HDS

Axens India Private Limited
(Private Limited Company formed under the

Companies Act, 1956)
Hydro-Treating/Hydro-Processing
on
Petroleum Federation of India

NIT Jalandhar,
&
Lovraj Kumar Memorial Trust
Mohan Lal
Hydrotreatment Technology
1 / 96
Introduction
Objective of the process
2/ 96
Introduction
The Distillates cuts from crude oils atmospheric and vacuum

distillations are in the temperature boiling range of 1505500C. Their chemical characteristics, for instance their sulfur
content, depend on the crude origin, and in most cases a
catalytic hydrotreatment process is required to improve their
qualities, to meet the commercial specifications of the
finished products or to prepare feeds for downstream
processes.
3/ 96
Introduction
Most common examples sorted by product are:
Naphtha pre-treatment of Catalytic Reforming feeds:
sulphur and nitrogen removal

Light Naphtha
preparagtion of feeds for steam cracking

Kerosene
sweetening of kerosene cut to produce on spec Jet Fuel, burning

properties improvement.
deep desulfurization for downstream separation of n-paraffins by

molecular sieve
4 / 96
Introduction
Gasoil Straight run eventually blended with cracked feeds:

deep HDS to produce Ultra Low Sulfur Diesel (10 to 50 wppm
sulphur content), and eventually Cetane Number enhancement
Cracked gasoil from FCC or Thermal cracking:
sulphur reduction for blending in LSFO (Light Sulfur Fuel Oil).
VGO
FCC feed pre-partial conversation into valuable light products
(naphtha and gasoil).
Hydrocracking pre-treatment: removal of nitrogen and deep

hydrogenation of aromatics at high pressure ahead of acidic
hydrocracking catalysts.
5 / 96
Introduction
Axens Hydrotreatment reactors are now equipped with

latest technology of Equiflow internals, including distributor
trays, quench boxes and bottom collectors which allow the
best hydrodynamic performance of the catalyst beds.
6 / 96
Process Overview
7/ 96
Process Overview
Reaction Section
Sour Gas to
H.P Amine
absorber
Hydrogen
Make-Up
Recycle gas
compressor
TCO From
FCC
CGO from
Coker
SR from CDU
Hydrotreatment
section
HP
separator
To MP
Amine
Absorber
MP
separator
To Stripper
8 / 96
Process Overview
Separation Section
From MP
separator
S
t
r
i
p
p
e
r
S
t
a
b
i
l
i
z
e
r
Wild
naphtha
Diesel
Product
To LP
Amine
Absorber
Naphtha
From
DHDS Unit
Stabilized
Naphtha
9 / 96
Process Overview
Amine Section
To MP Off
Gas
Off Gas to
fuel gas
M
P
From MP
separator
A
b
s
o
r
b
e
r
L
P
From
Stripper &
Stabilizer
Overheads
A
b
o
s
r
b
e
r
Rich Amine
10 / 96
Example Typical Flow Diagram (ULSD)

EquiFlowTM Distributor
+ Quench Mixing Boxes
Steam Stripper to avoid

off gas compressor
Multibed Reactor
Interbed
Temp
Control
Feed
H2 Recycle
High H2/HC Ratios
Off-Gas
ULSD
(dryer required)
Amine Scrubber
(usually necessary)
M/U H2
11 / 96
Chemical Reactions
and Catalysts
12/ 96
Chemical Reactions and Catalysts
Different types of reactions

Hydrocracking
Hydrogenation
Hydrogenolysis
Removal
Removalof
ofimpurities
impurities
(S,
(S,N,
N,O)
O)
HH2 addition
to
2 addition to
unsaturated
unsaturated
hydrocarbons
hydrocarbons
(Diolefins,
(Diolefins,Olefins
Olefins
&&Aromatics)
Aromatics)
Breaking
Breakinglarge
large
hydrocarbon
hydrocarbon
molecules
moleculesinto
into
smaller
smalleror
oropening
opening
cycles
cycles(achieved
(achievedby
by
breaking
breakingC-C
C-Cbonds)
bonds)
Product quality improvement: HDS, HDN, Cetane...

