PSPT3 2 PDF

2020-12-04
Petroleum Secondary Processing

Technology
Lecture (3) part (2)
Refinery Reaction Systems(Hydrocracking)
(Gerald Kaes , REFINERY PROCESS MODELING,1st edition , 2000, Kaes Enterprises, Inc.)
Prepared by : Mr. Serwan Ibrahem

MSc. Degree in Chemical Engineering
For 4th year students of Chemical and Petrochemical
Engineering Department .
Salahaddin University
Chemical & Petrochemical ENG _ Petroleum Secondary Processing
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Technology_4th Year
Hydrocracking and Hydrotreating

Both of these reactors are catalytic and both use a high hydrogen
environment to treat the feed stock. In the hydrocracking reactor,
the operating conditions are severe, and the strategy is to crack
the feed stock into lighter products and to saturate olefinic
and aromatic compounds with hydrogen.
Chemical & Petrochemical ENG _ Petroleum Secondary
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Processing Technology_4th Year
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Sulfur and nitrogen are converted to hydrogen sulfide and
ammonia and removed in the reactor. The chemical hydrogen
consumption is high for the hydrocracking process, and a refinery
must have an additional source of hydrogen available from that
normally produced by the other process units. The most common
supplemental source is a hydrogen generating plant that steam
reforms natural gas.
3

Hydrotreating is a mild form of hydrocracking. The strategy in
hydrotreating is to remove sulfur and nitrogen and to saturate
olefinic and some aromatic compounds in the feed stock.
Cracking is not desirable since the treated feed is usually a finished
product. Hydrogen consumption is much lower for hydrotreating
and most refineries have sufficient hydrogen available from the
catalytic reforming process.
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Hydrocracking: General Information:

