrotreating and under the right
set of process conditions. In the era of leaded gasoline, gasoline re-run through the naphtha
hydrotreater also required hydrodemetallation to prevent lead and other metals from poisoning the
naphtha reforming catalyst.
Desulfurization (HDS for hydrodesulfurization) difficulty depends on the type of sulfur molecule,
such as mercaptan, sulfide, thiophenol, thiophene, or benzothiophene sulfur. Relatively, mercaptan
sulfur is the easiest type of sulfur to remove, whereas benzothiophene is approximately 15 times
harder to remove than mercaptan sulfur. Sulfurs contained in an aromatic structure are removed by
initially opening the ring, removing the sulfur molecule, and saturating the resulting olefin molecule.
Denitrogenation (HDN for hydrodenitrogenation) is generally more difficult than desulfurization
due to the structure of the nitrogen compound. Nitrogen contained in an aromatic structure is
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Table 3 Reformer feed specifications

Product
Sulfur, wppm 0.5 max
Nitrogen, wppm 0.5 max
Silicon, wppm Nil
Diene, wt% Nil
Olefins, wt% Nil
removed via a different mechanism than sulfur contained in an aromatic compound. In

denitrogenation, the aromatic ring is first saturated, then the ring is cleaved, and finally the nitrogen
molecule is removed. Since aromatic saturation is required to remove aromatic bound nitrogen, the
design pressure of the hydrotreating unit is more sensitive to the nitrogen content of the feed rather
than the sulfur content of the feed.
Olefin saturation is a relatively rapid reaction that occurs alongside with desulfurization and
denitrogenation. There are two main types of olefins to consider when processing cracked naphtha
stock: diolefins or dienes (molecules containing two double bonds) and monoolefins (molecules
containing a single double bond).
Dienes can potentially polymerize and form gums if introduced to hydrotreating catalyst and
hydrogen at the typical temperatures required for hydrodesulfurization and denitrogenation. Gum
formation can either occur in feed heat exchangers or at the top of the first reactor catalyst bed,
leading to fouling and pressure drop issues, which could ultimately lead to an unplanned unit
shutdown and shortened cycle length.
For combined naphtha streams with a significant amount of diene content, the stream can first be
treated in a separate diolefin saturation reactor to minimize the risk of gum formation. The diolefin
reactor utilizes a relatively low-activity hydrotreating catalyst and operates within a low enough
temperature range to ensure the diolefin saturation reaction preferentially occurs instead of the
polymerization reaction. After the dienes are stabilized, the naphtha stream can then be heated up
and sent to a second reactor loaded with the main hydrotreating catalyst to complete the removal of
sulfur and nitrogen.
Once the diene content of a cracked naphtha blend is addressed, the next consideration focuses on
the monoolefin molecules. The olefin saturation reactions occur fairly rapidly in the main
hydrotreating reactor and result in a substantial amount of heat release. The reaction occurs so
readily that at start of run conditions the majority of the olefins are saturated within the first bed of a
hydrotreating reactor, resulting in a significant heat rise across the first bed, and smaller temperature
rises in the following bed. It is important to manage the heat released due to olefin saturation in order
to prevent coking, catalyst sintering, or uneven catalyst utilization across the different catalyst beds.
This can be achieved by recycling some of the olefin-free reactor product with the fresh feed in order
to dilute the olefins available for saturation. Ultimately, the proper management of olefin heat release
is required to achieve the desired catalyst cycle length in the main hydrotreating reactor.
Potential for Recombination with Cracked Stock

Due to presence of olefins in coker naphtha material, the potential for mercaptan recombination
exists. The below equation describes the equilibrium between mercaptans and olefin and H2S
present in the reactor. It is desirable to favor the left-hand side of the equation so that the sulfur
content from the feed is present in the off-gas from the unit instead of the liquid product. This can be
done by installing a relatively small posttreat reactor that operates at a lower condition than the main
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Table 4 Naphtha hydrotreater operating conditions

SR naphtha only SR and coker naphtha
Pressure, psig (barg) 300–500 (21–35) 500–800 (35–50)
Main HT reactor LHSV, h1 4–12 2–8
Gas-to-oil ratio, scf/bbl (Nm3/m3) 250–400 (40–75) 900–3,000 (150–500)
hydrotreating reactor, which favors the left-hand side of the equation and reduces the amount of
mercaptan sulfur than can be found in the hydrotreated naphtha material:
R ¼ R0 þ H2 S $ R-R0 -SH
Typical Operating Conditions

Table 4 compares the general range of operating conditions for the main hydrotreating reactor for
both a straight-run naphtha hydrotreating unit and a coker naphtha hydrotreating unit.
Pressure
Hydrotreating feeds with a significant amount of coker naphtha material typically contain higher
amounts of nitrogen, which requires the hydrotreating reactor to operate at higher pressures to ensure
the appropriate denitrogenation reactions take place to meet the 0.5 wppm nitrogen specification for
reformer feed.
LHSV
In addition to higher sulfur and nitrogen contaminant levels in coker naphtha feed blends, the
presence of Si also requires the addition of trapping material, which lowers the liquid hourly space
velocity (LHSV) in the hydrotreating unit. Liquid hourly space velocity is the liquid feed rate
divided by the catalyst volume and is expressed in units of inverse time. LHSV is inversely
proportional to the liquid residence time in the catalyst. The amount of Si trap required depends
on the concentration of Si in the feed blend, the trapping capacity of the hydrotreating catalyst or
guard material, and the desired cycle length:

Charge rate ft3 =h or m3 =h
LHSV ½1=h ¼
Volume catalyst ft3 or m3
Gas-to-Oil Ratio
A minimum H2 partial pressure in the reactor is required to ensure reasonable rates of reactions and
additionally to prevent possible coking of the catalyst. As summarized in the table above, higher
levels of contaminants require higher levels of gas-to-oil ratio in the hydrotreating unit.
The gas-to-oil ratio is calculated as follows:
Total gas to reactors ðSCFH or Nm3 =hÞ

Gas to oil ratio ½SCFB ¼
Raw oil charge ðBPH or m3 =hÞ
Diene Reactor
A diene reactor typically operates with a LHSV varying from 3 to 6 h1 and a gas-to-oil ratio ranging
from 250 to 1,000 scf/bbl (40–170 Nm3/m3).
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Make-up Recycle Gas

Hydrogen Compressor
Feed
Main
Hydrotreating Separator Stripper
Reactor
Fig. 10 Simplified process flow diagram of a naphtha hydrotreater
Posttreat Reactor
The posttreat reactor LHSV can range from 12 to 18 h1. Since the total reactor effluent is sent to the
posttreat reactor prior to any gas-liquid separation, treat gas is primarily introduced as a quench to
ensure the posttreat reactor operates at a low enough temperature to favor the formation of H2S and a
saturated hydrocarbon over the formation of a mercaptan. For additional assurance of satisfying
naphtha reforming and paraffin isomerization feed sulfur requirements, a sulfur guard can be applied
to treat the stabilized product. NiS-based adsorbents are typically applied in sulfur guard bed
services.
Figure 10 provides a simplified flow diagram of a straight-run naphtha hydrotreating unit. Typically
a recycle gas scrubber is not required when hydrotreating straight-run naphtha alone. The stabilized
product from the bottom of the stripper unit can either be sent directly to the reforming unit as feed or
be split into light and heavy naphtha portions in a downstream naphtha splitter.
Figure 11 presents a simplified flow diagram of a typical coker naphtha hydrotreating unit.
Additional pieces of equipment are required to address the higher levels of sulfur and nitrogen
contaminant as well as the presence of olefins in coker naphtha material. As discussed earlier, the
coker naphtha hydrotreating unit will also contain a diene reactor and a posttreat reactor. Another
differentiating feature in the coker naphtha flow scheme is the recycle of treated product with fresh
feed to manage the exotherm in the main hydrotreating reactor. Lastly, a recycle gas scrubber will
typically be specified to remove H2S and NH3 from the recycle gas stream to minimize inhibition of
catalyst activity in the main hydrotreating reactor.
Desulfurization of FCC Gasoline

Introduction
While hydrotreating of most other feedstocks is characterized by a desire for the most active catalyst
to effect a given conversion (whether of sulfur, nitrogen, or aromatics), the case of desulfurization of
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Recycle Gas RG
Make-up Compressor Scrubber
Hydrogen
Amine
Feed
Liquid Recycle
Main
Diolefin Post Treat
Hydrotreating Separator Stripper
Reactor Reactor
Reactor
Fig. 11 Simplified process flow diagram of a coker naphtha hydrotreater
FCC gasoline is unique in that it is characterized by selectivity rather than activity considerations.
Specifically, it is desired to reduce the sulfur level to the required specification while minimizing the
saturation of olefins and subsequent octane loss.
Composition of FCC Gasoline

FCC gasoline is composed of n-paraffins, i-paraffins, n-olefins, i-olefins, cyclic olefins, naphthenes,
and aromatics. The desirable, high-octane, components are olefins and aromatics and, to a lesser
extent, i-paraffins.
Sulfur compounds present in FCC gasoline include mercaptans, sulfides, and thiophenes as well
as benzothiophenes. While these compounds do have differences in reactivity, i.e., some undergo
desulfurization more easily than others, the differences in reactivity are not nearly as pronounced as
observed for sulfur compounds present in distillates. The most difficult sulfur compounds to
desulfurize in FCC gasoline are thiophenes with substituent groups in the 2- position, e.g.,
2-thiophene, 2-ethylthiophene. 2,5-dimethyl thiophene, and 2-ethyl-5-methyl thiophene. While
these compounds may be more difficult to desulfurize than the sulfides and mercaptans, the greatest
complicating factor in the desulfurization of FCC gasoline is recombination, i.e., the formation of
mercaptans from the olefins present in the feed and the H2S formed during desulfurization.
Recombination
Recombination is the name applied to the reaction of olefins with H2S to form mercaptans:
R ¼ R0 þ H2 S $ R-R0 -SH
Recombination is a reversible reaction that approaches equilibrium at conditions used to effect

desulfurization. It is an exothermic reaction and becomes less favorable with increasing temperature.
To fully appreciate the complications caused by this reaction consider the following expression for
the equilibrium between the species involved, olefins, H2S, and mercaptans:
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PRSH
K¼
P0 PH2 S
This may be rewritten as
WRSH ¼ f KWo PH2 S
where WRSH is the weight fraction (in wppm) of mercaptan in the liquid hydrocarbon, Wo is the
weight fraction of olefins in the liquid hydrocarbon, PH2S is the partial pressure of H2S, K is the
equilibrium constant, and f is a conversion factor.
The amount of recombinant mercaptan remaining in the liquid hydrocarbon is dependent upon the
concentration of olefins present and the partial pressure of H2S. One may simplify this a bit further
for clarity as follows:
WRSH ¼ f KWo WFS
where WFS is the sulfur content of the feed, in wppm.