13 / 96
Chemical Reactions
Hydrodesulfurization (HDS)
Hydrodenitrogenation (HDN)
Diolefins Hydrogenation (HDDO)
Olefins Hydrogenation (HDO)
Aromatics Hydrogenation (HDA)
Hydrocracking (HDC)
14 / 96
Chemical Reactions
Hydrogenation of Sulfur Compounds
Large variation of sulfur content in crude oils:

Low Sulfur : Sweet crude
High Sulfur : Sour crude
Sulfur compounds have different forms:

Reactivity under H2 are very different
Operation severity depends on the feed structure
Chemical reaction of these compounds with hydrogen:

Exothermic reaction
Formation of H2S, eliminated from the treated cut by stripping in
the separation section
15 / 96
Chemical Reactions
Sulfur Compounds
Mercaptans
RSH
Disulfides
RSSR
Sulfides
RSR
Thiophenic
Benzothiophenic
R1
R1
S
Dibenzothiophenic
R1
S
16 / 96
Chemical Reactions
Sulfur Compounds
R1
Benzonaphtothiophenic
R1
Benzodibenzothiophenic
S
17 / 96
Chemical Reactions
Typical distribution of Sulfur Compounds
Arabian
light
GASOLINE
crude
KEROSENE
GAS-OIL
VACUUM
DISTILLATE
RESID
R-S-H
R-S-R
S
S wt%
1.2
0.02
0.2
0.9
1.8
2.9
18 / 96

Desulfurization Reactions (exothermic)
Favored reactions to meet product total sulfur
and mercaptans specifications
Mercaptans
R-SH + H2
R-H + H2S
Sulfides
R1-S-R2 + 2 H2
R1-H + R2-H + H2S
19 / 96

Thiophenic Compounds
RX
ThiopheneRX
+ H2
+ 2 H2
MercaptanRX
RX + H2S
RX
+ H2
ThiopheneRX + 4 H2
RX
R RX + H2S
20 / 96

Benzothiophenic Compounds
RX
+ 2 H2
RX + H2S
S
(Benzothiophene) RX
BenzothiopheneRX + 2 H2
R RX + H2S
21 / 96
Understanding Reactivity
H2
H2
SH
Hydrogenolysis pathway
S
3H2
2H2
Hydrogenation pathway
H2
H2
SH
HDS rate is no longer

the best criterion to
estimate difficulty
Refined knowledge
of the feed structure
required
Hydrogenolysis pathway
S
3H2
2H2
S
Hydrogenation pathway
22 / 96
Chemical Reactions
Desulfurization Reactions
Mercaptans
Sulfides
+
Reactivity
Thiophenics
Dibenzothiophenics
23 / 96
Sulfur Compound Reactivities

CH3
CH3
S
Toward more refractory

compounds
4,6-DiMeDBT class
S
CH3
H3C
Dibenzothiophene (DBT) class
Benzothiophene (BT) class
RSH, R'-S-S-R
Sulfides class
200
250
300
Boiling Point, C
350
400
24 / 96
Chemical Reactions
Hydrocracking (HDC)
25 / 96
Chemical Reactions
Hydrogenation of Nitrogen Compounds
Nitrogen compounds have different forms:

Reactivity under H2 are very different
Operation severity depends on the feed structure
Chemical reaction of these compounds with hydrogen:

Exothermic reaction
Formation of NH3, eliminated from the treated cut by water washing
and decantation in the separation section
26 / 96
Chemical Reactions
Nitrogen Compounds
Pyridine
Quinoline
N
Acridine
Pyrrole
N
Indole
Carbazole
N
H
Amines
N
H
N
H
R-NH2
27 / 96

