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SOR(*) EOR(*)
HDS Reactors
Temperature (°C)
SOR EOR
H 2S 0.72 0.72
NH3 0.03 0.03
C1 0.03 0.05
C2 0.03 0.05
C3 0.06 0.1
C4 0.08 0.12
C5 - 302°F 0.08 1.4
100.84 100.89
In order to limit the catalyst temperature to the maximum acceptable, the catalyst is installed in three
beds on two reactors in such a way that the temperature increase on a bed is limited to a maximum
value.
Between the first and second catalyst beds and the second and the third catalyst beds, cold recycle
gas quenches are injected to cool the reactants entering beds.
The catalyst bed volume is calculated to give an increase of temperature lower than 20°C. The
quantity of cold quench injected between two beds is adjusted to bring the control of reactor
temperature profile.
1- TEMPERATURE
a - In and out temperatures
b - Temperatures profile
Feed
Temperature °C
Bed 1
1st quench
Bed 2
Thanks to the quench with recycle gas,
the inlet temperature of second and third
bed are reduced.
- to be as close as possible of
isothermal profile
Bed 3
D PCD 381 B
Effluent
c - Average temperature
The temperature is an operating parameter under permanent control, as it is directly related to the
furnace outlet temperature.
Nevertheless, the furnace outlet temperature (or reactor inlet temperature) is not the correct approach
to the reaction temperature on the catalyst. For this purpose another temperature is considered more
representative. For a catalytic bed and for a reactor with several beds: it is the Weight Average Bed
Temperature (WABT). WABT is the most practical means of averaging catalyst bed temperature.
WABT = = °C
From a kinetic point of view, when temperature increases, the rate of all the chemical reactions
increases, i.e. both the desirable and the undesirable reactions.
(From a thermodynamic point of view, desirable reactions are exothermic, thus are favored by a
decrease in temperature; thermodynamical limitation of reaction).
Remark: hydrogenation reactions of aromatics, olefins and diolefins decrease after a maximum with
increased temperature.
The process philosophy is to keep the temperature as low as possible because the most desirable
reactions (HDS, HDN and HDO) do not need high temperature to remain at desirable rates. By this
way, coking and cracking are limited and thus cycle length is increased.
Temperature is the main control variable because it has the greatest effect on reaction severity and
because most of the other variables are relatively fixed by unit design. Reactor inlet temperature is
gradually increased throughout the cycle to compensate for a decline in catalyst activity. Temperature
must also be routinely changed to accommodate changing product specifications and/or feed quality
throughout the cycle.
Too much heat, i.e. operation at temperatures in excess of that required to meet product specifications,
is detrimental to the catalyst because the higher temperatures increase the rate of catalyst
deactivation.
- HDS reactions start as low as 300°C, with the rate of reaction increasing markedly with
temperature
- aromatic saturation reactions slow down above about 380°C because dehydrogenation
reactions start to become favoured over hydrogenation reactions. The onset of this effect
can be delayed to a higher temperature by increasing the H2 partial pressure
- the maximum reactor outlet temperature in gas oil service is generally limited to between
380-390°C by either mechanical design considerations or product colour problems
- above 390°C, feedstock cracking occurs which rapidly accelerates coke laydown, increases
the H2 consumption and reduces product yield
Two sets of reactor temperatures are normally quoted - start of run (SOR) and end of run (EOR). EOR
temperatures are higher than at SOR in order to compensate for lost catalyst activity.
At any point in a cycle, there is a temperature rise across the reactor because the hydrotreating
reactions are exothermic. In gas oil service, this temperature rise normally ranges between 10-40°C.
Higher temperature rises can be produced when there is a high percentage of cracked cuts in the
feedstock.
The reactor temperature rise slowly reduces from SOR to EOR conditions because heat liberating
aromatic saturation reactions are reduced. There is a corresponding reduction in hydrogen
consumption from SOR to EOR conditions.
Exothermic temperature runaways do not occur under normal hydrotreating conditions for three
reasons:
- the heat liberating sulfur and olefin containing compounds react to extinction
- the endothermic dehydrogenation reactions that occur above circa 380°C act as an inherent
brake on any temperature increase
- typical hydrotreating catalysts do not have sufficient acid function to initiate the exothermic
hydrocracking reactions that are required to sustain an exothermic runaway
Isothermal conditions are the best for the desulfurization reaction. For this reason the increase of
temperature is limited to 20°C max. In order to limit the catalyst temperature to this maximum, the
catalyst is divided in three beds. The feed quality may vary within a certain range depending on
cracked cuts content. The total exothermicity across the reactors will also fluctuate accordingly, this
has to be controlled by the duty of the heater.
Considering the above definitions it is clear that to operate the first catalytic bed at the same WABT
requires a lower reactor inlet temperature with a cracked feed (important exothermicity) than with a
straight run feed.
Between the 1st and 2nd catalyst beds and between the 2nd and 3rd catalyst beds, cold recycle gas
quenches are injected to cool the reactants entering beds.