What can be gleaned from this is that the amount of recombinant mercaptan that will remain in the
gasoline is dependent on the weight fraction of olefins and the sulfur content of the feed, where it was
assumed that all the sulfur content originally present in the feed is converted to H2S. The higher the
olefin content of the product (it is desired to preserve olefins) and the higher the sulfur content of the
feed, the higher the recombinant mercaptan sulfur that will remain in the gasoline, thus placing a
limit on the extent of “desulfurization” that is possible to achieve.
An additional complication arising from recombination is the loss of olefins by the desulfurization
of the mercaptans:
R ¼ R0 þ H2 S $ R-R0 -SH
R-R0 -SH þ H2 ! R-R0 þ H2 S
Thus, while the formation of recombinant mercaptans is a reversible, equilibrium-dominated

reaction, there is also the “drainage” reaction, the desulfurization of the mercaptan, which, in
combination, provides an alternate path for olefin loss in addition to the conventional olefin
saturation reaction. Complications presented by the recombination reaction in FCC gasoline desul-
furization are covered by Leonard and Kokayeff (Leonard et al. 2006).
Process Considerations
The three main process licensors of hydrotreating technology for processing FCC gasoline are
ExxonMobil (SCANfining™ Process), IFPEN/Axens (Prime-G+™ process), and Honeywell UOP
(SelectFining™ Process). While all three process licensors offer a number of different flow schemes
based on feed characteristics, e.g., sulfur level, and product targets, these technologies have much in
common.
Saturation of Diolefins
Besides olefins, FCC gasoline contains diolefins which may cause fouling of heat exchanger
surfaces as well as pressure drop in the hydrotreating reactor and catalyst deactivation by deposition
of coke. The removal of diolefins is accomplished in a similar manner as is done for coker naphtha
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hydrotreaters, i.e., by processing the feed at mild conditions over a hydrotreating catalyst.
This simple procedure effects the saturation of diolefins to monoolefins. In the Axens Prime-G+™
process, this step contains a catalyst that is also active for the reaction of mercaptans with olefins to
form thioethers:
R1 ¼ R2 þ RSH $ R1 -R2 -SR
The thioether boils at a much higher temperature than the mercaptan, thus allowing for the
conversion of low-boiling, low-molecular-weight mercaptans to be converted to much higher-
boiling sulfur compounds. This allows for the separation of the light cracked naphtha (LCN)
which is sulfur-free and contains C5 and C6 olefins from the sulfur-rich, higher-boiling portion of
the feed, which needs to be processed. The benefit is that the removal of these olefins preserves them
from undergoing saturation in the hydrotreating reactor and also allows for a lower olefin content of
the stream that is hydrotreated, thus allowing for the attainment of lower sulfur levels while
minimizing octane loss due to olefin saturation.
Desulfurization
A common feature to all the process licensors is the selective desulfurization reaction of the FCC
gasoline carried out over a catalyst specifically designed to effect desulfurization with minimal
saturation of olefins. In all cases, the feed to the selective desulfurization reactor has been processed
in a DIOS (diolefin saturation reactor) to saturate the diolefins. In some cases, the effluent of the
DIOS may be split into two in a splitter with the splitter overhead (LCN) either being sulfur-free
(Prime-G+™) or being subjected to a mercaptan extraction process (e.g., Merox or Exomer) and the
splitter botts then routed to the selective desulfurization reactor.
Reactions occurring in the selective desulfurization reactor include:
Desulfurization
R-S-R0 þ 2H2 ! RH þ R0 H þ H2 S
Olefin saturation
R ¼ R0 þ 2H2 ! RH-R0 H
Recombination
R ¼ R0 þ H2 S $ R-R0 -SH
Olefin drainage
R ¼ R0 þ H2 S $ R-R0 -SH
R-R0 -SH þ H2 ! R-R0 þ H2 S
While all these reactions are exothermic, the catalysts are so selective that desulfurization takes
place to a much greater degree than olefin saturation, and hence the temperature rise can be kept to
manageable levels.
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Process Configurations
The simplest process configuration consists of a DIOS followed by a selective desulfurization
reactor and a product stripper to remove H2S (Fig. 12).
Such a simple process configuration would be satisfactory when feed sulfur levels are low,
typically less than 300 wppm. In such cases, it is possible to achieve very low product sulfur
levels, <10 wppm, with minimal saturation of olefins and good octane retention.
A more complex process configuration would be required when the feed sulfur content is higher
than 300 wppm. In this case, the feed is first routed to a DIOS reactor to saturate the diolefins with
the effluent of the DIOS entering a splitter with the LCN sent overhead and the bottoms routed to a
selective desulfurization reactor. The splitter overhead may be subjected to a process such as UOP’s
Merox Process™ to extract the light mercaptans (Fig. 13).
A modification of the above process is Axens Prime-G+™, wherein the thioetherification function
inherent in the diolefin saturation/selective hydrogenation catalyst, or SHU™, is also applied. The
light mercaptans are converted to higher-boiling sulfides by reaction with olefins. The sulfides thus
formed boil at a much higher temperature and appear in the splitter bottoms and are subsequently
desulfurized in the selective desulfurization reactor(s). The effluent from the SHU™ reactor is routed
to a splitter which separates the light cracked naphtha (LCN) as an overhead product which is
essentially sulfur-free. The splitter bottoms is routed to the selective desulfurization reactors HDS-1
and HDS-2 (Fig. 14). The second desulfurization reactor operates at a higher temperature. Decom-
position of the remaining sulfur compounds, due to the higher temperature, limits the remaining
recombinant mercaptans to meet the desired sulfur specification.
At high feed sulfur levels, the amount of H2S produced is so high, and the formation of
mercaptans is so extensive that low product sulfur levels cannot be achieved without separation of
the H2S between two stages of desulfurization. This type of flow scheme is represented below by
two-stage SelectFining (see Fig. 15). The FCC gasoline enters the DIOS reactor to saturate diolefins.
The effluent of the DIOS reactor is mixed with recycle gas, heated to reaction temperature, and
routed to the first selective desulfurization reactor. The effluent of the first desulfurization reactor is
cooled, stripped of H2S, mixed with recycle gas, heated to reaction temperature, and routed to the
second selective desulfurization reactor. Finally, the effluent of the second selective desulfurization
reactor is stripped of H2S and routed to product blending/storage.
Process Conditions
Typical process conditions are shown in Table 5.
FCC Feed Pretreating

Hydrotreating the feed to an FCC is usually practiced to remove sulfur and limit SOx emissions but
also impacts the FCC in other ways. Hydrotreating the feed to the FCC results in hydrogen addition
to the feed due to saturation of aromatics, thus rendering the resulting molecules easier to crack in the
FCC and increasing conversion and gasoline yield. An additional benefit is the reduction in the
sulfur content of the FCC gasoline, thus reducing the severity required of the FCC gasoline
posttreater and consequently limiting olefin saturation and octane loss.
FCC feedstocks are vacuum gas oils boiling in the range of 650–1,100 F. Sulfur levels may
vary widely from 0.5 to 3 wt%. Nitrogen levels may vary from 500 to 3,000 wppm. Additionally,
depending on the end point, metals (Ni and V) may also be present. While decreasing the sulfur
content of the FCC feed has beneficial effects, reducing the nitrogen content and adding hydrogen
will increase conversion and gasoline yield.
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RGC + KOD Make-Up H2

DOI 10.1007/978-3-319-05545-9_4-1
Recycle Gas
DIOS Reactor
Lean Amine
Rich Amine
Selective
Desulfurization
Reactor
Off-Gas to Treating
Hydrogen Stripper
Source
Full Range Gasoline Lt Gas Product

and/or LPG (if any)
Feed Surge
Drum
Cold Sep
Desulfurized Gasoline
Fig. 12 Simplified process flow diagram of an FCC gasoline desulfurization unit – single stage
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Make-Up H2
DIOS
Reactor RGC
Selective Lean Amine

Desulfurization
Reactor Rich Amine Off-Gas to Treating
Splitter
Water Lt. Gasoline Product
Extractor
Full Range Wash Product Stripper
Gasoline Caustic Salt Bed
Settler
Lt Gas or LPG
Cold Sep
Disulfide Oil
Lean
Caustic Heavy Gasoline
H2 Source HP
Steam Oxidizer
Air
Fig. 13 Simplified process flow diagram of an FCC gasoline desulfurization unit – single stage with extractive Merox Process™
Page 33 of 59
Light Gasoline Recycle Gas RGC + KOD Make-Up H2

DOI 10.1007/978-3-319-05545-9_4-1
Lean Amine
Rich Amine
SHU
Reactor HDS-1
HDS-2 Off-Gas to Treating

Splitter
Stripper
Hydrogen Source
Full Range Gasoline Lt Gas Product

and/or LPG (if any)
Feed Surge
Drum
Liq. Quench Cold Sep
Heavy Gasoline
Fig. 14 Simplified process flow diagram for FCC gasoline desulfurization
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Make-Up H2 RGC
DIOS
KOD
Reactor
First Stage Lean Amine
Selective
Off-Gas Second Stage
Desulfurization to Treating
Rich Amine Selective Off-Gas to Treating
Reactor
Desulfurization
Inter-Stage Reactor Product
Stripper Stripper
Lt Gas Product
and/or LPG (if any)
Cold Sep
Full Range Cold
Gasoline Sep
Low Sulfur Gasoline
Fig. 15 Simplified process flow diagram of a two-stage SelectFining process unit
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Table 5 FCC gasoline desulfurization process conditions