The catalytic hydrocracking process predates catalytic cracking. The process was invented in
Germany prior to 1930 and brought to the United States by Esso Research and Engineering
Company. There was little commercial use of the process until the 1980's, when low values for
*fuel oil products and environmental demands for clean fuels made it economic to upgrade
low-grade fuel oils to more salable products.
*In general terms, fuel oil is any liquid fuel that is burned in a furnace or boiler for the generation of
heat or used in an engine for the generation of power, except oils having a flash point of
approximately 42 °C (108 °F) and oils burned in cotton or wool‐wick burners.
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Hydrocracking is unquestionably the most flexible cracking process
and it is used in a wide range of applications. In fact, it is often
possible to vary the process conditions significantly on a single unit
to process a variety of feed stocks. This process complements
catalytic cracking by cracking the more refractory cycle oils from
thermal operations. It is sometimes used to upgrade the cycle oils
from catalytic cracking to lighter products.
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A typical hydrocracking proces5 flowsheet is shown in the next
Figure. Gas oil feed is combined with recycle hydrogen, heated by
exchange with the reactor product followed by a furnace , and fed
to a reactor bed. The net heat of reaction is exothermic, and the
reacted mixture is cooled by injection of quench hydrogen prior to
entering a second ‘ reactor bed.
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The resultant product from the second reactor bed is cooled by
exchange with the feed and sent to a series of separators where the
liquid products are removed from the unreacted hydrogen and
light gases. A water wash is used to remove some of the impurities
from the hydrogen recycle stream.
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An amine treating process removes any remaining ammonia and
hydrogen sulfide from the recycle gas prior to re-circulation to the
process, Fresh hydrogen is added to the system as needed to
replace the hydrogen consumed in reaction and to maintain a
desired level of hydrogen in the recycle gas.
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The flowsheet of the last Figure has been simplified. Hydrocracking
processes may have multiple trains of reactor beds; however, the
principle is the same, and quench hydrogen is injected between the
reactor beds to control the reaction temperature.
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Depending on the process and the feed stock, there may also be a
"guard" reactor prior to the hydrocracking reactor(s) to remove
catalyst poisons and improve the product distribution and catalyst
life for the hydrocracking reactor(s).
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Hydrocracking reactors have fixed beds of catalyst that must be
taken off-line from time to time for regeneration of the catalyst
and/ or catalyst replacement. The run cycle is dependent on the
feed stock being processed and the severity of the operating
conditions: Catalyst may be regenerated several times before
replacement is necessary.
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Process Conditions
Process conditions vary widely for hydrocrackers because of the
variety of feed stocks that are processed. There is a relatively
large amount of hydrogen that is consumed, and it is usually
necessary for a refinery with hydrocracking to have a supplemental
source of fresh hydrogen, such as a hydrogen plant.
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Process Conditions
Reactor operating pressures range from 1000 to 2000 psig (70 to
139 bars), depending on the process and the feed stock.
Temperatures are in the range 600 to 850 (316 to 455 ). The
reaction temperature is controlled between reaction beds with
quench hydrogen.
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Process Conditions
Hydrogen consumption is a function of the feed stock being
cracked and the severity of the operating conditions. It may run
anywhere from 500 to 3000 *SCF/ barrel charge (89 to 534 SCM /).
The various processes call for a hydrogen to feed hydrocarbon ratio
of 1500 to 4000 SCF/barrel (270 to 712 SCM/ ) entering the reactor.
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Process Conditions
Cracking feed stocks include diesel fuel, atmospheric and vacuum
gas oils, FCC cycle oils, coker cycle oils, and residual oils. Cracked
feed stocks contain higher concentrations of unsaturated
compounds than virgin products and have higher consumptions of
hydrogen in the reactor.
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Process Conditions
A key reaction in the hydrocracker is the hydrogen saturation and
conversion of aromatic rings into naphthene rings that may be
cracked. Aromatic rings are very stable and cannot be cracked with
standard catalytic cracking processes.
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Process Conditions
Hydrogen saturation of olefins and aromatics results in a
substantial volumetric increase, and liquid volume gains of up to 25
percent are not unusual for hydrocrackers.
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Process Conditions
This process also produces less propane and dry gas than the other
cracking processes. Saturation of feed olefins and olefins produced
by cracking is very rapid and complete. Depending on the feed
stock and the operating severity, significant saturation of aromatic
rings may also be accomplished.
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Reactions:
Hydrocracking catalysts are a crystalline mixture of silica-alumina
(early cat cracking catalyst) with a small uniformly-distributed
quantity of a rare earth metal within the crystalline lattice structure.
Rare earth metals most commonly used are platinum, palladium,
tungsten, and nickel.
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Reactions:
The silica-alumina portion of the catalyst promotes cracking
reactions, while the rare-earth metals promote hydrogenation
reactions. These reactions are complementary, with the exothermic
hydrogenation reactions providing reaction heat for the
endothermic cracking reactions. Hydrocracking catalysts are
susceptible to poisoning by metalic salts, oxygen, organic nitrogen
compounds, and sulfur in the feed stock.
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Reactions:
Guard reactors typically use a catalyst of cobalt-molybdenum on
silica-alumina to remove sulfur and nitrogen compounds and to
protect the precious metals in the hydrocracking catalyst.
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Reactions:
For hydrocracking of heavily contaminated feeds, such as residual
materials, it is necessary to use guard reactors to prolong the
hydrocracking catalyst life and maintain the desired product
distribution.
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Reactions:
The gas oil feed to a hydrocracker may have dozens of actual
components from several chemical classes. The many combinations
of cracking and hydrogenation reactions result in hundreds of
reactions occurring. Next table gives a brief list of some of the
typical reactions that occur in the hydrocracker reactor.
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Chemical&Petrochemical ENG _ Chem Reactor Design I_3RD
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Year
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Year
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Reactions:
Feed olefins and olefins created in the reactor are rapidly saturated
in the high hydrogen atmosphere. Isomerization is also favored in
the reactor and high octane iso-paraffins are present in the reactor
product. Condensed aromatic rings are also saturated to
cycloparaffins that may be cracked to smaller molecules.
29
Reactions:
There are no unsaturated non-ring structures in the reactor
effluent. Hydrogen sulfide tends to inhibit the saturation of
aromatic rings. This conserves hydrogen and produces a gasoline
of higher octane than a straight naphthenic gasoline.
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Reactions:
The overall reaction provides an excess of heat because the amount
of heat released by the exothermic hydrogenation reactions far
exceeds the heat required for the endothermic cracking reactions.
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Reactions:
This excess heat causes the reactor temperature to rise and
accelerates the reaction rate. This is controlled by the injection of
cold hydrogen quench into the reactors to absorb the excess
reaction heat.
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End of Lecture 3 part 2.
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2020-12-04

Petroleum Secondary Processing

Prepared by : Mr. Serwan Ibrahem

Hydrocracking and Hydrotreating

Hydrocracking and Hydrotreating

Hydrocracking and Hydrotreating

Hydrocracking: General Information:

Hydrocracking: General Information:

Hydrocracking: General Information:

Hydrocracking: General Information:

Hydrocracking: General Information:

Hydrocracking: General Information:

Hydrocracking: General Information:

Hydrocracking: General Information:

End of Lecture 3 part 2.

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