The quantity of cold quench injected between two beds is adjusted to bring the temperature at the top
of the lower bed to the same value as the temperature at the top of the upper bed.
The bed temperatures are adjusted to the lowest values that enable to meet the product
specifications.
The lower and longer the reactor WABT can be kept, the longer will be the catalyst cycle. To extend
the catalyst cycle lenght at EOR conditions is much more difficult than at SOR because of the
accelerated deactivation rates at higher temperature.
The inlet temperature to the first catalyst bed at start of run (SOR) conditions is adjusted to 325°C
through the temperature control value on the fuel gas to the reactor heater.
The average reactor catalytic bed temperatures have to be carefully adjusted (SOR = 335°C -
EOR = 375°C):
– they should be high enough to get the product specifications in accordance with the feed
analysis and with the catalyst ageing
– they should be as low as possible to optimize the length of cycle between two
regeneration and finally the catalyst life
Due to a slow and continuous loss of catalyst activity with time, the temperature must be increased to
compensate this low of activity.
Molecular % mol H2 H2
kg/h
mass
kmoles/h Nm3/h H2 kmoles/h Nm3/h
Make up gas
Recycle
Total
Make up =
Gas flow rate Nm3 of gas/m3 of feed = =
Recycle =
Make up =
H2 flow rate Nm3 of H2/m3 of feed = =
Recycle =
Conclusion
Hydrogen partial pressure is the part of the total pressure only due to the molecules of hydrogen in the
gas phase.
Reactor H2 partial pressure is calculated from the knowledge of treat gas rate and composition, fresh
feed rate and distillation, reactor temperature and reactor pressure. An equilibrium flash calculation
must be performed to identify the amount and composition of the vapor existing within the reactor (for
info % at SOR wt vapor is 35% at reactor inlet and 53% at reactor outlet) when fresh feed is mixed with
treat gas and heated to reaction temperature, a certain amount of fresh fed vaporizes. The HDT
reactors operate thus in a partially vaporized region which adds complexity because of the variability in
feed vaporization. H2 partial pressure decreases from catalyst bed inlet to outlet due to chemical
consumption of H2 and bed pressure drop and HC vaporization due to the increase of temperature.
- H2 chemical consumption
- dilution because higher feed vaporization (Toutlet > Tinlet) and light products produced by
the chemical reactions
It is equal to:
TOTAL HYDROGEN
kmoles/h kmoles/h
H2 chemically consumed –
PP H2 = . =
PP H2 = bar abs.
High hydrogen partial pressure favours the desirable HDS reactions, while limitating the
undesirable reactions (coking and crocking). For this reason, hydrogen partial pressure must be
kept as high as possible.
From an operating point of view, PPH2 is a function of the purge (hydrogen excess compared to the
hydrogen consumption), the recycle gas flow, the temperature at the reactor outlet, the composition of
the effluent and the reactor outlet pressure. It is directly related to the HP separator pressure which is
kept constant at the maximum value allowed by the design.
The PPH2 outlet of the reactor must be kept above 70 bar abs (minimum recommended).
A chemical reaction takes place at a certain reaction rate, thus the amount of manufactured products
is a function of time.
The reactor represents a volume, available to the reactants, in order to allow them the required
residence time for their transformation. Residence time is the average time during which a chemical
component remains in the reactor.
The amount of catalyst is determined to ensure sufficient residence time to achieve the desired
performance with the fixed feed flow rate. Residence time is characterized by the LHSV: liquid
hourly space velocity, defined by:
As catalyst volume is fixed, feed flow rate is the only parameter to vary the residence time: the
smaller the feed flow rate, the smaller the LHSV, the longer the residence time.
The higher the LHSV, the lower the residence time of the feed in the reactor, and the more limitated
the chemical reactions (both desirable and undesirable reactions).
LHSV in operation
The LHSV is an operating parameter under permanent control as it is directly related to the feed flow
rate.
The LHSV has to be kept below 0.57 h–1 (maximum recommended at design).
An increased space velocity (i.e. an increased flow rate) results in a lower performance (hydrogenation
rate and hydrodesulfurization rate), all other conditions being equal. The performance can be
maintained if the temperature is increased, however it is at the expense of a higher coking rate.
Conversely a lower space velocity (reduced flow rate) means higher hydrogenation and desulfurization
rates.
The LHSV is low in order to insure a high residence time mandatory to achieve the very high
desulfurization rate.
5- HYDROGEN CONSUMPTION
H2 consumption is generally expressed as standard Nm3 of H2 per m3 of feed. There are four
components making up total unit hydrogen consumption.
* Chemical consumption
This is the H2 which is consumed by the hydrotreating reactions and is normally the largest component
of total consumption. The main hydrogen consuming reactions are:
- contaminant removal, i.e. sulfur, nitrogen, oxygen
- olefin saturation
- aromatic saturation
The chemical H2 consumption for contaminant removal depends on the distribution and percent
removal of each contaminant.