LHSV, h1 Pressure, psig (barg) Temperature, F ( C) H2/oil, SCF/B (Nm3/m3)
™
DIOS/SHU 3–12 200–400 (14–28) 200–400 (90–200) 50–1,000 (8–170)
Selective HDS, first stage 1–3 200–400 (14–28) 475–600 (250–315) 1,500–4,500 (250–760)
Selective HDS, second stage 1–3 200–400 (14–28) 475–600 (250–315) 1,500–4,500 (250–315)
Feedstock Characteristics
Generally the chemical nature of the FCC feed is similar to that of distillates but of higher molecular
weight.
Sulfur Compounds
Sulfur compounds, even in structures without rings, are more complex higher in molecular weight
and may contain more than one sulfur atom:
7-Ethyl-2-(4-ethylheptyl)-3-propyldodecanethiol
2-(4-Ethyl-5-methylhexyl)-3,5-dimethyl-8-(3-methylpentylthio)nonanethiol
Similarly, structures containing rings are also larger, more complex, and higher in molecular
weight:
7-(2,3-Dimethylpentyl)-2-isobutyl-1-methyl-9-thiafluorene
Analytical Characterization
As described in the section on distillate hydrotreating, comprehensive GC has become a very
valuable tool in the characterization of the composition of vacuum gas oils. A comprehensive GC
3D image of the hydrocarbon composition of a VGO is shown in Fig. 16. The saturates all appear
along the x-axis with increasing boiling point. Aromatic compounds appear as “families,”
mono-aromatic, di-aromatic, tri-aromatic, and 4+ ring aromatic structures, of peaks according to
the extent of substitution of the ring.
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Fig. 16 Comprehensive GC 3D image of hydrocarbon compounds in a VGO
Fig. 17 Comprehensive GC image of sulfur compounds in a VGO

A similar 3D representation of the sulfur species present in a VGO appears in Fig. 17. The sulfur
compounds appear as families of thiophenic structures with increasing numbers of both aromatic
rings (polarity) and substitution (boiling point).
The characterization of the VGO by these methods allows for much more accurate determinations
of reactivity and the application of the optimal catalysts and process conditions to effect the desired
conversion.
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Both Co/Mo and Ni/Mo catalysts have been applied in the hydrotreatment of FCC feed. Co/Mo
catalysts are sufficiently active for desulfurization at lower pressures, while Ni/Mo catalysts are
more active for denitrogenation and saturation of aromatic rings at higher pressures, both of which
increase the activity of the FCC catalysts and increase gasoline yield. Tri-metallic catalysts that
provide average activities for all functions (hydrodesulfurization, hydrodenitrogenation, and aro-
matics saturation) have also been successfully applied.
Hydrodesulfurization, hydrodenitrogenation, and saturation reactions are similar to those occur-
ring in distillate hydrotreating except the reacting species are of higher molecular weight.
Feedstocks
Feedstocks to an FCC feed pretreating unit may include vacuum gas oils (VGO) as well as heavy
coker gas oil (HCGO). Sulfur contents may range from 0.5 to 3 wt% and nitrogen from 500 to
3,000 wppm. The higher values, especially for nitrogen, are found in HCGO. HCGO additionally
contains olefins with bromine numbers ranging up to 20. The olefinic nature of the HCGO feed
requires consideration of catalyst bed distribution and temperature management due to the highly
exothermic nature of the very rapid olefin saturation reactions.
Process Configuration
A simplified process flow diagram of a typical FCC feed pretreater is shown in Fig. 18. The feed is
pumped from the feed surge drum and mixed with recycle gas, and the mixture is then heated in a
bank of feed/effluent exchangers and then passes to the reactor charge heater where it is heated to
reaction temperature and then enters the reactor. The reactor is shown with three beds of catalyst with
recycle gas being routed to the quench zones to reduce the temperature of the effluent of each bed to
the desired inlet temperature of the next catalyst bed. The number of catalyst beds is dependent on
the heat release and allowable temperature rise in each bed. Reactor effluent is first cooled against the
combined feed or individual fresh feed and recycle gas streams in the feed/effluent exchangers and is
then passed to a series of separators to recover the liquid hydrotreated hydrocarbon and the recycle
gas. The recycle gas is scrubbed free of H2S in an amine scrubber and then compressed and routed
back to the reactor. Water is added to the hot separator vapors to dissolve the NH3 and prevent the
formation of ammonium hydrosulfide salts in the cold sections of the plant. The hydrocarbon liquid
from the separator system is routed to a fractionation section to recover a wild naphtha stream, a
diesel stream and the hydrotreated FCC feed.
Process Conditions
Process conditions applied in FCC feed pretreating have been getting more severe with the necessity
to reduce SOx emissions from the FCC regenerator to ever lower levels. While desulfurization of the
FCC feed to sulfur levels of 2,000 wppm has been acceptable in the past, the trend has progressed
past 1,000 wppm sulfur to <500 wppm sulfur and recently to lower levels in efforts to minimize or
eliminate the posttreatment of FCC gasoline. Typical process conditions are shown in Table 6.
The more severe (lower LHSV, higher pressure and temperature, etc.) conditions are applied to
blends containing HCGO, DAO, or both. Typically the FCC pretreating unit is designed to operate
with a cycle that matches the FCC turnaround cycle, which typically is 4–5 years.
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FCC Feed Pre-treating

Process Flow Diagram
Recycle Gas
Compressor
Makeup
R-1
Reactor Charge Hydrogen
Heater
Lean Amine
Wash Water Amine
Scrubber
Rich Amine
Fresh Cold
Feed Separator
Fractionaton Section
Hot
Separator Wild Naphtha
Flash Gas
Hot
Flash Cold Diesel
Drum Flash Sour
Drum Water
FCC
Feed
Fig. 18 Simplified process flow diagram of an FCC feed pretreater
Table 6 FCC feed pretreating process conditions

LHSV, h1 0.7–2.0
Temperature, F (oC) 670–730 (355–390)
Pressure, psig (barg) 800–1,600 (55–110)
H2/oil, SCF/B (Nm3/m3) 1,500–4,000 (250–675)
Hydrocracker Pretreat
Introduction
Hydrotreating and hydrocracking share many common elements. Both processes catalytically
upgrade the feedstock by adding hydrogen under moderate to high operating pressures and elevated
reactor temperatures. However, a key differentiator is that hydrocracking catalysts have a stronger
acid function compared to that of hydrotreating catalysts, which allows the hydrocracking catalysts
to facilitate deeper cracking reactions as well as naphthenic ring-opening reactions.
A hydrocracking unit requires the use of both hydrotreating and hydrocracking catalysts to obtain
the desired product qualities in the naphtha, jet, and diesel products as well as the desired operating
cycle length. This section briefly touches upon the hydrotreating reactor section in the context of a
hydrocracking unit.
Feedstock Types
A hydrocracking unit can be designed to handle a wide range of feedstock types. Ultimately, unit
design is constrained by the economic return of processing the most severe feedstock in comparison
to the associated capital expenditure and operating expense.
Vacuum gas oil (VGO) and heavy coker gas oil (HCGO) are more commonplace feedstocks for a
hydrocracking unit, but as the product quality specifications for clean fuel become more stringent
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and the demand for transportation fuel continues to increase in lockstep with the ever-growing
global population, refiners have increasingly found interest in processing feeds such as light cycle oil
(LCO) from the FCC and DAO (deasphalted oil) from solvent deasphalting (SDA) units to produce
high-quality fuel, such as diesel.
All four of these feedstock types will have an appreciable amount of organic sulfur (1–3 wt%) and
nitrogen (500–3,500 wppm) that will need to be nearly completely removed in the hydrotreating
section to protect the downstream hydrocracking catalyst from these poisons.
Light cycle oil is a highly aromatic diesel boiling range stream produced in the FCC unit. Due to
the high concentration of two- and three-ring aromatics, LCO has a low cetane value, which makes it
a poor blend stock for the refinery’s diesel pool. Conventional hydrotreating pressure is frequently
inadequate to completely remove the native sulfur species in LCO to meet ULSD specifications.
Therefore, processing the LCO in a hydrocracking unit becomes an attractive alternative. The
difficult sulfur species in LCO can be more effectively removed in the high-pressure hydrotreating
section of the hydrocracking unit. Furthermore, the LCO quality is further improved by the higher
operating pressure of the hydrocracking unit, since additional aromatic saturation can take place to
improve the cetane qualities of the stream.
Deasphalted oil is another feedstock that some refiners find economical to send to a hydrocracking
unit. Processing DAO in a hydrocracking unit requires additional catalyst system considerations to
account for the higher metal content (Ni and V) as well as the potential for the presence of very heavy
molecules as condensed-ring aromatics. DAO is created in a solvent deasphalting unit that separates
on the basis of molecular type rather than boiling point. Therefore, for moderate to heavy lifts,
increasing extent of extraction, in the SDA unit the heaviest molecules in the DAO are not
adequately characterized by boiling point due to the limitations of the current distillation test
methods. The higher metal content in DAO is addressed by specifying an adequate amount of
metal trapping material in the hydrotreating section of the hydrocracking unit. Due to the presence of
very heavy molecules, the potential for a higher deactivation rate should also be considered when
selecting the design operating pressure and sizing both the hydrotreating and hydrocracking
catalyst beds.
Optimization Between the Hydrotreating and Hydrocracking Function

In a typical hydrocracking flow scheme, the hydrotreating section effluent is directly routed to the
inlet of the hydrocracking section without any removal of the H2S and NH3 that are formed from the
hydrotreating reactions. Ultimately, the catalyst loading for the hydrotreating section depends on the
concentration of contaminants, organic sulfur and nitrogen, the fresh feed, and the permissible level
of these contaminants entering the hydrocracking section. There is some degree of flexibility in the
level of contaminants permitted to enter the hydrocracking section, particularly organic nitrogen,
from the hydrotreating section. The permissible concentration will depend on the relative reactor
volumes available for loading hydrotreating versus hydrocracking catalyst, the target conversion
rate, and the desired product quality from the hydrocracking unit.
Residual Oil Hydrodesulfurization

Residual oil, as the name implies, is the material remaining after distillation. Atmospheric residue
(AR) is the bottoms of the atmospheric column and generally has the boiling range of 650 F+.
Vacuum gas oil is contained within AR. Vacuum residue (VR) is the bottoms of the vacuum column.
With the vacuum gas oil (VGO) removed, the boiling range of the vacuum residue is 1,050 F+.
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One of the defining characteristics of the residual oils is the presence of metals, primarily Ni
and V, although smaller amounts of other metals may also be present. Ni and V are typically present
in concentrations ranging from 25 to 1,000 wppm. Sulfur concentrations are also quite high,
sometimes exceeding 3 wt%. A further defining feature of the residual oils is their high Conradson
carbon residue (CCR), frequently exceeding 20 %. Additionally, the presence of condensed-ring
aromatics and asphaltenes necessitates the application of high pressures and specialized catalysts to
achieve reasonable cycles, typically 12–18 months.