Typical Distribution of Nitrogen Compounds (ppm)
Gasoline Kerosene
Gas oil
Vaccum
Distillate
Resid
R-NH2
NH
R
N
RX
RX
RX
RX
N content
0-5
1-20
10-300
SR cuts
0-1
100
1000
Pyrolysis
cuts
10-100
20-300
2001000
500-3000
3000
28 / 96

Denitrogenation Reactions (exothermic)
Pyridine
N
N
H2N
C5H5N + 3 H2
Pyridine
C5H10N
Phenylamine
+ H2
C5H11NH2
+ H2
Pentane amine
Quinoline
+ 7 H2
C5H12
Pentane
+ NH3
+ NH3
C9H7N
C9H18
Reaction pathway is going through hydrogenation before nitrogen removal

Denitrogenation is slower than Desulfurization
29 / 96
Nitrogen Compound Reactivities

8
1
2
7
6
Basic
N
R
2
3
10
Acridine class
NH2
Quinoleine class
6
5
Aniline class
1,9- DiMeCarbazole class
Neutral
H
N
R
2
8
H
N
N
H
Carbazole class
.
N
H
Indole class
Pyrrole class
200
250
300
Boiling Point, C
350
400
30 / 96
Chemical Reactions
Hydrocracking (HDC)
31 / 96

Olefin and Diolefin Compounds
Diolefin : Two double-bound hydrocarbon
R-C=C-C=C-R
Olefin : Single double-bound hydrocarbon
R-C=C-R
32 / 96

Diolefins and Olefins Hydrogenation
They are part of Hydrocarbons structures
They are more concentrated in light cuts
Presence mainly in cracked feedstock's from conversion units
without Hydrogen:
- Steam cracking
- Thermal cracking, Coking, Visbreaking,
- Catalytic Cracking (FCC or RFCC/R2R)
Presence sometime in Straight Run gasoil :
- CDU or VDU Bottom temperature too high
33 / 96

Olefins and Diolefins Hydrogenation (HDO / HDDO)
Target: To limit their polymerization inducing
- Coke formation on catalyst acid sites
- Gums formation in light cuts
Note: This needs a catalyst with neutral carrier.
Typical Reaction:
R-CH=CH-R + H2 R-CH2-CH2-R
Olefin (or diolefin)
Saturated hydrocarbon
paraffin
34 / 96

HDO / HDDO Reactions Main Characteristics
HDO and HDDO are very exothermic reactions

Reactions occur easily with a short residence time
They are complete at Typical HDT operating conditions
The hydrogenation of unsaturated hydrocarbons is
characterized by an important heat release (exothermic
reaction) and a reduction of volume.
Consequently, the reactions are favored by low temperature
and high pressure (Le Chateliers Principle)
35 / 96
Summary on HDDO and HDO Reactions

Hydrogenation reactions of unsaturated compounds have
the following characteristics:
Consuming Hydrogen
Highly Exothermic
They are quite easy for the diolefins and olefins
36 / 96
Chemical Reactions
Hydrocracking (HDC)
37 / 96

Aromatic Composition and Compounds
Aromatics for the same MW are multiple and reactivity
depends on the energy of each link:
Benzenic cycles (1 or more) link with different alkyl chains
Each cycle has 6 AC (Aromatic Carbon)
HDT reaction is similar to Mono-aromatics, not easy
Polycondensed from 2 (Naphthalene) to more (ovalene: 7)
CA number depends on the polycondensation mode
HDT reaction are successive reduction of Cycle number in
Naphtheno-aromatics
38 / 96

Aromatics Hydrogenation (exothermic)
+ 3 H2
+ 2 H2
Naphtalene
Tetraline
Dicyclohexane
Aromatic with 10
aromatic carbons
Aromatic with 6 aromatic carbons
Naphthene with 0
aromatic carbons
HDA = HDAC = 0 %
HDA = 0 %
(still an aromatic molecule)
(no hydrogenation)
HDAC = 40 %
HDA = 100 %
HDAC = 100 %
(4 carbon over 10 have been hydrogenated)
HDA = total hydrogenation of an aromatic

