Welcome

Hydro-Processing Operations in Refinery

for
Online Summer Internship Programme, IIChE

Subhajit Sarkar
Chief General Manager (Technical), IOCL - Gujarat Refinery
 Contents
 What is Hydro-Processing – About Hydroprocessing
 Why Hydro-Processing  Uses & Advantages
 Types of Hydro-Processing
 Pre-Treatment for Removing Catalyst Poisons
 Sulphur Reduction in Diesel Product – DHDS / DHDT Units
 Pre-Treatment before feeding to FCCU / Hydrocracker – VGO HDT
 Post Treatment of FCCU / DCU Products
 Hydrocracking

 Catalysts: Activities & Operational Parameters

 Reactor Internals
 Incidents & Accidents in Hydro-Processing Units
2
 What is Hydro-Processing ?

 Hydroprocessing is a catalytic process where Hydrogen

reacts with hydrocarbons

 to remove the poisons for catalysts used in subsequent processing –

Hydrotreating

 To reduce Sulphur from Petroleum Products in line with Govt norms –

KHDS / DHDS / DHDT etc

 To break bigger hydrocarbon molecules to smaller hydrocarbon molecules

thereby producing more value added products – Hydrocracking

3
 Why Hydroprocessing ?

Hydro-Processing

• Improves quality of product by removing

contaminants (like S, N, O) with the help of Hydrogen

• Saturates Olefins (gum forming agents) and aromatics

• Cracks bigger hydrocarbon molecules into more valuable

smaller molecules

4
 HDS Reactions

S
H +H2 + H2S
Heptanethiol Heptane

+2H2 + H2S
S
Thiophene Butadiene
S +2H2 + + H2S
Butylpropyl Sulfide Butane Propane

S CH3+2H2
+ CH4 + H2S
Methylphenyl Sulfide Benzene Methane

5
 HDN Reactions

H2

+ NH3
N N
“A”

6
 Olefin Saturation Reactions

+H2
1-Heptene n-Heptane

+H2

Cyclohexene Cyclohexane

+H2

3-Ethyl-2-Pentene 3-Ethylpentane

7
 Aromatics Saturation Reactions

CH3 CH3
+ 3H2

Toluene Methylcyclohexane

+ 2H2

Naphthalene Tetralin
(Tetrahydronaphthalene)

+ 3H2

Tetralin Decalin
(Decahydronaphthalene)
8
IMPORTANT APPLICATIONS OF HYDROPROCESSING

FEED APPLICATION
SRN + BLEND WITH PRETREATMENT FOR HDS, HDN, HDO TO PREPARE
CN CHARGE FOR CRU, ISOM, H2 PLANT

FCC GASOLINE FOR SULFUR REDUCTION WITHOUT O.N. LOSS

Pyrolysis Gasoline FOR STABILIZATION OR BT PRODUCTION

KEROSENE SMOKE POINT IMPROVE OR ATF PRODUCTION

SR & CRACKED HDS, HDN, CETANE IMROVEMENT
DIESEL

AR HDM, HDS, HDN TO PROCESS DOWNSTREAM, FO

VGO FCC & HYC FEED PRETREATMENT
LUBES HIGH QUALITY BASE STOCKS
VR HYDROPROCESSING
Hydro-Processing Units in Refinery Configuration

10
Hydrotreating Vs Hydrocracking

11
Hydro-Treating

for Sulphur Reduction

in Diesel

(DHDT)

12
 SULFUR IN DIESEL

 Sulfur compounds naturally occur in crude oil

 Sulfur in diesel enhances the pollution & contributes significantly

to particulate matters in exhaust emissions

 Sulfates are formed in the exhaust streams

 It leads to corrosion and wear of engine systems

 SULFUR IN TYPICAL CRUDES & GAS OIL

Crude Crude S Gas Oil Gas Oil

Wt% Boiling Sulfur,
range,0 C Wt.%
Assam Mix
0.22-0.24 250-370 0.18-.23
Bombay High
0.17 250-370 0.17
Arabian Light
1.79 235-343 1.03
Arabian Heavy
1.97 235-343 1.3
Dubai
1.97 240-350 1.49
Bonny Medium
0.23 232-342 0.16
 Fuel Sulfur Reduction - India
Date Diesel Gasoline
1995 10,000 ppm (nationwide) –