The main feature that differentiates residual oil hydrotreaters from hydrotreaters in other applica-
tions, e.g., distillate and FCC feed pretreaters, is the presence of high concentrations of metals and
the necessity of removing these prior to the main hydrotreating reactors. This is accomplished by the
use of specialized catalysts having larger pore diameters to accommodate the metals containing
molecules (typically, but not always present in porphyrin structures; see figure below). The large
pore diameters are required to allow the metal-containing molecules to penetrate to the center of the
catalyst pellet rather than depositing at the pore mouth and plugging the pore, rendering it inactive
despite having a “fresh” and active interior.
Vanadyl porphyrin
Nickel porphyrin
Sulfur and nitrogen atoms are also generally located in condensed-ring aromatic structures
making residual oils much more difficult to process.
As mentioned above, the key feature of hydroprocessing residual oils is the necessity to provide
guard reactors containing large pore catalysts for the removal of metals. The guard reactors may or
may not be arranged in a swing reactor system where one reactor may be taken off-line for catalyst
removal and replacement while the spare reactor is placed into service. A typical process configu-
ration of a resid hydroprocessing unit is depicted in Fig 19. The first two reactors in fig 19 are the
“guard” reactors filled with hydrodemetallation catalysts while the remaining two are hydrodesul-
furization reactors.
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Fixed Bed Reactors
Residue
Feed Feed
Filters Hot
Separator
H2
Makeup
Fractionator
H2
Gas
Recovery
Purge Naphtha
To Fuel Gas
Distillate
H2 S Cold
Scrubber Separator
Cold Hot
Flash Flash Hydrotreated
Residue
Fig. 19 Simplified process flow diagram of a residual oil hydrotreater
Table 7 Typical process conditions for a residual oil hydrotreater

LHSV, h1 0.2–0.7
Temperature, F ( C) 670–730 (355–390)
Pressure, psig (barg) 1,800–2,500 (125–170)
H2/oil, SCF/B (Nm3/m3) 3,000–5,000 (500–850)
Process Conditions
Process conditions depend on a number of factors including, feed type (AR or VR), degree of
desulfurization, metals levels, carbon residue, and required cycle length. Typical process conditions
are presented in Table 7.
Catalysts
Hydrotreating catalysts, in general, are high-surface-area materials consisting of an active compo-
nent and a promoter, which are uniformly dispersed on a support. The catalyst support is normally
gamma alumina (g-Al2O3), doped sometimes with small amounts of silica, phosphorus, fluoride,
and/or boron and prepared in such a way so as to offer a high surface area upon which to disperse the
active metals and an appropriate pore structure, so that pore plugging with coke and/or metals is
sufficiently mitigated to achieve the desired operating cycle. The active component is normally
molybdenum sulfide, although tungsten-containing catalysts are also used (though seldom, and that
generally for special applications such as lube oil processing). Regarding molybdenum catalysts,
both cobalt (CoMo) and nickel (NiMo) are used as promoters. The promoter has the effect of
substantially increasing (approximately 100-fold) the activity of the active metal sulfide. The acidity
of the support (which itself may be increased with dopants, beyond the nascent acidity) can be
increased to boost the catalyst activity for hydrocracking and isomerization reactions. The commer-
cially available catalysts have varying amounts of promoters and active components, depending on
the desired applications, but in general they can contain up to about 25 wt% promoter and up to
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Cylinder 4-Lobe Sphere
Hollow Ring 3-Lobe
Fig. 20 Hydrotreating catalyst shapes
25 wt% active component as oxides. Hydrotreating catalysts come in different sizes and shapes and
vary depending on the manufacturer (Fig. 20):
Cylindrical 1/3200 –1/400
Trilobe 1/2000 –1/1000
Quadrilobe 1/2000 –1/1000
Spheres 1/1600 –1/400
Hollow rings Up to 1/400
Other shapes include nodular beads and wagon wheels. In general, the size and shape of the
catalyst pills is a compromise between the desire to minimize pore diffusion effects in the catalyst
particles (requiring small sizes) and pressure drop across the reactor (requiring large particle sizes).
The physical characteristics of catalysts also vary from manufacturer to manufacturer and the
intended use of the catalyst but in general are as follows:
Surface area 100–250 m2/g (typ.)
Pore volume 0.5–1.0 cc/g
Median pore diameter 65–150 Å
Compacted bulk density 35–55 lbm/ft3
Crushing strength 4–20 lbf/in2
Average length (except spheres) 1/8–3/8 in.
Cobalt-Molybdenum Catalysts
CoMo catalysts have been designed primarily for desulfurization with minimum hydrogen addition;
nevertheless, modest denitrogenation and demetallation is also achieved. These catalysts can treat
feedstocks of widely varying properties. CoMo catalysts have the lowest hydrogenation activity;
therefore, they have the lowest hydrogen consumption per mole of sulfur removed. They also have
the lowest sensitivity of H2 consumption to changes in operating pressure. CoMo catalysts have
sufficient desulfurization performance at low operating pressures (<600 psig, or <40 barg). These
catalysts also have the lowest denitrogenation performance due to low hydrogenation activity.
Because CoMo catalysts exhibit the highest sulfur removal per unit of hydrogen consumed, they
are best suited for desulfurization at lower pressures and when hydrogen is in short supply.
Nickel-Molybdenum Catalysts
NiMo catalysts have been designed for hydrodesulfurization but particularly for hydrogenation and
hydrodenitrogenation. Metal removal can also be achieved. These catalysts can treat feedstocks of
widely varying properties. NiMo catalysts have higher denitrogenation activities than CoMo and are
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therefore used for cracked stocks or other applications where denitrogenation and/or saturation is as
important as desulfurization. The higher hydrogenation activity of NiMo catalysts allows them to be
used as a topping layer to saturate olefins and other gum precursors to mitigate catalyst bed fouling,
leading to pressure drop accumulation and poor liquid flow distribution through the catalyst bed.
The performance of NiMo catalysts is very good at high pressures. NiMo catalysts show a greater
response in denitrogenation and desulfurization performance to changes in H2 partial pressure than
CoMo. High-pressure operations, such as FCC and hydrocracking feed pretreatment, therefore favor
the use of NiMo catalysts. NiMo catalyst use is also favored for naphtha hydrotreaters upstream of
catalytic reforming units as the modern reforming catalysts are very sensitive to the nitrogen content
of the feedstock.
Other Catalysts
Other catalysts that have been used in hydrotreating are supported NiCoMo (still in use for
hydrotreating) and NiW (very rarely in use for hydrotreating). NiCoMo catalysts attempt to combine
the benefits of CoMo and NiMo at intermediate pressures, achieving sufficient hydrodesulfurization
(primarily) at the minimum required hydrogen consumption. NiW catalysts are more widely
practiced in hydrocracking applications than hydrotreating applications. Historically, sulfided
NiW exhibits hydrocracking activity surpassing that of both CoMo and NiMo. Increasing the
activity of the support material with promoters, amorphous silica alumina, or zeolite can further
enhance the hydrocracking activity.
Type I vs. Type II Hydrotreating Catalysts

The designations “Type I” and “Type II,” as originally applied by Topsøe et al. refer to the nature of
the bonding between the active phase (e.g., CoMoS, NiMoS) and the support, the extent of stacking
of the active phase as dispersed MoS2 nanosheets, and the coordination of the promoter metal at the
edges of the nanosheets. The promoted active phase along the edges, as Co(Ni)-Mo-S structures, is
believed to be responsible for the relatively greater hydrotreating activity of Type II catalysts.
Catalysts of the former type consist predominantly of an active phase that is more strongly bound
to the support, as in Mo-O-Al where the support is g-alumina, with relatively shorter stacks of MoS2
nanosheets, and wherein a relatively smaller portion of the promoter metal is coordinated into the
MoS2 nanosheets’ edges. Catalysts of the latter type consist predominantly of an active phase that is
more weakly bound to the support via dipole-dipole (van der Waals) interactions, with relatively
taller stacks of MoS2 nanosheets, and wherein a relatively greater portion of the promoter metal is
coordinated into the MoS2 nanosheets’ edges. The active phase is, in general, fully sulfidable
(Topsøe et al. 1996; Hensen et al. 2002; Topsøe and Clausen 1984). This description may require
some revision, especially as regards the necessity for taller stacks of MoS2 nanosheets.
Unsupported or Bulk Transition Metal Sulfide (TMS) Catalysts