HDAC = hydrogenation of aromatic carbons
Favored reaction to limit coke formation by saturating the coke precursors

39 / 96

Aromatics Hydrogenation
+
Tri-Aromatics into Di-Aromatics
Di-Aromatics into Mono-Aromatics
Reactivity
Mono-Aromatics into Saturates
40 / 96

HDA Reactions Main Characteristics
HDA is characterized by an important heat release and a
reduction of the reactants volume
From a Thermodynamic view point HDA is favored by :
- Low Temperature
- High Pressure
Operating conditions result from a compromise between:
- The above thermodynamic considerations
- The minimum temperature required by the Kinetic aspect
- The catalysts HDT Activity function and its inhibitors
41 / 96

HDA (or HDAC) Reactions Main Characteristics
Consuming H2
Highly exothermic (8-12 kcal/mol of H2)
Typical heats of reaction (per mole of reactant):
Alkenyl-aro to Alkyl-aro : 47 kcal/mole
Aromatics to Naphtenics : 50 kcal/mole
Thermodynamically limited
Difficult to achieve specially with high number of aromatic cycles
Reversible reactions and favored by low temperature and high H2
pressure
Limit coke formation by saturating the coke precursors
42 / 96
Chemical Reactions
Hydrocracking (HDC)
43 / 96

Hydrocracking
Different Hydrocracking reactions occur
Breaking of C-C bond in aliphatic molecules,
Dealkylation of benzenic molecules
Opening of cycles.
Hydroisomerization reactions also occur, improving the products

quality (octane for gasoline, cloud point and pour point for
diesel fuel, viscosity index for bleed)
44 / 96

Hydrocracking Reactions (HDC)
HDC are thermodynamically favored by high temperature
HDC are exothermic (10-15 kcal/mol) but less than
hydrogenation reactions
HDC are slow (long residence time)
HDC promote coke formation when ppH2 is not high enough
to ensure complete hydrogenation
45 / 96

Hydrocracking Reactions
Aromatics Dealkylation (easy)
Lateral Chain Breaking
+ H2
+ H2
46 / 96

Naphtenic Cycles Opening (easy)
+ 2 H2
47 / 96

Aromatics Hydrocracking
First Step : Hydrogenation
Second Step : Naphtenic Cycle Opening
+ 2 H2
+ H2
48 / 96

Naphteno-Aromatics
+ H2
+ H2
+ H2
49 / 96

Paraffins
More difficult with small hydrocarbon chain
R1
R2
+ H2
R1
R2
50 / 96

Hydroisomerization
51 / 96

Hydroisomerization
R
R
52 / 96
Other Reactions
Oxygen Compounds Hydrogenation
Coking
Demetalisation
53 / 96

Other Reactions
Oxygen Compounds Hydrogenation (HDOx)
Oxygen content in crudes is usually small
Some crudes contain Naphtenic acids (TAN (Total Acid Number))
Oxygen compounds in the gas-oil cuts are mainly naphthenic acids
and phenols
Chemical reaction of these compounds with hydrogen leads to the
formation of water (H2O), easily eliminated from the treated cut by
decantation in the separation section
54 / 96

Other Reactions
Naphtenic Acid Removal
O
OH
+ 3 H2
+ 2 H2O
55 / 96

Other Reactions
Phenol Removal
OH
+ H2
+ H2O
56 / 96

Other Reactions
Oxygen compounds hydrogenation reactions characteristics:
hydrogen consuming
produce water
exothermic
easier than the HDN reactions
usually negligible
57 / 96
Other Reactions
Coking
Demetalisation
Amine Section
58 / 96

Coking
Coke deposit is the main source of catalyst deactivation
Coking is limited by:
Operating temperature as low as possible
High hydrogen partial pressure (dilution effect of the
hydrocarbons by hydrogen)
Short residence time of hydrocarbons on the catalyst
Reduced quantity of large molecules in the feed (asphaltenes)
which are difficult to hydrogenate and plug the catalyst pores.
59 / 96

