Refining-Petrochemicals-Chemicals-Engineering

OPERATION OF A DISTILLATE
HYDROTREATMENT UNIT (2)

DESCRIPTION OF THE REACTION SECTION .................................................................................. 1

1 - Overall description ........................................................................................................................1
2 - Operating conditions.....................................................................................................................3
3 - Estimated ex-reactor yields ..........................................................................................................4
4 - Control philosophy of the process ................................................................................................ 4
5 - Operating parameters...................................................................................................................5
6 - Action of process variables on reactions ....................................................................................14

RA REF - 00679_C_A - Rv. 0 04/03/2009

2009 - IFP Training
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DESCRIPTION OF THE REACTION SECTION

The simplified flow scheme of the reaction section is given in figure B1 (SOR) and B2 (EOR).

1- OVERALL DESCRIPTION
HDS reactors (hydrodesulfurization) - Diesel feedstocks
The feeds to the Diesel HDT are combined and then preheated by the bottom product of the
fractionator in the Diesel charge heater exchanger E-01. The hot Diesel feed is sent to the Diesel feed
surge drum D-01. The drum pressure is controlled by either a split range fuel gas to flare pressure
control.

The feed is pumped under flow control via the Diesel feed pumps G-01 A/B to the Diesel feed/effluent
exchangers E-02 A/B/C.

The refinery H2 make-up gas coming from battery limit is sent to the make-up K.O. Drum D-07. It is
then compressed by the H2 make-up compressors G-03 A/B. The make-up hydrogen is mixed with a
part of the recycle gas. Before mixing the gas with the Diesel feed, it is preheated in the Diesel
hydrogen preheater E-05.

The gas and the Diesel feed are mixed and then preheated in the Diesel feed/effluent exchangers. The
reactor feed is brought up to the required temperature in the Diesel heater B-01. The furnace outlet
temperature is controlled by acting on fuel gas to the heater burners.

The fluid is routed to the Diesel reactors D-02 and D-03, which operate down flow. In order to limit the
temperature increase inside the reactors, the catalyst is installed in two reactors, respectively with two
and one bed and cold quench gas is injected at the interbed section and between the reactors, under
flow control reset by catalyst bed inlet temperature.

Details of the reactors are given in figure B3 and B4.

At the top of each bed, a distributor tray and a bed of alumina beads are installed to overcome any
distribution irregularities of the feed flux entering the bed. It is important to avoid channelling, which
causes heterogeneities in the catalyst bed (and for example formation of hot zones that would cause
deterioration of the catalyst). In the first reactor, the first catalyst bed is supported by a grid. An
alumina beads bed supports the second catalyst bed. In the second reactor, the catalyst is supported
by an alumina bed.

Baskets, installed at the top of the upper bed into the first and second reactors, trap the residual fines
from the feed.

Cold quenches of hydrogen coming from recycle compressor are added at the inlet of each new bed
under TC/FC cascade to control the bed inlet temperature.

The interbed spaces are equipped with a mixing tray, specially designed to ensure a proper contact
between quench and effluent.

At the outlet of the reactor, the effluent is used to preheat the reactors feed in E-02 A/B/C and is then
collected in the Diesel hot separator D-04. The temperature in this drum is controlled by adjusting the
amount of feed by-passed around E-02 A/B/C.
The gas phase from hot separator is cooled and partly condensed successively by heat exchange with
hydrogen treat gas in E-05 and in the high pressure air cooler E-07.

To avoid ammonium salt deposits and risk of corrosion, water is injected at the inlet of the air-cooler
E-07. The washing water is a mixture of water recovered at the sour water stripping section, BFW and
water from the fractionator. This mixture is collected in the wash water tank D-12.

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The wash water tank pressure is maintained by a split-range fuel gas to flare pressure control on the
drum. The washing water is circulated by the wash water pumps G-07 A/B.

Liquid hydrocarbon, coming from the cold low pressure separator D-11, is pumped by HC wash pumps
G-05 A/B to the air cooler E-07 inlet in order to increase the hydrogen concentration in the gas phase.

The air cooler effluent is collected in the cold high pressure separator D-10, where three phases are
separated: gas, hydrocarbons and water. The pressure of this drum is controlled by the spill-back
around the make-up compressors G-03 A/B. The sour water containing ammonium salts is removed
under level control and routed to the sour water stripper section though the sour water flash drum
D-24 to disengage dissolved hydrocarbons. This vessel is also equipped with a naphtha skimming
system.