The quantum improvement in hydrotreating catalyst performance can be observed in the activity of
unsupported TMS catalysts. Unsupported catalysts appear to represent a hearkening back to the very
early history of hydrotreating, when most hydrotreating catalysts were unsupported (Čejka 2003). In
principle, today’s unsupported catalysts are comprised only of active phase, representing a much
higher population density of active phase per unit volume than Type I and Type II supported
catalysts, without the limitation of active phase-support interactions. Such catalysts are comprised
almost entirely of metals, as in NiMoW. Their HDS and HDN hydrotreating activities (RVAs) can
exceed those of the contemporary Type II supported catalyst by 50–100 %. It is for this reason that
unsupported catalysts are typically loaded in addition to supported catalysts, since the hydrogen
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consumption and heat release of a full reload with an unsupported catalyst could exceed process
design allowances. The active phase appears to take many forms. One might observe active phase
structures similar to those seen on Type II supported catalysts as well some others. In general, these
catalysts are prepared via precipitation of the oxidic precursor followed by the sulfidation of the
precipitate or based on the direct precipitation of the (mixed) sulfide (Chianelli et al. 2009).
Measuring Catalyst Performance

Catalyst performance is measured by several criteria shown below, which are more or less self-
explanatory:
• Initial activity, which is measured by the temperature required to obtain desired product at the start
of the run. During the cycle, the catalyst activity can be calculated as shown below:
Ds ¼ D0S eAt
where
Ds = desulfurization activity
D0S = initial desulfurization activity
A = deactivation rate, F/bpp
t = catalyst life, bpp
• Stability, which is measured by the rate of temperature increase required to maintain product
quality
• Product quality, which is a measure of the ability of the catalyst to produce products with the
desired use specifications, such as pour point, smoke point, or cetane number
Catalyst Manufacture
Hydrotreating catalysts contain metals dispersed on a support. That support is g-lumina which is
arrived at by synthesis. Several raw materials can be used to produce the g-alumina:
• Gibbsite (a-alumina trihydrate)

• Bayerite (b-alumina trihydrate)
• Boehmite and pseudoboehmite (g-AlO(OH))
Hydrotreating catalysts are typically manufactured by several methods:
• Dry (incipient wetness) or wet impregnation

• Co-mulling
• Hot soaking/dip impregnation
Forming of the Support

Figure 21 shows the preparation of a spherical support by the oil dropping method. Figure 22 shows
support preparation by extrusion. In the typical case where pseudoboehmite is used to prepare the
catalyst support, the powder is blended with an acid solution, either organic or inorganic, and mixed
and/or mulled until reaching a colloidal state, suitable for extrusion. The process of converting the
powder to an extrudable colloid using an acid solution is referred to as peptization. The colloidal
“dough” is then extruded through fixed dies in the desired shape and size, before being dried and
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Alumina Hydrosol
NH3 Generating
Agent, (i,e., Urea)
Sprayer
Finished
Hot Oil Spherical
Support
Filter
Fig. 21 Oil dropping (spherical support preparation)
Alumina Mixer Extruder
Finished
Drier Calciner Support
Fig. 22 Support preparation by extrusion
converted to g-alumina in a high-temperature calcination step (usually 900–1,300 F). Many factors
influence the final pore volume distribution, surface area distribution, and the mechanical strength:
the raw pseudoboehmite itself, the type and concentration of the acid solution, the presence of burn-
out agents and extrusion aids, the type of blending and its intensity, the extrusion flux and die plate
pressure, the drying, and the calcination (duration, temperature, application of steam). More
recently, syntheses utilizing surfactants are being developed in the case of g-alumina supports, to
more directly tailor pore structure and increase surface area (Eijsbouts et al. 2007).
Support Impregnation
The support, either spherical or extruded, is then finished with an impregnation as shown in Fig. 23.
Figure 24 depicts hydrotreating catalyst manufacture by co-mulling. Figure 25 shows the schematic
of catalyst manufacturing by hot soaking. Impregnation solutions are prepared after a measurement
of the pore volume of the support, typically via Hg intrusion. An appropriate volume of impregna-
tion solution is then prepared to fill the available pore volume, usually with a slight percentage
excess. The species to be deposited on the catalyst support are introduced into the impregnation
solution as precursors, such as nickel nitrate (hydroxycarbonate), cobalt nitrate (carbonate), ammo-
nium heptamolybdate, molybdenum trioxide, and ammonium metatungstate. The volumes of
support and impregnation solution are then mixed, excess water is removed by drying if necessary,
and the catalyst is heat-treated to convert the metal precursors to metal oxides. In the case of Type II
hydrotreating catalysts, it is typical to include at least one additive to the impregnation solution.
EDTA and NTA are common examples of chelating agent additives. It is also typical that the heat
treatment is not carried out at temperatures which would completely remove the additive. The
purpose of the additive or additives is to facilitate formation of the Type II active phase when the
catalyst’s metal oxides are converted to metal sulfides during activation/sulfidation. This may occur
via multiple pathways: stabilize the impregnation solution especially in the case of high metal
loadings, improve the dispersion of the active phase during the course of impregnation (buffering
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Support Impregnation
Calciner Drier
Finished
Catalyst
Fig. 23 Dry (incipient wetness) and wet impregnation
Dry Alumina
Active Metal(s)
Solution
Mix-Muller
Extruder Drier
Calciner
Finished
Catalyst
Fig. 24 Co-mulling
Alumina Metals–or-
Active Metal(s)
Solution
Mixer (at Elevated

Temperatures)
Drier
Finished
Calciner
Catalyst
Fig. 25 Hot soaking
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effect), bind with those support species which would otherwise bond with the active phase, act as an
inert support upon which the active phase may deposit, and adjust the sulfidation rate of one or more
of the metal oxides (an effect of chelation) during the activation to facilitate greater coordination of
the promoter to active phase nanosheet edges (Frizi et al. 2008; Breysse et al. 2008).
Catalyst Loading and Activation

Catalyst Loading
There are two methods of catalyst loading: sock loading and dense loading. Pouring catalyst into a
hopper mounted on top of the reactor and then allowing it to flow through a canvas sock into the
reactor is sock loading. Dense loading or dense bed packing is done with the aid of a mechanical
device. Dense loading techniques were first introduced in the mid-1970s. Catalysts loaded by sock
loading will have a higher void fraction than catalysts that were dense loaded, typically 10–15 %
lower loaded density. Dense bed loading/packing and the resulting higher pressure drop provides a
more even distribution of liquid in a trickle-flow reactor, which is the prevalent flow regime in the
hydrotreating of diesel-range streams and heavier. Dense loading of at least the primary
hydrotreating catalyst bed(s) is usually preferred in order to maximize the reaction rate per unit
reactor volume throughout the catalyst life cycle. Dense loading delivers catalysts into a reactor at a
controlled rate, varied according to the rising bed height, so that the catalysts are oriented similarly
throughout the dense bed. This uniform orientation helps facilitate a uniform vapor/liquid flow
distribution and catalyst utilization. Catalyst particle orientation is especially critical with respect to
shaped, extruded catalysts in trickle-flow reactors. Of all the factors influencing catalyst utilization,
catalyst loading has generally proven to be the most important factor. Another advantage of dense
loading is that it allows loading more catalyst in the reactor because of the reduced void fraction in
the catalyst bed. Thus, the catalyst life can be extended, or else the unit can be operated at more
severe conditions (lower product sulfur level, increased feed rate) than if the catalyst had been sock
loaded. Except for the hydrotreaters that have reactor pressure drop limitations mainly due to
operation at higher-than-design throughputs, most hydrotreaters are dense loaded. Ex situ
presulfurized catalysts (see catalyst activation) are self-heating materials. Thus, they should be
loaded in an inert atmosphere though some loading contractors do load them under air atmosphere.
Catalyst Activation
Hydrotreating catalysts have to be activated in order to be catalytically useful. The activation of the
catalyst is performed by conversion of metal oxides to metal sulfides and is commonly called
sulfiding, though several other names are used to describe the same thing. Other names that are used
to describe catalyst activation techniques are pre-sulfiding or pre-sulfurizing. The metals on the
catalysts are in an oxide form at the completion of the manufacturing process. More often than not,
this is typically accomplished in situ; however, more refiners have started to use catalyst which had
the sulfiding compound loaded onto the catalyst outside the unit (ex situ pre-sulfidation). It is likely
that more and more refiners will opt to receive the catalyst at the refinery site in pre-sulfided state to
accelerate the start-up of the unit and because it is more environmentally friendly (eliminates the
VOC and odors evolved when the sulfiding compound is introduced into the unit).
In situ sulfiding can be accomplished either in vapor or liquid phase. In vapor phase sulfiding, the
activation of the catalyst is accomplished by injecting a chemical which decomposes easily to H2S,
such as dimethyldisulfide (DMDS) or dimethylsulfide (DMS). The usage of H2S/H2 was common
up until the end of the last century, but now it is only rarely used because of environmental and safety
concerns. Liquid phase sulfiding can be accomplished with or without organo-sulfur compounds
added to the feedstocks. In the latter case, the feedstock is generally a straight-run gas oil that
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contains sulfur compounds in ranges from a few thousand to 20,000 parts per million. The H2S
necessary for the activation of the catalyst is generated by the decomposition of the sulfur com-
pounds. This method is in very little use today, but it was “state of the art” in the 1960s and early
1970s. The preferred sulfiding procedure in the industry is liquid phase with a sulfur-containing
component added to the feed (generally a form of DMDS or a polysulfide). It results in savings of
time when compared to either vapor phase or liquid phase without these agents. In addition to the
time savings, liquid phase sulfiding is desirable because the liquid phase provides a heat sink for the
exothermic sulfiding reactions which helps prevent high catalyst temperatures and temperature
excursions which could otherwise result in sintering and metals reduction. The active phase in
Type II hydrotreating catalysts, orders of magnitude more active than Type I at start of run, is
especially susceptible to such damage during the sulfiding process. Another advantage of liquid
phase over gas phase sulfiding is that by having all the catalyst particles wet from the very beginning,
there is very little chance of catalyst bed channeling which can occur if the catalyst particles are
allowed to dry out. The in situ sulfiding occurs at temperatures between 450 F and 650 F
(230–345 C) regardless of the method used. Some catalyst manufacturers recommend that the
sulfiding be conducted at full operating pressure, while others prefer it be done at pressures lower
than the normal operating pressure. It is also very typically recommended that cracked feedstocks
should be introduced very gradually, over a period of 3–7 days. Cracked feedstocks are composed of
relatively more olefins and aromatics, and so introducing these during the start of run period would
lead to excessive heat release, leading to catalyst damage via sintering of the active phase.
In the case of ex situ presulfurization of the catalyst, sulfur compounds are loaded onto the
catalyst. The activation occurs when the catalyst, which has been loaded in the reactor, is heated up
in the presence of hydrogen and the sulfur compounds decompose to H2S. During this period, the
H2S scrubber is off-line so that the H2S can accumulate in the recycle gas circuit.
Catalyst Deactivation, Regeneration, and Rejuvenation