* Solution losses
This is the H2 which leaves the reactor circuit dissolved in the hydrocarbon leaving the high pressure
separators. Increased H2 partial pressure and increased temperature at the product separator both
increase solution losses.
* Purge losses
This is the H2 which leaves the reactor circuit when using a recycle gas purge to improve recycle gas
purity.
* Mechanical losses
The H2 which is lost through mechanical leakage around the make-up and recycle gas compressors,
i.e. packing vents and seals. Mechanical losses are generally estimated to be about 3-5% of the total
H2 consumption.
H2 make-up gas
Composition Vol %
H2 (hydrogen) 90
C1 (methane) 5
C2 (ethane) 2.5
C3 (propane) 2.0
C4 (butane) 0.5
100.0
MW = 4.54
H2 recycle gas
H2 (hydrogen) 84.3
H2S (hydrogen sulfide) 1.0
C1 (methane) 10.0
C2 (ethane) 2.9
C3 (propane) 1.3
C4 (butane) 0.3
H2O (water) 0.2
100.0
MW = 5.28
Treat gas delivers essential H2 to the reactor. Reductions in treat gas purity reduce the amount of H2
being delivered.
The H2S content in the recycle gas builds up to an equilibrium level at the product separator. The
presence of H2S in treat gas acts in two ways; firstly it inhibits the desulfurization reaction and
secondly it reduces the reactor H2 partial pressure. There are two ways to deal with H2S in treat gas.
The first way is to compensate for the reduced desulfurization either by an increase in reactor WABT or
a decrease in LHSV. The penalty in doing so however is reduced catalyst life and/or reduced unit
throughput. The second way which has been selected for this unit is to use a recycle gas scrubbing to
remove the H2S. This option has the advantage of tackling both of the detrimental effects of H 2S,
which together allows an increase in catalyst life and/or unit throughput.
The recycle gas H2S level should be maintained at approximately 0.5/1% vol.
Inert gases (eg. nitrogen) in the reactor circuit are only harmful as a diluent that reduce treat gas purity,
and hence, H2 partial pressure. If the minimum H2 partial pressure cannot be maintained then it will be
necessary to commission a small continuous purge of recycle gas to remove the inerts.
7- WASH WATER
Waste water is not normally considered as a process variable, however it is important for continuous
trouble free operation of a Diesel hydrotreater. Wash water is introduced into reactor effluent to remove
the ammonia (NH3) formed as a result of HDN. If not removed, the ammonia can combine which
chlorine and hydrogen sulphide to form salts that would otherwise foul the colder sections of the plant.
Gas oil units normally employ continuous water wash due to high nitrogen levels in the feed. In
general, the higher the feed nitrogen content and the higher the H2S in recycle gas, then the more
important in the wash water. The need for wash water is evaluated by calculating the partial pressures
of H2S, HCL and NH3 and then checking on the sublimation graphs for NH4HS and NH4Cl wether
there is a risk of solid deposition (see figure B5).
There are three wash water injection criteria that must be simultaneously met, all of which target to
avoidance of accelerated corrosion conditions that can occur with incorrect water injection rates:
- the wash water must be injected at a point in the process upstream of where ammonium salt
sublimation can occur, i.e. the process temperature at the injection point must be higher
than the salt sublimation temperature
- the total wash water injection rat should be set to achieve a minimum of 1 LV% on feed of
unvaporized water or 25% of the injected water unvaporized, whichever is greater,
immediately downstream of the injection point, i.e. all the water is not allowed to vaporize at
the air cooler inlet
- the ammonium bisulphide concentration in wash water effluent from the product separator
shall not exceed 4 wt % NH4HS for carbon steel metallurgy to avoid corrosion
- select operating conditions ensuring a steady operation and a slow ageing of the catalyst.
the deactivation rate is reduced with lower temperature and higher hydrogen pressure
- select operating condition profitable considering investments and operating cost
The compromise between these two requirements is done when designing the unit.
1 - HYDRODESULFURIZATION
Under the usual industrial conditions this reaction has no thermodynamic limitation.
2 - HYDROGENATION OF AROMATICS
This reaction has thermodynamic limitation.
For a given pressure, when the temperature increases, the thermodynamic equilibrium is displaced
towards the aromatic, i.e. the hydrogenation is limited. This reaction is strongly exothermic.
For a given temperature, the theoretic maximum hydrogenation rate increases rapidly with the
pressure.
6- HYDROCRACKING
It is an undesirable reaction which is to be minimized, because it consumes hydrogen, reduces the
yield and the hydrogen purity of the recycle gas.
It is limited by the selection of catalysts with low hydrocracking capacity and working at low
temperature.
7- COKING
The coking is limited by operating at the lowest temperature possible, with a sufficient hydrogen partial
pressure and liquid hourly space velocity.
8- SUMMARY TABLE
Desulfurization
Denitrification
Hydrogenation
Deoxygenation
Hydrocracking
D CH 2218 A
Coking