Coking
Polynuclear aromatics,
resins, asphaltenes
+ Olefin
Alkylation
+ H2
Cyclization
+ H2
Coke
precursors
60 / 96
Other Reactions
Coking
Demetalisation
Amine Section
61 / 96

Demetalisation Reactions
Metals are present only in heavy feeds, or in feed polluted with
crude
They could be present in Heavy VGO feeds from RFCC
Organometallic compounds are cracked and the metals are
trapped on the catalyst pores
This may concern mainly the Ni and V but also As, Pb, Cu
Fe is deposited as Iron sulfide
Si comes from Silicones used as antifoaming additives (Coker,
Visbreaker)
62 / 96
Other Reactions
Coking
Demetalisation
63 / 96
Thermodynamics and Kinetics Bases

Feed Chemical Composition
Products Specifications
Chemical Reactions
Catalysts
Catalysts Contaminants
64 / 96

Catalyst Structure
Catalyst Support
(earth oxide, alumina, silica...)
Metal finely deposited on the support
responsible for the hydrogenation
activity and the selectivity of the
catalyst
The selected catalyst metal takes

into account impurities related to
the nature of the feedstock
65 / 96

Catalyst Support Choice
Improve metal dispersion (many active sites)
Mechanically resistant
(to avoid breaking during loading and operation)
Chemically inert to prevent any undesirable reactions
Withstand steam, H2, air + nitrogen treatments (T > 400C)
for regeneration, reduction, reactivation phases
66 / 96
Principle of Heterogeneous Catalysis

Catalyst and reactants are not in the same phase
Key parameters:
External surface of
the catalyst grain
Gas or liquid phase

containing the reactives
Micropores
Macropores
Specific surface area of

the catalyst support
Dispersion rate of the

active agents on the
support
Pore distribution of the

support
67 / 96
Catalysis Mechanism
Adsorption of reactant on specific active site
Pore inside the catalyst

grain
Chemical reaction on catalysts surface

Product desorption
tion
sp o r t a
n
a
r
t
s
an t
R e act
Adsorbed
reactants
Chemical
reaction
Products evac
uation
Adsorbed
products
Inside surface of the

catalyst
Active site
68 / 96

Required Catalyst Characteristics
Activity
Ability to increase the rate of the reactions involved.
Activity evaluation temperature at which the catalyst must be
operated to produce a product on-specification, for a given feed,
all other operating conditions being equal
Selectivity
Ability to favour desirable reactions rather than others
Stability
Catalyst performance change with time
Polymers or coke deposits affect stability Active surface sites
change
69 / 96

Choice of the DHDT Catalyst Main Criteria
Feedstock Type
Desirable chemical reactions of HDX

HDX = HDO, HDS, HDN, HDA or HDCA, HDC,
Choice of catalyst carrier
Choice of catalyst metals
Choice of appropriate catalysts
Catalyst contaminants
70 / 96

Middle Distillates (Kerosene or Diesel) HDS
Feedstocks from Topping (SR feedstocks):
HDS needed for Diesel specification
HDN could be needed for Stability criteria
Middle Distillates(Kerosene or Diesel) HDT
Feedstocks from Catalytic Cracking, with Di-Olefin, Olefin, Sulfur
and Nitrogen compounds:
HDDO, HDO for stability criteria
HDS, HDN needed for Diesel specification achievement
HDA for Diesel (Aromatics, Cetane)
71 / 96

The best Combination Carriers and Active Metals
Carriers:
Macroporous Neutral Alumina for HDM
Neutral Alumina for HDDO and HDO
Pure or promoted Alumina for HDS, HDA, HDN
Promoted Alumina or Silica/Alumina for MHDC
Zeolite/Alumina for HDC
Metals:
NiMo for HDM
CoMo for HDS
NiW or Pt for Deep HDT
NiMo for combination HDS,HDA,HDN and MHDC
72 / 96