The gas phase is partly sent to the high pressure amine scrubber D-09, where H2S is removed. In D-
09 the amine wash is followed by a water wash circulated by the pump G-06. The other part by-passes
the absorber and is directly routed to the recycle compressor G-04. This by-pass allows the control of
H2S concentration in the recycled gas.

The hydrocarbon liquid phase from the high pressure cold separator D-10 is sent, under level control,
to the low pressure separator D-11. This drum receives also the partly condensed vapors from the low
pressure air cooler E-08. D-11 separates three phases. The vapor phase is routed to the top of the
stripping section. The water is combined with the waste water from D-10 through
D-24 sour water flash drum and goes to the sour water stripper section.

The hydrocarbons are divided into two streams: the first one represents the hydrocarbon wash to
E-07, the second one is sent to the H2S stripper feed. This stream is heated by the bottom product of
the fractionator in E-09.

The hot low pressure separator D-13 collects the effluent from Diesel hot separator D-04. The liquid
phase is directed, under level control, to the H2S stripper. Before leaving the reaction section, the liquid
phase from D-13 and the hot naphtha from E-09 are combined to the H2S stripper D-14.

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2- OPERATING CONDITIONS
The main operating conditions are reported in the table hereafter.

SOR EOR

HDS Reactors

Temperature (C)

Inlet 325 365

Outlet 345 385

Pressure (bar rel)

Inlet 105 114

Outlet 100 105

Vaporization of the feed (wt %)

Inlet 34.7 50.6

Outlet 52.9 73.7

Flow rate (/T/h)

Diesel feed 218.0 218.0

Hydrogen gas 33.2 34.6
Total feed to reactor 251.2 252.6
Quench 16.9 16.4
Reactor effluent 268.1 269.0

Reactor WABT (C) 335 375

Minimum H2 partial pressure reactor outlet (bar rel) 69 69

Space velocity LHSV (h1) 0.57 0.57

Min H2 recycle ratio (quenches excluded) 400 400

(Sd m3/m3)

Capacity (m3/h) 253.6 253.6

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3- ESTIMATED EX-REACTOR YIELDS (% wt)

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 - 302F 0.08 1.4

302F+ 99.09 98.42

100.84 100.89

4- CONTROL PHILOSOPHY OF THE PROCESS

a - Unit feed flow rate

The unit feed is a mixture of various gas-oils received from storage or other units under different
control modes. As it is of prime importance to have a steady feed flow rate towards the reaction
section, a feed surge drum receives the gas-oils from battery limits and feeds the reaction section
under flow control.

b - Reaction section pressure control

The unit feed quality may be unsteady and therefore the hydrogen consumption may also be unsteady.
This means that the hydrogen make-up flow rate has to follow the fluctuation of the hydrogen demand
in order to keep the reaction section pressure constant.

For this reason, the hydrogen make-up flow rate to the reactor is variable, and controlled by the
pressure at the cold separator D-10 (off-gas can be sent to fuel gas from the overhead of the HP amine
absorber).

In addition, it is important to keep steady operating conditions for the hydrogen make-up compressor.
This is achieved by means of a recycle of the compressor excess flow, back to compressor suction
(spill-back).

An increase in pressure favors the desirable reactions (see Le Chatelier's principle for chemical
reactions with decrease in the number of moles). However, practically, the pressure is not an operating
parameter, and is usually kept constant at the maximum value allowed by the plant design.

Hydrotreaters are normally operated as close as possible to design operating pressure to maximize
reactor H2 partial pressure. On occasions, however, the product separator pressure is reduced to
either cater for an increased reactor circuit pressure drop associated with an increase in unit
throughput, or to cope with a catalyst bed pressure drop build-up problem. Such operations come with
an attendant reduction in reactor outlet H2 partial pressure.

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c - Reactor catalytic temperature control

The unit feed quality may vary within a certain range and as a result the total exothermicity across the
reactor will also fluctuate within corresponding limits.

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 20C. The
quantity of cold quench injected between two beds is adjusted to bring the control of reactor
temperature profile.