1996 5,000 ppm (Delhi + selected cities) –

1998 2,500 ppm (Delhi) –

1999 500 ppm (BS II, Delhi, limited supply) –

2000 2,500 ppm (nationwide) –

2001 500 ppm (BS II, selected cities) –

500 ppm (BS II, nationwide)

500 ppm (BS II, nationwide)
2005 150 ppm (BS III, selected
350 ppm (BS III, selected cities)
cities)
150 ppm (BS III,
350 ppm (BS III; nationwide) nationwide)
2010
50 ppm (BS IV; selected cities) 50 ppm (BS IV, selected
cities)
2017 50 ppm (BS IV;nationwide) 50 ppm (BS IV; nationwide)

2020 10ppm (BS VI; nationwide) 10 ppm (BS VI; nationwide)

15
Hydrotreater - Typical Flow Diagram

16
Effect of Flow Distribution in Reactors
Factors Affecting DHDT Operation

 Catalyst
 Reactor volume
 Reactor internals
 Reaction kinetics and thermodynamics
 H2 partial pressure effect
 H2S partial pressure effect
 Reaction temperature & constraints
 H2 consumption
 Hydro-Cracking

for Converting Lower Value Products

to Higher Value Products

19
 HYDROCRACKING…
 The process of converting higher molecular
weight hydrocarbons into more valuable lower
molecular weight hydrocarbons
 C22 H46 + H2  C16H34 + C6H14

In presence of Hydrogen

at high temperatures(290 – 455 deg C) & high

pressures (105-190 Kg/cm2g)

in presence of a catalyst

The products are clean, saturated & high in value 20

 BENEFITS OF HYDROCRACKING

 Middle Distillate yield is 80% as compared to

45% in FCCU

 Entire feed stock can be converted to the

product range i.e. no coke or by products

 Low Sulphur, Nitrogen and Aromatic content in

Products

21
 Typical Composition of VGO from
different crude sources

Crude Source Bombay Minas Arabian Maya California

High Heavy

LV% Yield of 26 37 24 23 24
340 – 540°C
API Gravity 28 34 22 21 14
LV%, P 46 44 17 11 1
N 23 34 25 29 42
A 31 21 58 58 57
Sulfur Wt. % 0.5 0.1 3.0 3.1 1.0
Nitrogen ppm 410 610 150 1880 6470
22
Source : R. L> Howell et.al., Pet. Ref. Conf. Tokyo
 Hydrocracker feedstocks

 Heavy Gas Oils in North America for the production of naphtha.

 Vacuum Gas Oils in India & the Middle East.

 Specific Gravity: 0.89 – 0.92

 Distillation, ASTM D 1160, Deg C

 IBP / 5% 340 / 390
 95% / FBP 550 / 575
 Asphaltenes, ppm < 100 ppm
 Metals, ppm < 2
 PNA, vol% 40 / 25 / 35 (Typical)
 Sulphur, ppm3000 – 5000
 Nitrogen, ppm 400 - 1200

23
 PRODUCT SPECIFICATIONS
PRODUCT PROPERTY SPEC
Vapour Pres.@ 65 OC Max 16.87 kg/cm2
LPG Vaporisation @2 OC & 760 mmHg 95% min
Copper Strip Corrosion Not worse than 1
Reid Vapour Pressure Max 0.4 kg/cm2 (a)
Light Naphtha
Sulphur Content Max 5 ppmw
Sulphur Content Max 5 ppmw
Heavy Naphtha
Nitrogen Content Max 1 ppmw
ASTM D86 VOL% 10 / FBP Max 205OC / 300 OC
Kerosene Sulphur Content Max 30 ppmw
Freezing Pt/Flash Pt /Smoke Pt -51OC/40OC/21mm
Cetane Number 56 min
HSD
Sulphur Content Max 50 ppmw