Catalyst Active Metals Selection vs Reaction to Promote
Metals
HDS
HDO
HDA
HDN
HDM
Co Mo
****
***
**
**
**
Ni Co Mo
***
***
***
***
***
Ni Mo
***
***
***
***
***
Ni W
**
***
****
****
**
Pd, Pt
**
***
****
***
73 / 96

Catalyst Metals Choice
vs Reaction to Promote
HDS HDO HDA HDN HDC HDM

NiMo
HMC945, HMC841
**
***
****
HR945
**
****
**
**
**
HR538, HR548
***
***
***
***
**
**
HTH648
***
**
***
***
***
HYC642, HYC652
***
*
NiCoMo
***
***
****
HR568
***
***
CoMo
***
***
**
**
HR506, HR526, HR 426
****
**
NiW
**
**
**
****
**
**
HR354
**
**
74 / 96
Thermodynamics and Kinetics Bases

Feed Chemical Composition
Products Specifications
Chemical Reactions
Catalysts
Catalysts Contaminants
75 / 96
Catalyst Contaminants
Inhibitors or Activity Moderators

Compete with the reactants for the catalyst active surface: P of the
available active surface (reversible adsorption).
When no more contaminants: no specific treatment for activity
recovery
Temporary Poisons
Strong adsorption: accumulation over the active surface.
Specific treatment is needed to restore activity, ex : hot H2 stripping
Permanent Poisons
Not removable by procedures available on site: the catalyst must be
unloaded and replaced by a fresh catalyst
At very low levels, the effect of certain contaminants is negligible

76 / 96

Reactivation or
Regeneration Treatment
Activity
No Impurity
Present
Impurity
Present
No Impurity
Present
Inhibitor
(Reversible
Effect)
Poison
Activity Recovery
No Impurity Present
Temporary
Poison
Permanent
Poison
D
Time
77 / 96
Operating Parameters
Reaction Operating Parameters

Temperature
Capacity, Space Velocity or Residence
Time
H2 Partial Pressure and Total Pressure
H2/HC Ratio
78 / 96
Reactor Temperature
Hydrotreating reactions are exothermic and

reactors are adiabatic:
Exotherm Temperature Rise (Axial Delta T)
A single temperature is used to classify the

overall reactor temperature:
Weighted Average Bed Temperature (WABT)
79 / 96
WABT
ABT for a Single Catalyst Bed
t1
t2
Average Bed Temperature (ABT)
tn
ABT =
(t1 + t2 + ....... tn)

n
80 / 96
WABT
WABT for a Multi-Bed Reactor
Catalyst Weight
WABT
bed 1
M1
ABT1
bed 2
M2
ABT2
Reactor
WABT =
(M1 x ABT1 + M2 x ABT2)

M1 + M2
81 / 96
WABT
Impact of WABT on Reaction
Increase of WABT has the following effects
(assuming constant feed rate and quality):
Increase of catalyst activity
Decrease of recycle gas purity
Increase of coke deposit rate
At a constant WABT
Aging of catalyst results in slight but steady loss
of activity
Slight increase of WABT through the life of the
catalyst makes up for loss
82 / 96
WABT
For a given catalyst, feed composition, LHSV and pressure the

WABT is the main handle that is adjusted to meet the process
objectives.
WABT is increased to compensate the deactivation up to End

of Run Temperature (EOR WABT), which is driven by:
Equipment limitations
Maximum heater duty, reactor maximum allowable working
temperature, ...
Product specifications
Diesel color, FCC feed PNA, ...
Operating temperature adjustment is a compromise between:

Long catalyst life
Optimal quantity of catalyst
Process objectives
83 / 96
LHSV
Fresh Feed Rate

Liquid Hourly Space Velocity (LHSV)
Reactor Residence Time
Definition:
LHSV =
Liquid Feed Volume per Hour at 60F