Catalyst deactivation is the gradual loss of the catalyst’s ability to produce the desired specification
product unless reactor temperatures are increased (or feed rate is decreased). The catalyst activity
determination is shown under the “Catalysts” section of this chapter. Typically, as the run progresses,
the catalyst loses activity. Catalysts will lose activity in several ways described below.
Coke Deposition
Coke is the term used to describe the formation of hydrogen-deficient carbonaceous materials, most
particularly on the catalyst surface. Coke is generally formed by thermal condensation, catalytic
dehydrogenation, and polymerization reactions. A schematic of this is shown below:
(1) (3)
Hydrocarbons →
← Coke precursors → Coke
(2)
Where:
1. Dehydrogenation
2. Hydrogenation
3. Condensation/polymerization
The coke level rapidly rises to an equilibrium level during the early part of a catalyst cycle. This
initial coke is often referred to as “soft” coke. During the rest of the cycle, the total amount of coke
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remains almost constant; however further structural changes occur to produce what is often referred
to as “hard” coke. Thus, the observed catalyst deactivation during a cycle is primarily the result of
structural changes to the coke rather than an actual marked increase in the total amount of coke.
Short-term recovery of catalyst activity has been observed on a number of occasions after a period of
hot hydrogen stripping. This fits with the expectation that soft coke should be able to be partially
stripped or washed from the catalyst.
As can be seen from the reaction schematic, the route to coke precursor formation is dehydroge-
nation. Hydrogen-deficient feedstocks (i.e., cracked stocks) therefore result in faster coke deactiva-
tion. High temperatures favor faster coke deactivation because the laydown of coke on a catalyst is a
time-temperature phenomenon in that the longer the exposure and/or the higher the temperature the
catalyst is subjected to, the more severe the deactivating effect. Coke is not a permanent poison.
Catalyst, which has been deactivated by coke deposition, can be, relatively easily, restored to close to
original condition by regeneration. Low hydrogen partial pressures also favor coke formation. In
general, the heavier feedstock will produce higher levels of coke on the catalyst. In general, the
maximum coke laydown is about 20 wt%.
Metals Deposition
Deposition of metals is not reversible, even with catalyst regeneration. The metals may come into the
system via additives, such as silicon compounds used in coke drums to reduce foaming, or feedstock
contaminants such as Pb, Fe, As, P, Na, Ca, and Mg, or organometallic compounds in the feed
primarily containing Ni and V. The deposition of Ni and V takes place at the pore entrances or near
the outer surface of the catalyst, creating a “rind” layer – effectively choking off access to the interior
part of the catalyst, where most of the surface area resides.
Catalyst Support Sintering

This is another reason for loss of catalyst activity and it also is irreversible. This is also a result of
high temperatures and particularly in connection with high water partial pressures. In this case the
catalyst support material can lose surface area from a collapse of pores or from an increase in the
diameter of pores, with the pore volume remaining approximately constant.
Catalyst Regeneration
The activity decline due to coke laydown can be recovered by burning the coke off in a controlled
atmosphere. The regeneration can be accomplished in any of three ways: in situ with steam/air, in
situ with nitrogen/air, or ex situ. The majority of commercial catalyst regenerations, at least in the
industrialized world, are performed ex situ, by specialized contractors, because of environmental
considerations as well as because it results in a superior regenerated catalyst. Prior to regeneration,
the spent catalyst must be de-oiled; this activity can be done in situ at the refinery or ex situ at the
service provider’s facility. De-oiling is needed to prevent the formation of sulfates during the
regeneration. The formation of sulfates will lead to disappointing catalyst performance and shorter
cycle length. During regeneration/combustion, coke is converted to CO2 and H2O. In the absence of
excess oxygen, CO may also form. Hydrotreating catalysts contain sulfur, as metal sulfides. In the
regeneration process, the metal sulfides are converted into the corresponding metal oxides and the
sulfur is emitted as SO2. In general, sulfur dioxide emission starts at lower temperature than CO2
emission. Regeneration service providers rely on several forms of equipment. One vendor uses a
continuous rotolouver, which is a cylindrical drum rotating slowly on a horizontal axis and enclosing
a series of overlapping louvers. The spent catalyst passes slowly through the rotolouver, where it
encounters a countercurrent of hot air. Another uses a belt furnace. The catalyst is conveyed with the
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stainless steel belt through a stationary furnace. A third vendor makes use of an ebullated bed
furnace/reactor to perform the catalyst regeneration. Regardless of the process, the spent catalyst is
submitted to de-oiling prior to regeneration, which eliminates as much hydrocarbon as possible and
which removes as much sulfur as possible, preventing the formation of sulfates which could deposit
on the catalyst and not be removed during regeneration. Sulfates are deleterious to catalyst
performance. While the in situ regeneration results in about 90 % catalyst activity recovery, ex
situ catalyst regeneration can result in 95–97 % catalyst activity recovery. Following regeneration,
Type II hydrotreating catalysts require a rejuvenation step, wherein the active phase is re-dispersed
as it was when fresh.
Design and Operation of Hydrotreating Reactors

Design and Construction of Hydrotreating Reactors
Hydrotreating reactors are downflow, fixed-bed catalytic reactors, generally operating in trickle-flow
regime. Because hydrotreating occurs at moderately high pressure and relatively high temperature
and in the presence of hydrogen and hydrogen sulfide, the reactors are vessels with relatively thick
wall. The reactors are usually cylindrical vessels, and while those used for naphtha hydrotreating as
well as many of the older vintage reactors are made from lower alloys, most of those designed in the
last 10 years are typically constructed of 1¼ Cr–½ Mo or 2¼ Cr–1 Mo base metal with a lining of
stabilized austenitic stainless steel for added corrosion protection. This choice of alloys gives the
high strength of the base metal and the excellent corrosion resistance of the inner lining. There are
several items concerning the selection of materials that must be taken into consideration during the
operation of the unit. Concerning the use of austenitic stainless steels in hydrotreating units, the
possibility exists for corrosion cracking to occur if proper procedures are not followed. Corrosion
cracking in a hydrotreating unit can occur through chloride attack or polythionic acid attack.
Chloride attack can be prevented by minimizing the amount of chloride in the process material
that will come in contact with the austenitic stainless steel during normal operations. In addition,
during start-up and shutdown operations, precautions should be taken to limit the chloride content in
any flushing, purging, or neutralizing agents used in the system.
Polythionic acids occur as the result of the action of water and oxygen on the iron sulfide scale that
forms on all items made of austenitic stainless steel. Once formed these acids can attack the
austenitic steel and cause intergranular corrosion and cracking. To prevent polythionic acid attack,
it is necessary to maintain the temperature above the dew point of water in those areas containing
stainless steel. Under normal operating conditions, the system is essentially free of oxygen.
However, when the system is depressurized and the equipment is opened to air, it becomes necessary
to maintain a nitrogen purge to prevent air from entering. In cases where adequate temperatures or
purges cannot be maintained, a protective neutralizing environment should be established. Gener-
ally, a 5 % soda solution is used to neutralize the austenitic stainless steel.
Figure 26 shows a hydrotreating reactor with two beds of catalyst and one interbed quench zone
pictured, but the number of beds can vary for different designs. As already indicated, most naphtha
hydrotreaters only have one catalyst bed. Many reactors processing cracked feedstocks will have
several beds to facilitate temperature control by cooling with hydrogen quench between the catalyst
beds. For example, a reactor design could require three catalyst beds and two interbed quench zones.
The reactor vessel is designed to allow maximum utilization of catalyst. Creating equal flow
distribution, providing maximum liquid/vapor mixing, and providing multiple beds with quench
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Fig. 26 Two-bed hydrotreating reactor with interbed quench
zones for efficient catalyst usage achieve this. The internals of the reactor found in a reactor are the
following (though not all reactors necessarily have all of them):
• Inlet diffuser
• Top vapor/liquid distribution tray
• Quench section (present only when there are multiple catalyst beds)
• Catalyst support grid (present only when there are multiple catalyst beds)
• Outlet collector
The size of hydrotreating reactors varies widely depending on the design conditions and is
dependent on the desired mass velocity and acceptable pressure drops. Since heat release is a
common feature for all hydrotreaters, reactor temperature control has to be exercised. Generally,
the maximum allowable DT is 75 F (42 C). If that temperature is not expected to be exceeded, the
reactor will contain only a single bed, and temperature control will be exercised by changing the
reactor inlet temperature. If the overall maximum reactor temperature rise is expected to exceed
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Table 8 Chemical basis for product quality

Quality measurement Chemical basis
High smoke point Low concentration of aromatics
Low pour point Low concentration of n-paraffins
Low freeze point Low concentration of n-paraffins
Low cloud point Low concentration of n-paraffins
Low CFPP Low concentration of n-paraffins
75 F (42 C), a multiple-bed reactor should be installed with cold hydrogen quench inserted in the
quench section for temperature control.
Hydrotreater Reactor Operation