24
Typical Hydrocracker Product Pattern, wt%

Feed Streams Product Streams

VGO 100.0 FG 1.5
Hydrogen 2.25 LPG 4.5
Light Naphtha 12.5
Hy. Naphtha 3.0
ATF / Kero 39.45
Diesel 39.3
Bottoms 2.0
Total 102.25 Total 102.25

25
 COMPARISON OF ALTERNATE
CRACKING PROCESS

Hydrocracking FCC Thermal cracking

Op. Press. High Low Low
Naphtha Low High Low
Middle Distillates High Moderate Moderate
ATF Yes No No
Product Quality High Low Low
Post treatment No Yes Yes
of products
Capital, Maint Cost High Low Low

26
Once through Hydrocracker with Pre Treat Reactor:
Part & Full Recycle
Gas
M/up H2

Recycle Gas Comp. Naphtha

Feed

Recycle Gas

Kerosene
Pre Treat Quench Fractionator
Reactor Quench

HC
Reactor Diesel
HP Separator

Recycle Feed Bottoms

27
 Hydrocracking Unit Reactions

 Desired reactions
 Treating to remove contaminants
 Adding hydrogen to unsaturated
hydrocarbons
 Cracking to obtain desired boiling range
products
 Undesired reactions
 Coking
 Contaminant poisoning
28
 Why Pretreat Feedstock

 Improves cracking catalyst effectiveness

 By reducing organic nitrogen in cracking

reactor feed

 Reduces temperature rise in cracking beds

 Treating reactions can be very

exothermic

 Treating catalyst is less expensive

29
 Treating Reactions

Easiest

 Metals removal
 Olefins saturation
 Sulfur removal
 Nitrogen removal
 Oxygen removal
 Aromatic saturation Hardest

30
 By-products of Treating

 Organic Sulfur  H2S

 Organic Nitrogen  NH3
 Oxygen Compounds  H2O

31
 Metals Removal

Organo – Metallic
Compounds Adsorption Reaction

(Metal +Catalyst)
+
Hydrocarbons

32
 Metals Removal

Organo-Metallic Adsorption
(Metal + Catalyst) + Hydrocarbon
Compounds Reaction

Catalyst
Pill

Pore
33
 Hydrocracking Reactions

 Bi-functional mechanism

 Requires two distinct types of catalytic

sites to catalyze separate steps in the
reaction sequence

34
 Bi-Functional Mechanism

 Metal Function:
 Generates olefin or cyclo-olefin
 Acid Function:
 Generates Carbenium ion from olefin by proton
transfer
 Carbenium ion cracks
 Converts carbenium ion to olefin by proton transfer
 Metal Function:
 Saturates olefins

35
 Hydrocracking Reaction Mechanism

H + H
R c H H H
c H
H R c
c + R c
c H H
H R
3. Diffusion to H H
acid sites
H
4. Crack H H c H H
R c R
R c c 5. Hydrogenation
R H
c c H H H
H H
H
ACID SITE 2. Olefin METAL SITE
formation
1.
Dehydrogenation

H H
H H c
c R
c
R H
H

36
Hydrocracking Science and Technology; Julius Scherzer, A.J. Gruia. \ Organic Chemistry 5th addition TW Graham Solomons.
 Effect of Chain Length
on Hydrocracking Conversion

100

80 n-Decane
Degree of Conversion,%

n-Nonane
n-Octane
60 n-Heptane
n-Hexane

40

20

0
240 260 280 300 320 340
Temperature, °C
Influence of reaction temperature on hydrocracking
conversion of n-alkanes with different chain length
Figure From: J. Weitkamp, ACS. SYMP.SER. 20,6, (1975)
37
 Major Classes of Reactions in
Hydrocracking