5- OPERATING PARAMETERS
Process variables of the reaction section are mainly:
the reaction temperature
the hydrogen partial pressure
the space velocity
the pressure

a - Temperature

Action on the chemical reactions

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.

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The following guidelines are used:

- HDS reactions start as low as 300C, with the rate of reaction increasing markedly with
temperature
- aromatic saturation reactions slow down above about 380C 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

- product colour can sometimes become a problem at temperatures above 370-390C,

especially at low H2 partial pressure and/or high feed vaporization

- the maximum reactor outlet temperature in gas oil service is generally limited to between
380-390C by either mechanical design considerations or product colour problems
- above 390C, 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 10-40C.
Higher temperature rises can be produced when there is a high percentage of cracked material 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 380C 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

Weight Average Bed 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.

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For a reactor with one catalytic bed:

Feed

(t1 + t2 + ........ tn)

t1 WABT =
n

t2

tn
D PCD 381 A

Effluent
For a reactor with two catalytic beds:
Feed

(M1 x WABT1 + M2 x WABT2)

WABT for the reactor =
M1 + M2
Bed 1
M1: First catalyst bed weight
M2: Second catalyst bed weight

Bed 2
D PCD 382 A

Effluent
Remark: 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.

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Reactor catalytic bed temperature control

Isothermal conditions are the best for the desulfurization reaction. For this reason the increase of
temperature is limited to 20C max. In order to limit the catalyst temperature to this maximum, the
catalyst is divided in three beds (the unit feed quality may vary within a certain range and the total
exothermicity across the reactors will also fluctuate, which also requires to control by temperature
increase).

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 cooled 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 life. To extend the
catalyst life 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 325C
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 = 335C -
EOR = 375C):
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.

The end of a catalyst cycle (EOR) is reached when:

either the maximum allowable temperatures have been reached
or the catalyst deactivation is such that it is no longer possible to meet the product
specifications
or the pressure drop in the reactor is too high

In this case the catalyst must be regenerated. Regeneration is performed ex situ.

b - Hydrogen partial pressure

Hydrogen partial pressure is the part of the total pressure only due to the molecules of hydrogen in the
gas phase.

The hydrogen partial pressure PPH2 is defined by the following formula:

Number of H2 moles
PPH2 = Reactor outlet pressure x in vapor phase
Number of total moles

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Reactor H2 partial pressure is calculated from a 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.

Calculation of treat gas rate

Flow rate of gas and hydrogen:

Gas flow rate (excl. Quench) H2 flow rate

Molecular % mol H2 H2
kg/h
mass
kmoles/h Nm3/h H2 kmoles/h Nm3/h

Make up gas

Recycle

Total

Calculation of treat gas and make-up gas ratio relative to feed

Feed flow rate = m3/h

Treat gas rate Make up & recycle gas rate

Make up =
Nm3 of gas/m3 of feed = =
Recycle =

Make up =
Nm3 of H2/m3 of feed = =
Recycle =

Conclusion

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Hydrogen partial pressure calculation

Hydrogen partial pressure is lower at reactor outlet because:

- H2 chemical consumption

- dilution because higher feed vaporization (Toutlet > Tinlet) and light products produced by
the chemical reactions

- lower pressure at reactor outlet.

Calculation of total molecular flow rate at reactor outlet (including quench)

It is equal to:

number of kmoles/h of recycle gas

+ number de kmoles/h of make up gas
+ number de kmoles/h of produced H2S
+ number de kmoles/h of gas oil vaporized at reactor outlet
number de kmoles/h of H2 chemically consumed

The total number of moles can be then calculated as follows:

TOTAL HYDROGEN
kmoles/h kmoles/h

Recycle gas (with quench) +

Make up gas +

H2S produced +

Vaporized feed +

H2 chemically consumed

Total number of moles in gas phase

at reactor outlet

Total pressure at reactor outlet = bar abs.

H2 partial pressure calculation

PP H2 = . =

PP H2 = bar abs.

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Action on the chemical reactions

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.

Hydrogen partial pressure in operation

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).

It is recommended to operate at the highest hydrogen partial pressure.

c - Liquid Hourly Space Velocity (LHSV)

The purpose of a chemical reactor is to perform the desired chemical reaction, which is characterized
by the partial or total elimination of the reactants involved, and the production (to a greater or lesser
degree) of the desired product (and by-products).