During operation, the hydrotreating catalyst gradually loses some of its activity. In order to maintain
the desired quality of the products at the design feed rate, the average bed temperature is gradually
increased. The temperature increase in many cases is very small, less than 2 F/month (1 C/month).
When the average bed temperature reaches a value close to the design maximum, the catalyst has to
be replaced or reactivated. Because the required temperature increase per unit time is relatively
small, the reactor can be operated with the same catalyst for several years before regeneration or
replacement of the deactivated catalyst becomes necessary. Quite often, catalyst regeneration or
replacement is dictated by a high reactor pressure drop, due to catalyst fouling.
In hydrotreating, the key catalytic properties are initial activity, stability, and product quality. The
temperature required to obtain the desired product at the start of the run measures the initial activity.
Catalyst stability is a measure of change of reaction rate over time. The product quality is a measure
of the ability of the process to yield products with the desired use specification such as pour point,
smoke point, or octane. Table 8 shows some of the important product quality measurements and the
chemical basis for these measurements.
Hydrotreating Process Variables

The proper operation of the unit will depend on the careful selection and control of the processing
conditions. By careful monitoring of these process variables, the unit can operate to its full potential.
Reactor Temperature
Reactor temperature should be minimized while maintaining desired product quality. Increasing
reactor temperature will accelerate the rate of coke formation and reduce the length of the operating
cycle. The required temperature is dependent upon feed rate and quality and processing objectives.
The reactor inlet temperature is most easily and commonly controlled by the operator to adjust for
obtaining the desired product quality. The reactor outlet temperature is a function of the feed quality
and cannot be easily varied except by changing the reactor inlet temperature or the temperature
profile across the beds by the use of quench. The inlet temperature must always be controlled at the
minimum required to achieve the desired product properties. Temperatures above this minimum will
only lead to higher rates of coke formation and reduced processing periods. The weight average bed
temperature (WABT) is the kinetic parameter typically used to compare the relative catalyst activity.
The WABT can be calculated as shown in Fig. 27.
If the reactor only has inlet and outlet thermometry (as is the case in perhaps as many as two-thirds
of hydrotreaters), the WABT represents the average of inlet and outlet temperatures. The rate of
increase in this temperature is referred to as the deactivation rate expressed as F per barrel of feed
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A = 20% Catalyst Weight

B = 30% Catalyst Weight
A Tl1 +C = 50% Catalyst Weight
Total = 100% Catalyst Weight
B Tl2 Tl1 = Average Bed Temperature = 680°F (360°C)

Tl1 = Average Bed Temperature = 700°F (371°C)
Tl1 = Average Bed Temperature = 725°F (385°C)
WABT = 680*0.2 + 700*0.3 +725*0.5 = 708.5°F

C Tl3
WABT = 360*0.2 + 371*0.3 +385*0.5 = 375.8°F
Fig. 27 Weighted average bed temperature (WABT)
per pound of catalyst ( C per m3 of feed per kilogram of catalyst) or simply as F per day ( C per
day). During the course of an operating cycle, the temperature required to obtain the desired product
quality will increase as a result of catalyst deactivation. The maximum catalyst operating temper-
ature determines the temperature cycle and cycle length of the catalyst.
The metallurgical design temperature of the reactor(s) will determine the maximum allowable
catalyst operating value. The axial and radial temperature rise across the reactor(s) must be
monitored continuously in order to assure that the design limitation of the unit is not exceeded.
This can be especially important when changing feedstocks since olefin saturation results in
considerably higher heats of reaction. Units are typically designed for a maximum reactor bed
temperature rise <60 F (33 C).
Feed Quality and Rate

The amount of catalyst loaded into the reactors as well as other design parameters are based on the
quantity and quality of feedstock the unit is designed to process. While minor changes in feed type
and charge rate can be tolerated, wide variations 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 a constant desulfurization (or denitrogenation) as well as higher recycle gas rate to maintain
a constant ratio of H2 to hydrocarbon. The increased reactor temperatures will lead to a faster rate of
coke formation that will reduce the cycle length. A reduced feed rate may lead to bad flow
distribution through the catalyst, such that higher temperatures will be required to obtain good
product quality. A feed’s distillation range and API gravity best indicate the type of feed being
processed. An increase in the end point of the feed will make sulfur and nitrogen removal more
difficult, thus requiring higher reactor temperatures which, in turn, accelerate coke formation. Coke
deposition is also accelerated by the fact that heavier feed contains more of the precursors that favor
coke formation. In addition to the above, high boiling fractions also contain increased quantities of
metals which lead not only to higher reactor pressure drop but to rapid catalyst deactivation as well.
A reduction in the API gravity of the feed for the same boiling range is an indication of higher
unsaturates content. This type of feed will result in increased hydrogen consumption and higher
temperature rise across the catalyst bed. It also contains more of the materials that easily condense to
form coke in the reactor and associated equipment.
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Diesel Cetane Number
Hydrogen partial pressure
Fig, 28 Effect of pressure on aromatics saturation

Aromatics in Product
Hydrogen partial pressure
Fig. 29 Effect of pressure on distillate quality
Hydrogen Partial Pressure

The hydrogen partial pressure is calculated by multiplying the H2 purity of the recycle gas times the
pressure of the product separator. The hydrogen partial pressure required for the operation of a unit is
chosen based on the degree of sulfur (or nitrogen, or aromatic saturation) removal that must be
achieved and is generally an economic optimum that balances capital cost and operating costs
against catalyst life. Hydrogen partial pressure is also a critical design parameter for achieving the
desired degree of feed saturation. Figures 28 and 29 illustrate the effect of hydrogen partial pressure
on the quality of the products. A reduction of the operating pressure below the design level will have
a negative effect on the activity of the catalyst and will accelerate catalyst deactivation due to coke
formation.
Gas-to-Oil Ratio
This is an important variable for the satisfactory performance of a hydrotreater. If the unit is operated
at lower than design ratios, more rapid catalyst deactivation will result. The circulating gas also
provides the heat sink for the removal of the heat of reaction. Though various hydrotreating unit
designers and catalyst manufacturers use different values, it is generally accepted that the minimum
gas-to-oil ratio should be at least three to four times the amount of hydrogen consumption, although
this may be lower for distillate and naphtha hydrotreating operations.
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Liquid Hourly Space Velocity

The design quantity of catalyst per unit of feed will depend upon feedstock properties, operating
conditions, and product quality required. A simplified kinetic expression based on sulfur and/or
nitrogen removal determines the design liquid hourly space velocity for most feedstocks and
processing objectives. This initial value may be modified due to other considerations such as unit
size, extended catalyst cycle life, abnormal levels of feed metals, and requirements of other
processing units in the refinery flow scheme. A unit design is based on operation to achieve optimum
performance. One criterion is liquid mass flux across the catalyst bed. At reduced throughput, unit
operation may become difficult due to hydraulic considerations. Also, liquid distribution in the
reactor may become unequal as preferential flow paths are established. For these reasons, the unit
should not be operated below the minimum turndown capacity for extended periods. Unit turndown
will vary for each design and is typically 50–70 % of design capacity. Operation at too high of space
velocity (compared to original design) is not advisable because of increased catalyst deactivation
rates as well as increased system pressure drop.
Recycle Gas Purity

The effective completion of the hydrogenation reactions occurring over the catalyst requires that a
certain quantity of hydrogen be present at a minimum hydrogen partial pressure. As noted previ-
ously, both the quantity (gas-to-oil ratio) and partial pressure are dependent upon the hydrogen
content, i.e., purity, of the recycle gas. Practical considerations, such as the cost of compression,
catalyst life, etc., limit the purity of the recycle gas to a minimum value usually in the range of
70–80 mol%. Lower hydrogen purities are detrimental to the performance of the unit since higher
temperatures must be used to achieve the desired product quality. The purity of the recycle gas is
determined by the following factors:
• The purity of the makeup gas and introduction of light ends into the reactor circuit
• Vapor/liquid equilibrium at the separator that forms the recycle gas
• The amounts of light hydrocarbons and H2S that are allowed to accumulate in the recycle gas
In most instances, the makeup gas H2 purity cannot be easily manipulated since it is fixed by the
operation of the reformer or the hydrogen manufacturing plant. The light hydrocarbons present in
the recycle gas enter the system with the makeup gas in addition to those being formed in the reactor
and must be vented from the high-pressure separator to prevent their accumulation in the recycle gas.
The amount of hydrogen required is determined by:
(a) Chemical hydrogen consumption – the hydrogen consumed during the hydrotreating reactions.
(b) Solution losses – the hydrogen that is removed from the reactor circuit dissolved in the liquid
hydrocarbon leaving the high-pressure separator.
(c) Mechanical losses – the hydrogen lost through the makeup and recycle gas compressors’
packing vents and seals. This value may be roughly estimated at 3–5 % of the combined
chemical consumption plus solution losses.
(d) Venting losses – the hydrogen lost in the purge stream from the high-pressure separator to
maintain recycle gas purity.
The H2S formed in the reactors can reach equilibrium values as high as 5 mol% in the recycle gas.
This concentration of H2S has an inhibiting effect on the activity of the catalyst. Therefore, in many
cases it is desirable to remove the H2S from the recycle gas. The removal of H2S is performed in a
Page 56 of 59
DOI 10.1007/978-3-319-05545-9_4-1
scrubber where the recycle gas is contacted with an amine (generally MEA, DEA, or MDEA)
solution. In this manner, the H2S content of the recycle gas can be reduced to the parts per million
range.
Another method to increase hydrogen purity is membrane separation. This system removes the
hydrogen from the vent gas and recycles it back with the makeup hydrogen.
Feed Contaminants and Catalyst Poisons