Hydrotreating Beds Hydrocracking Beds

- HDM - Isomerization

- HDO - Hydrodealkylation

- HDS - Naphthene ring

- HDN opening
- HDA - Paraffin

hydrocracking
Coking is side reaction deactivating the catalyst

38
 Hydro-Processing
Catalysts
&
Optimal Operating
Parameters for max. life

39
 Catalyst appearance, shape and size
Catalysts or catalyst support
commonly formed into extrudates,
spheres or pellets. ΔP in fixed
bed reactor affected by catalyst
shape and size. Extrudate length
2 - 4 times it’s dia (typically 
about 1.2 mm). Simplest form of
extrudate is cylinder. Forms like
tri lobes / twisted tri lobes / tetra
lobes also found. Multi lobe cross
Source Axens
sections have higher surface to
Tri lobe volume ratio than cylinders.
Shaped catalyst particles reduce
diffusional resistance, create
Source- Haldor Topsoe
more open bed and reduce ΔP
CATALYST

Source Axens
 Hydroprocessing Catalysts
 HYDROTREATING
 Nitrogen and sulfur removal
 Non-noble metal on alumina base
 Ni-Mo for higher severity
 Co-Mo for lower severity

 HYDROCRACKING
 Bifunctional Silica - Alumina catalyst
 Acidic sites for cracking reactions
 Metal sites for hydrogenation, dehydrogenation
 Two types of hydrocracking catalysts
 Amorphous (SiO /Al O ) for producing middle distillates
2 2 3
 Zeolites for producing naphtha, LPG

42
 Catalyst Metals

 Base metal
 Metal sulfide is the active form
 Mo and W sulfides considered ‘Active’
 Ni and Co sulfides considered ‘Promoters’

 Combination Active + Promoter metals used

 Pd, Pt
 Strong hydrogenation function

 Sulfur intolerant

43
 Catalyst Support

 Amorphous
 Large pores
 Moderate acidity
 Lower surface area

 Zeolite
 Smaller pores
 Variety of structures
 High acidity

44
 Catalyst Sulfidation / Activation

Important to get the active sulfide form of the

catalyst which is not pre- sulfided.The metals in
the oxide form are sulfided by a sulfiding agent
such as DMDS (dimethyl disulfide) under the
conditions specified by the catalyst supplier

CH3-S-S-CH3 + 3H2 2 CH4 + H2S

MoO3 + 2 H2S + H2 Mo S2 + 3 H2O
3NiO + 2 H2S + H2 Ni3 S2 + 3 H2O
Hydrogenation Cracking
Function / Activity Function /
Activity

Pt(Pd)
Zeolite
Ni-W

Silica- Alumina
Ni-Mo

Co-Mo
46
 Catalyst Selectivity

Amorphous Silica Alumina

Zeolite

Naphtha Jet Diesel

47
CATALYST LOADING
 Catalyst loading methods

 Sock Loading
 Easiest and Fastest
 Must use proper technique

 Dense loading
 More catalyst in given volume
 May be slower than sock loading
 Closely monitor to ensure optimum loading
 Lower void fraction

49
 Choosing Catalyst Loading Method

 Available reactor volume

 Pressure drop higher for dense loading
 Review pressure drop history, particularly
for top bed
 Consider recycle compressor head
availability and catalyst support beam
system
 Flow distribution

50
 Reactor Unloading Methods

 Gravity Dumping
 6-7 m3/hr typical
 May not flow readily

 Vacuuming
 3-5 m3/hr typical
 Higher losses (10-30 %)

 Combination

51
Catalysts Unloading System

52
 Catalyst Regeneration
 With the progress of cycle, catalyst deactivates
approaching EOR conditions.The product may not meet the
specifications, the reactor ΔP may be high affecting the
recycle gas flow rate.
 The catalyst activity may be recovered by in situ or ex situ
regeneration. The coke on the catalyst is burnt under
controlled conditions of temperature and air- nitrogen flow.
Oxygen concentration in the reactor I/L nitrogen is
monitored & air supply is strictly regulated to control
reactor ΔT. Caustic scrubbing downstream of air cooler and
NH3 injection in effluent exchanger is carried out to protect
against sulfur oxides.
 Some of the latest super active catalysts may not regain
the high activity during in-situ regeneration. They are to be
properly regenerated ex- situ.
53
CATALYST MONITORING
PARAMETERS