Volume of Catalyst
Both volumes expressed in the same units of

measure
84 / 96
LHSV
If fresh feed rate (or LHSV) increases
Lower unit performance results if all else equal
Performance may be maintained by temperature
increase at expense of higher coking rate
If fresh feed rate (or LHSV) decreases

Unit performance improves if all else equal
having the same effects of raising temperature
Increase of catalyst activity
Decrease of recycle gas purity
Increase of coke deposit rate
85 / 96
Hydrogen Partial Pressure (H2pp)

H2pp of a stream is defined as the volume percent of
H2 in the vapor phase multiplied by the total pressure
Reactor outlet H2pp is the desired value to judge the
impact on catalyst performance
H2pp is difficult to calculate but the following rule-ofthumb may be used to estimate reactor outlet H2pp:
H2pp
Recycle Gas H2 (vol%)

100
x Reactor Outlet Pressure (abs)
F varies by feed type and is approx. 0.7 for

kerosene, 0.8 for diesel and 0.9 for gas oil material
86 / 96
As H2pp increases, catalyst activity increases and coke

deposition is limited.
H2pp is a function of:

Total system pressure
Hydrogen make-up purity
Purge gas rate (if any)
H2/HC ratio
Reactor temperatures
H2pp increase is possible by:

Purging at the high pressure separator
Purge increases recycle gas purity by the removal of inert
compounds, light hydrocarbons or other impurities
However, purge increases hydrogen losses
Use of higher purity hydrogen make-up

87 / 96
H2S Partial Pressure (H2Spp)
Similar to H2pp, H2Spp of a stream is defined as the volume percent

of H2S in the vapor phase multiplied by the total pressure
H2Spp is a function of:

Total system pressure
H2S content in the recycle gas
H2S has an inhibiting effect on the catalyst
An amine absorber is the classic solution to reduce H2Spp

H2S content mainly depends on amine absorber efficiency
Some H2S is required in the loop to prevent catalyst reduction
The HP purge can also reduce H2S
88 / 96
H2 / HC
Hydrogen to Hydrocarbon Ratio (H2/HC)

H2/HC at the reactor inlet is defined as:
H2
HC
Pure H2 in Recycle Gas

Fresh Feed Flow Rate at 60F
Does not include the H2 in the make-up or quench

streams
This ratio corresponds to the minimum H2 required at
the reactor outlet.
Practically, the recycle compressor is always run at
maximum capcity.
H2 supplied in the reaction includes:
H2 consumed by the reaction

H2 excess to obtain sufficient H2pp
89 / 96
H2 / HC
H2/HC may be modified by
Changing the high-pressure purge rate

Changing the recycle gas rate (typically set at
maximum flow)
Maintaining proper H2/HC
Maximizes catalyst activity and overall unit

performance
Maximizes catalyst life by reducing coke deposits
on the catalyst
Close relationship between H2/HC and H2pp
90 / 96
H2 / HC
H2/HC affects several parameters:

Lower H2/HC reduces the H2pp
Lower H2/HC increases the coke
formation
Lower H2/HC inhibits HDS activity by
increasing H2S and NH3 partial pressures
91 / 96
Typical Operating Conditions

Typical Operating Conditions by Feed Type
Range of operating parameters: LHSV, H2pp, WABT
Feedstock
Cut Point
(C)
LHSV
(h-1)
H2pp
(bar)
WABT at
SOR (C)
H2/HC
(Sm3/m3)
H2 Chemical
Consumption
(wt%)
Kerosene
160 230
24
15 30
300 340
150
0.1 - 0.2
Diesel
230 350
0.5 3
15 50
320 360
150 300
0.3 - 0.8
VGO
350 550
0.5 2
40 70
360 380
300 500
0.4 1.0
92 / 96
EquiFlow for Near-to-Perfect