Temporary
Process variables influence catalyst life by affecting the rate of carbon deposition on the catalyst.
There is a moderate accumulation of carbon on the catalyst during the initial days of operation. The
rate of increase will be reduced to very low levels under normal processing conditions. A carbon
level of 5 wt% may be tolerated without a significant decrease in desulfurization. However,
denitrogenation activity would be reduced.
The sulfur and nitrogen found in the feed could be considered contaminants to the extent that they
produce hydrogen sulfide and ammonia which can react to form ammonium bisulfide. The water
injected into the reactor effluent dissolves the ammonium bisulfide and prevents exchanger fouling.
Organic nitrogen in the feed, if present in amounts higher than expected, will require higher reactor
temperatures for processing and will lead to a reduction in catalyst life.
If the water injection should be stopped for any period of time, the H2S and NH3 may accumulate
in the recycle gas and result in a sudden loss in catalyst activity. The activity will return to normal
once wash water is reestablished. Catalyst bed temperatures should not be increased to compensate
for the temporary activity loss.
Small amounts of molecular nitrogen, CO, and CO2 that enter the system with the makeup gas are
not harmful to the catalyst, but must be vented to prevent accumulation in the recycle gas. Excessive
amounts of CO and CO2 may have an adverse effect on catalyst performance, as they may be
methanated by the catalyst taking up active sites and liberating heat. This will raise the outlet
temperature and reduce the apparent catalyst activity. The unit should never be pressured up with
high CO + CO2 containing makeup gas as a temperature runaway may result.
Permanent
Permanent loss of catalyst activity is usually caused by the gradual accumulation of inorganic
species picked up from the feed, makeup hydrogen, or effluent wash water. Examples include
arsenic, lead, calcium, sodium, silicon, and phosphorus. Low concentrations of these elements (and
other alkaline metals) can cause deactivation over time as they are deposited on the catalyst.
Organic metal compounds are decomposed and typically deposit in the upper section of the
catalyst bed as a metal sulfide. The graded catalyst bed, if used, may contain demetallation catalysts
that have a high metal retention capacity. Some of these catalysts may retain as much as 100 wt% of
the fresh catalyst weight as metals from the feed. These demetallation catalysts typically have a
lower activity for desulfurization and denitrogenation.
Hydrotreating catalysts exhibit a moderate tolerance for metals such as arsenic and lead. Total
metal content of 2–3 wt% of the hydrotreating catalyst have been observed. However, product
analysis frequency should be increased to monitor breakthrough when calculations show the metal
level on the hydrotreating catalyst exceeds 0.5 wt%. Metals cannot be removed by catalyst
regeneration. Catalyst replacement should be considered when metal loading of 1–2 wt% is
exceeded on the hydrotreating catalyst.
Apparent catalyst deactivation may be caused by the accumulation of deposits on top of the
catalyst bed. Solid material, such as corrosion products and coke, will lead to rapid fouling of the
Page 57 of 59
DOI 10.1007/978-3-319-05545-9_4-1
catalyst bed if allowed to enter the reactor. This problem is remedied by skimming a portion of the
catalyst, screening, and reloading. Feed filtering is a first defense and is quite effective in removing
solid material and as such results in longer operating cycles due to the lower rate of reactor pressure
drop buildup. The use of feed filtering will depend on the type of feed processed and its source.
A second line of defense is the use of specially shaped particle or reticulated media loaded above the
active hydrotreating catalysts to remove fines that pass through the feed filter or are formed in situ in
the reactor circuit.
Hydrotreating Technology Suppliers and Catalyst Manufacturers

Technology Suppliers
Historically many companies have offered to supply hydrotreating unit technology. Most types of
hydrotreating processes are offered through licensing arrangements and some are non-licensed
technologies. Today, CB&I/Chevron Lummus Global (CLG), Axens/IFP Energies Nouvelles,
Shell Global Solutions/KBR, Haldor Topsøe, DuPont, and Honeywell UOP are the main providers
of technology for the various types of hydrotreating units.
Catalyst Manufacturers
Through the years, there have been many manufacturers of hydrotreating catalysts. Some suppliers
have consolidated with others. Other manufacturers have absorbed some, some have changed
names, and some have discontinued hydrotreating catalyst manufacturing. Some suppliers simply
sell catalyst they have re-branded with their name. The following is a list of the current major
suppliers of hydrotreating catalysts: Advanced Refining Technologies (ART), Albemarle, Axens/
IFP Energies Nouvelles, Criterion Catalysts and Technologies (CRI)/Shell Global Solutions, Haldor
Topsøe AS, Orient Catalyst Co. Ltd., Clariant International Ltd./ S€ ud-Chemie Inc., and
Honeywell UOP.
References
P.E.M. Berthelot, Methode universelle pour réduire et saturer d’hydrogéne les composés organiques.
Bull. Soc. Chim. 11(278), 278–286 (1869)
M. Breysse, C. Geantet, P. Afanasiev, J. Blanchard, M. Vrinat, Catal. Today 130, 3–13 (2008)
J. Čejka, Appl. Catal. Gen. 254, 327–338 (2003)
F. Chainet, Ph.D. Thesis, Spéciation du silicium dans les charges d’hydrotraitement, 2012
R.R. Chianelli, G. Berhault, B. Torres, Unsupported transition metal sulfide catalysts: 100 years of
science and application. Catal. Today 147(3–4), 275 (2009)
A.I. Dugulan, High Pressure Sulfidation of Hydrotreating Catalysts – Genesis and Properties of the
Active Phase, Delft University Press (IOS Press, 2008)
S. Eijsbouts, S. Mayo, K. Fujita, Unsupported transition metal sulfide catalysts: from fundamentals
to industrial application. Appl. Catal. Gen. 322, 58 (2007). Active Phases for Hydrotreating
Catalysis
N. Frizi, P. Blanchard, E. Payen, P. Baranek, C. Lancelot, M. Rebeilleau, C. Dupuy, J.P. Dath, Catal.
Today 130, 32–40 (2008)
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E.J.M. Hensen, V.H.J. de Beer, J.A.R. van Veen, R.A. van Santen, Catal. Lett. 84(1), 59 (2002)
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442–451 (2003)
T. Ho, Deep HDS of diesel fuel: chemistry and catalysis. Catal. Today 98, 3–18 (2004)
V.N. Ipatieff, Russkoe Fiziko-Kimischeskoe Obshchestvo, 33, 143–154, 496–506, 532–545,
632–643 (1900–1902)
L. Jones, P. Kokayeff, Distillate hydrotreating to ULSD – the impact of aromatics, in Paper 90a,
AIChE 2004 Spring National Meeting, 27 Apr 2004
L. Jones, P. Kokayeff, Equilibrium limitations in distillate hydrotreating, in Paper 61d, AIChE 2005
Spring National Meeting, 10 Apr 2005
L. Leonard, P. Kokayeff, Recombination – a complicating issue in FCC naphtha desulfurization, in
Paper 177c, AIChE 2006 Spring National Meeting, 26 Apr 2006
M. Pier, Z. Elektrochem. 53, 297 (1949)
P. Sabatier, J.B. Senderens, Action du nickel sur l’éthyléne. Compt. Rend 124, 1358 (1897)
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Handbook of Petroleum Processing

Hydrotreating in Petroleum Processing

Fig. 1 Schematic ﬂow diagram of a hydrotreater

Reactor Charge Heater

Makeup Hydrogen System

Vgo unionfining unit

Fresh To off gas

Fig. 2 Schematic ﬂow diagram of a reactor section

Recycle Hydrogen System

Recycle Gas Scrubbing

Reactor Efﬂuent Water Wash

Vgo unionfining unit

Fig. 3 Schematic ﬂow diagram of a fractionation section

• Sulfur removal, also referred to as desulfurization or hydrodesulfurization (HDS) in which the

• Hydrodesulfurization and oleﬁn hydrogenation are the most rapid reactions.

R1-S-R2 þ 2H2 ! R1-H þ R2-H þ H2 S

R1-S-S-R2 þ 3H2 ! R1-H þ R2-H þ 2H2 S

H2 C ¼ CH-CH ¼ CH2 þ 2H2 ! H3 C-CH2 -CH2 -CH3

Easiest to remove ! hardest to remove

Relative Reaction Rates of Selected Sulfur Species

Fig. 5 Relative reaction rates of selected sulfur species

Some typical examples of denitrogenation reactions are shown below:

H3 C-CH2 -CH2 -CH2 -NH2 þ H2 ! H3 C-CH2 -CH2 -CH3 þ NH3

+ 4H2 H3C-CH2-CH2-CH3 and H3C-CH-(CH3)-CH3 + NH3

+ 5H2 H3C-CH2-CH2-CH2-CH3 and H3C-CH-(CH3)-CH2-CH3 + NH3

ðCH3 Þ3 -C-O-CH3 þ 2H2 ! ðCH3 Þ3 -CH þ H2 O þ CH4

Two rings – naphthalene

Three rings – phenanthrene

Metals and Nonmetal Removal

R-Me þ H2 S ! R-H2 þ MeS

Catalytic Chemistry of Diesel Desulfurization

Fig. 6 Comprehensive GC 3D image of hydrocarbon content of distillate

methyldibenzothiophene and 4,6-dimethyldibenzothiophene and similar structures, present the most

Fig. 7 Comprehensive GC 3D image of sulfur compounds in distillate

Catalysts and Reactions

Fig. 8 Comprehensive GC 3D image of nitrogen compounds in distillate

The “hydrogenation” pathway, in simpliﬁed form, is

Saturation reactions of aromatic compounds proceed sequentially

Simplified Process Flow Diagram

Reactor Recycle Gas

Fig. 9 Simpliﬁed process ﬂow diagram of a distillate hydrotreater

Table 1 Distillate hydrotreater typical process conditions

Straight-Run Versus Cracked Naphtha

Table 2 Properties of naphtha streams

Processing Objectives and Considerations

Table 3 Reformer feed specifications

removed via a different mechanism than sulfur contained in an aromatic compound. In

Potential for Recombination with Cracked Stock

Table 4 Naphtha hydrotreater operating conditions

Typical Operating Conditions

Total gas to reactors ðSCFH or Nm3 =hÞ

Make-up Recycle Gas

Fig. 10 Simpliﬁed process ﬂow diagram of a naphtha hydrotreater

Desulfurization of FCC Gasoline

Fig. 11 Simpliﬁed process ﬂow diagram of a coker naphtha hydrotreater

Composition of FCC Gasoline

Recombination is a reversible reaction that approaches equilibrium at conditions used to effect

WRSH ¼ f KWo PH2 S

WRSH ¼ f KWo WFS

WABT = 6800.2 + 7000.3 +725*0.5 = 708.5°F