54
Weighted Average Bed Temp. (WABT)
 Attribute a weight fraction of the Catalyst
bed to each TI
A=25% catalyst
B=35% A
catalyst
T1

C=40% B
catalyst
T2 eight
C T3

WABT = 0.25*T1+0.35*T2+0.4*T3
55
 Conversion

 Defined as % of feed that is converted to products in

the hydrocracking unit
Conversion = ( Feed  UCO)

*100%
Feed

 Conversion to XXX oC – final boiling point of heaviest

product – For Diesel, it is calculated upto 360oC
 Effects catalyst stability and product properties
 Reactor Temperature ≈ Conversion

56
 H2 to Oil Ratio

 It affects bed t

 Improves distribution of materials

 Reduces over-cracking

 Suppresses coke formation

57
Liquid Hourly Space Velocity (LHSV)

High LHSV Leads to

 Poorer product properties at same average

temperature.

 Higher temperature to meet product

properties reducing cycle length.

58
 Pressure

 Hydrogen Pressure is key

 Required Pressure is determined by:
 Feedstock
 Desired product quality
 Desired Cycle life
 Higher pressure or higher purity
 Inhibits coke formation

H2 Partial Pressure = Recycle Gas H2 purity *

Pressure
59
 Wash Water

 Removes Ammonia from recycle gas

 Maintains catalyst activity

 Prevents exchanger fouling due to

ammonia salt formation

60
 Water Injection Point

 Upstream of effluent condenser with even

distribution of wash water. Restriction orifices

may be used for good distribution. 20% of

injected water to remain in aqueous phase to

avoid acidic dew point corrosion.

61
 Ammonium Bi-sulfide Corrosion

May be common in conventional hydrocrackers

particularly using demetallized oil. Main source of
potential under deposit corrosion and tube pitting occur
by NH4HS.

The Important parameters are :

• The NH4 HS concentration is wash water

• The fluid velocity in tubes of condenser.
• The hydraulic symmetry of the circuit.
• The water injection point, water quality and quantity
• Condenser outlet temperature

62
 Air Cooler Pipings - Symmetrical

• Pipings should be symmetrical to ensure equal

distribution of oil, water and vapor phases.

• Effluent condenser tubes and piping to have

velocity of 10-20 fps for CS.

63
64
 Good Flow Distribution

 Characteristics
 Good radial temperature profiles
 No hot spots
 Not sensitive to minor upsets
 Results
 Minimized risk of temperature excursion
 Longer cycle length
 Improved selectivity

65
Reactor Internals

66
 Reactor Internals
Typical internals of the reactor are:
•Inlet nozzle and inlet distributor
•Distribution Trays
•Trash Baskets
•Thermowells
•Beds of alumina of different sizes and beds of catalysts
•Catalyst support grids
•Quench injectors
•Remix distributors with mixing and distributing trays
•Catalyst withdrawl pipes and draw off nozzle
•Outlet collectors and withdrawl nozzle
REACTOR INTERNALS

68
 Good Distributors
• Decreases radial thermal maldistribution.
• Increase volume for catalyst loading.
LEADING TO
 increased cycle length

 reduced catalyst deactivation rate

 higher throughput

 increased conversion

 improved product quality

 improved product consistency.

69
 Bubble Cap Trays

 Liquid distribution uniformity may be higher

than for conventional tray.
 Number of distribution sources restricted by
minimum size of bubble cap.
 Often a layer of distributive packing is
required with this distributor type.
 Can be expensive to construct.
 Bubble caps difficult to inspect during service

72
 High performance distributors
increases catalyst utilisation

conventional tray bubble cap tray New design

73
 Pressure drop control
Size grading
Activity grading

Void Activity

Inert ceramic ring 55% None

3/6” rings 53% Low

1/8” rings 53% Medium

1/16” extrudates 45% High

75
 Reactor MPT (Min. Pressurising Temp.)

2 ¼ Cr -1 Mo
93 oC (200 oF)
Old
Metallurgy
2 ¼ Cr – 1 Mo
150 oC -1/4 V
(300 oF) or
3 Cr – 1 Mo – ¼ V
66 oC (150 oF)