Gas/Liquid Distribution
93/ 96
Why Gas/Liquid Distribution

is Important
A poor gas/liquid distribution will induce

High H2/HC ratio in the dry zones and low H2/HC
ratio in the wet zones resulting in an overall
15 to 30% loss of catalyst efficiency
Local hot spot in dry zone with accelerated
catalyst coking
Increased risk of channelling in case of
inhomogeneous catalyst loading
A near-to-perfect gas/liquid distribution is a

must for the most severe services such as ULSD
94 / 96
Chimney Tray/Equiflow Comparison

X-Ray tomographic cross-sectional
images at 0.5 m from top of bed
EquiFlow
Low
Liquid Flux
Chimney Tray
High
Low
Liquid Flux
High
EquiFlow
EquiFlow distributor tray allows a near to perfect

gas/liquid distribution at the top of the bed
95 / 96
EquiFlow:
A Case Study (3/3)
Radial/Axial Delta T, % as a function of time on stream
Regular Trays
120
EquiFlow
120
Axial T: 9C
80
80
40
40
60
120
180
240
300
360
420
480
Time on stream, days
120
Axial T: 8C
Regular Tray
EquiFlow
HR 448
HR 448
Regular Tray
EquiFlow
HR 448
HR 448
0
120
80
40
40
60
120
180
240
300
360
420
480
60
120
180
240
300
360
420
480
360
420
480
80
Axial T: 8C
Axial T: 4C
60
120
180
240
300
No radial delta T with EquiFlow distributor tray
96 / 96

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Axens India Private Limited

(Private Limited Company formed under the

Petroleum Federation of India

Objective of the process

The Distillates cuts from crude oils atmospheric and vacuum

sulphur and nitrogen removal

preparagtion of feeds for steam cracking

sweetening of kerosene cut to produce on spec Jet Fuel, burning

deep desulfurization for downstream separation of n-paraffins by

Gasoil Straight run eventually blended with cracked feeds:

Hydrocracking pre-treatment: removal of nitrogen and deep

Axens Hydrotreatment reactors are now equipped with

Example Typical Flow Diagram (ULSD)

Steam Stripper to avoid

Chemical Reactions and Catalysts

Different types of reactions

Product quality improvement: HDS, HDN, Cetane...

Chemical Reactions and Catalysts

Chemical Reactions and Catalysts

Large variation of sulfur content in crude oils:

Sulfur compounds have different forms:

Chemical reaction of these compounds with hydrogen:

Chemical Reactions and Catalysts

Chemical Reactions and Catalysts

Chemical Reactions and Catalysts

Chemical Reactions and Catalysts

R1-H + R2-H + H2S

Chemical Reactions and Catalysts

Chemical Reactions and Catalysts

Desulfurization Reactions (exothermic)

HDS rate is no longer

Chemical Reactions and Catalysts

Sulfur Compound Reactivities

Toward more refractory

Dibenzothiophene (DBT) class

Benzothiophene (BT) class

Chemical Reactions and Catalysts

Chemical Reactions and Catalysts

Nitrogen compounds have different forms:

Chemical reaction of these compounds with hydrogen:

Chemical Reactions and Catalysts

Chemical Reactions and Catalysts

Chemical Reactions and Catalysts

Reaction pathway is going through hydrogenation before nitrogen removal

Nitrogen Compound Reactivities

Chemical Reactions and Catalysts

Chemical Reactions and Catalysts

Chemical Reactions and Catalysts

Chemical Reactions and Catalysts

Chemical Reactions and Catalysts

HDO and HDDO are very exothermic reactions

Chemical Reactions and Catalysts

Summary on HDDO and HDO Reactions

Chemical Reactions and Catalysts

Chemical Reactions and Catalysts

Chemical Reactions and Catalysts

Aromatic with 6 aromatic carbons

(4 carbon over 10 have been hydrogenated)

HDA = total hydrogenation of an aromatic

Favored reaction to limit coke formation by saturating the coke precursors

Chemical Reactions and Catalysts

Mono-Aromatics into Saturates

Chemical Reactions and Catalysts

Chemical Reactions and Catalysts