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:

Hourly volume of liquid feed at 15C (m3/h)

LHSV (h1) =
Volume of catalyst (m3/h)

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.

Action on the chemical reactions

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 h1 (maximum recommended at design).

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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.

LHSV calculation (design)

Volume of feed per hour m3/h

Volume of catalyst 443 m3

LHSV (h1) = =

The LHSV is low in order to insure a high residence time mandatory to achieve the very high
desulfurization rate.

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 chemical consumption is estimated at 81 Nm3/m3 (0.84% wt on feed) and total H2 consumption is

estimated at 100 Nm3/m3 (1.05% wt on feed).

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Treat gas purity

Treat gas purity is primarily a function of make-up gas purity, chemical H2 consumption, product
separator temperature and recycle gas purge rate. Treat gas purity increases with increasing make-up
gas purity, decreasing chemical H2 consumption, decreasing product separator temperature and
increasing reactor purge.

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
Composition (SOR) Vol %

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 H2S,
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.
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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

6- ACTION OF PROCESS VARIABLES ON REACTIONS

The choice of operating conditions tries to satisfy simultaneously two requirements:

- 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.

a - Hydrodesulfurization

Under the usual industrial conditions this reaction has no thermodynamic limitation.

b - 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.

c - Hydrogenation of olefins and diolefins

When increasing the pressure the hydrogenation rate of olefins and diolefins increases faster than the
hydrodesulfurization rate.

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d - Hydrogenation of nitrogen compounds

These reactions have commun features with olefins and diolefins hydrogenation.

e - Hydrogenation of nitrogen compounds

These reactions have commun features with the hydrogenation of aromatics:

- hydrogenation of aromatic cycles

- hydrogenation of bond C-N

f - 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.

Hydrocracking increases with the temperature.

g - Coking

The coking is limited by operating at the lowest temperature possible, with a sufficient hydrogen partial
pressure and liquid hourly space velocity.

h - Summary table

Hydrogen Partial Pressure Temperature Liquid hourly space velocity

Desulphurization

Denitrification

Hydrogenation
Deoxygenation

Hydrocracking
D CH 2218 A

Coking

00679_C_A 2009 - IFP Training

 ESTIMATE OF MEAN AVERAGE BOILING TEMPERATURE
OF A PETROLEUM CUT FROM ITS ASTM DISTILATION CURVE

Figure 1

Follow the successive steps indicated hereunder

1 - A.S.T.M. data

% vol Temperature C

10 t10
50 t50
70 t70
90 t90

2 - Calculation of the slope S

t - t10
S = 70
60

3 - Calculation of the volumetric mean temperature tV

t + 2t50 + t90
tV = 10
4

4 - tV correction to get the "mean average" temperature (tMAV)

Correction (C)
+ 20

+ 10

0
tv =
- 10 300
C
- 20 27
5
C
25
0

- 30
10

20 0
15

C
0

0
C

- 40
1 2 3 S slope (C/%)

tmav = tv + correction
D PCD 1272 B

2009 - IFP Training

 Figure 2
KUOP DIAGRAM - AVERAGE MOLECULAR WEIGHT
Mean average temperature (tmav) C
50 100 150 200 250 300 350

50 00 750
0.6 0.7 : 0.
y 1 5
vit
ic gra
Sp ecif 0.8
00

34
Characterization factor : KUOP = 13

0
30

32
29
28

0
27
26

0
0
50

25

0
24

0
0
0.6

22
18
10

19

23
14

0
20

21
15

16

17

0
11

13

0
12

0
0

0
0

0
0
0

0
0

0
0
90
80
70

50
0.8
60

Mo
lec
KUOP = 12

0
ula
350
00

27
0.7
rw

0
eig
ht

26
0
25
0

Mean average temperature (tmav) C

Mean average temperature (tmav) C

24
KUOP = 11

0
23
50
0.7

0
22
0
21
0
60

70

80

-50

20
0
KUO = 300
90

10

P 10
0

11

00
0

0,8
Sp.

12
0

13
gr 1

19
0

14

0
5

15
00

16

17
C :0.9

0
)

0
5

18
(t mav 1
ity

0
c g rav
cif i
50 Spe 50 00
0.8 0.9 1.0

D TH 1078 C
-50 0 50 100 150 200 250

2009 - IFP Training