Pre 1990 Metallurgy Newer Metallurgy

76
 Reactor Startup Procedure for MPT

 For heavy wall reactors – heat to MPT

before pressurizing above 20% shop
test pressure
 For older reactors, may need to reduce
pressure and increase temperature if
cracks exist
 For newer units, lower temperatures
may be used

77
 Temperature Runaway !!
 The overall reaction rate is significantly exothermic.
 Under some situations the exothermicity may
increase the bed temperature to high level, the
heat generated leading to higher rate and more
heat. This can spiral running out of control and
potential loss to vessel or pipings by excessive
temperature.
 In normal operation quench sweeps the heat. In
emergency situation the depressurization can
reduce and stop reaction. De-pressuring can be
fast or slow based on the use of either of the
systems, as deemed necessary.

78
Source : E. M. Marszal, Exida
 Causes of Temp. Run-away

1. Recycle Compressor Failure

The hydrogen flow decreases. The quench gas
flow stops. So heat removal from the reactor stops.
Due to ample hydrogen pressure the reactions may
continue to result in starting of runaway phenomenon
so start slow depressuring or manual activation of slow
depressuring.

79
 Causes of Temp. Run-away….

2 Reactor Internals Failure

Failure of Cat. Support screens, distribution boxes

can initiate temperature runaway. Sometimes the
quench management may help. If the damage is
severe, it may be difficult. So depressuring for safe
state.

80
 Causes of Temp. Run-away….

3. Quench Failure
Low or no quench flow due to controller failure or CV
failure. Sometimes manual operations of valve from
control room/field by hand jacking the CV.

4. Plugging/ Channeling/ Coking and contamination

leading to hot spots

5. Improper catalyst loading leading to channeling.

81
 Causes of Temp. Run-away….

6. Bed temperature measurement failure

Failure of bed temperature can lead to runaway if the failure
action decreases/ stop the quench. Manual operation of CV
can prevent the initiation of runaway.

7. Failure of recycle gas flow controller

8. Change in feed flow and gas to oil ratio

9. Failure of fired heater O/L temperature control

This may lead to high heater O/L temperature. & a run-away
may occur
82
 Arresting Temperature Runaway !!

Depressurize (Reduce Hydrogen Partial pressure)

• Operator may first try slow system
(7kg/cm2/min). If response is not satisfactory
he may opt for fast system.(21 kg/cm2/min.)

• Safety Integrated Function (SIF) may also

initiate depressurizing on detecting high
temperature.
83
An Example of Operational Mistake

84
 Reactor quench Problem
 High Back Pressure in inter-bed Quench distributor
 Control valve used to become flat open and still adequate quench flow was
not obtained
 Quench control valve operation checked & found OK
 Suspected pressure drop across quench orifice
 Chokage in Quench distributor

During SD, Boroscopy revealed that in addition to an RO at the inlet of each

spider leg, an RO was provided in the common inlet pipe of the distributor.
The inlet pipe was cut open, RO was removed and re-welded.
 Reactor Problems
• Leak in Hydrocracker reactor bed thermo-well
- Thermo-well was removed for catalyst un-loading
- Was kept on reactor platform was DP testing
- After feed cut-in leak was observed from the thermo-couple
- Unit had to be brought down
- SS Box was welded on the thermo-well cover to contain the leak

Since the thermowell was lying on Reactor platform during SD, crack must
have developed on its body due to impact of some heavy object
 Reactor Problems
• Crack in parent pipe near Inter-reactor quench

Q
Crack
Q
Regions

Pipe
Quench
weld
seam
Pipe injection
nozzle weld
seam

ctor line cracked near quench

 Furnace Tubes Tilted
• Re-cycle Gas Furnace Tubes detached from hangers
 U-Tubes could not expand downwards as space below Spigots were plugged with
debris & refractory chips
 Debris could not fall out as there was no opening in furnace shell

Hangers
~ Tubes came
~ out from
hangers

Refractory Spigots

Opening should be made at these locations on furnace’s bottom shell so that debris do not accumulate
and tubes can freely expand downwards
89