Naphtha Hydrotreating Unit

Prepared by :
Mohamed Fathy Mohamed
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Naphtha

Naphtha is a complex mixture of liquid

hydrocarbons, with boiling ranges of about 38 to
205 C and with vapour pressures of about 0.69
bar.
Crude distillation, catalytic cracking, delayed
coking and visbreaking units produce naphtha
with low octane number and contains deferent
types of contaminants at the same time .
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Octane no. Improvement

As more demand for high Gasoline Octane no. to

match with modern motor.
Chemical structure modification is achieved on
an expensive Platinum catalyst at Catalytic
reforming and Isomerization unit.
Sulfur, Nitrogen, Oxygen and other impurities in
Naphtha work as a poisonous for Pt catalyst
activity.
Hydrotreating is used to prepare a clean
feedstock to protect catalyst used in naphtha
reforming.
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History of Naphtha Hydrotreating

1897 : Paul Sabatier, French chemist discovered the

fixation of hydrogen on hydrocarbon (ethylene, benzene)
double bonds using nickel containing catalyst.

1903 : Wilhelm Normann, German chemist applied

catalytic hydrogenation to Saturate Organic acids.

1950's : First catalytic reforming process was

commercialized. At the same time, the catalytic
hydrodesulfurization of the naphtha feed to such
reformers was also commercialized.

Currently : All petroleum refineries world-wide have one

or more HDS units.
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Straight Run Naphtha

Catalytic
Catalytic cracking Naphtha. Reforming
Naphtha
Delayed Coking Naphtha. Unit
Hydro-
Visbreaking Naphtha.
treating Gasoline
FCC Naphtha Light
Naphtha
Isomerization
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Catalytic Reforming Unit

Using expensive Platinium catalyst on chlorinated alumina.
Dehydrogenation of Nahthenes , Dehydrocyclization & Isomerization of
Paraffins.
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Light Naphtha Isomerization

Using Pt catalyst on highly chlorinated alumina.

Isomerization of Pentane and Hexane
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Impurities Removal

Sulfur Removal
Nitrogen Removal
Oxygen Removal
Metallic Compounds
Unsaturated Products
Halide Removal
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Sulfur Removal
Mercaptans:

Sulfides:

Disulfide:

Cyclic sulfide:
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Sulfur Removal

Thiophenes:

Benzothiophenes:

Dibenzothiophenes
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Sulfur Removal
Distribution of sulfur compounds in the cuts from distillation of a crude
with 1.2%wt sulfur.
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Nitrogen Removal
Pyridines:

Quinoline:

Isoquinolines:

Pyrroles:
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Nitrogen Removal

Indoles:

Carbazoles:

Methylamine:
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Oxygen Removal

Phenols:
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Oxygen Removal

Naphthenic acids:
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Metallic Compounds
Catalyst Maximum
Impurities Source Main Cut
Poison content (%wt)
Distillates Strong, deposit inside
Ni,V Crude
Residues catalyst and plugging
10

Strong, deposit at top

As Crude All
of reactor
0.2-2
Slight, only slightly
Hg Crude Naphtha
retained
Traces

Strong, deposit at top

NaCl Crude Residues of reactor, generates 1
pressure loss

Slight, deposit at top

Crude and
Fe corrosion
All of reactor, generates 1
pressure loss
Very slight, deposit
Anti-foaming
Si agents
Distillates inside catalyst and 0.1-0.5
plugging
Strong, deposit at top
Pb Recycled gasoline Gasoline
of bed
5-10
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Unsaturated Products

Linear olefin:

Cyclic olefin:

Aromatics Saturation: the-main unsaturated compounds present in oil,

The number of aromatic rings increases with the distillation temperature
of the cut.
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Halide Removal

Organic halides can be decomposed in the Naphtha Hydrotreating Unit to

the corresponding hydrogen halide, which is either absorbed in the
reactor effluent water wash or taken overhead in the stripper gas.
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Hydrotreating Processes

The Naphtha Hydrotreating Process is :

Catalytic refining process employing a selected
catalyst and a hydrogen-rich gas stream
Decompose organic sulfur, oxygen and nitrogen
compounds contained in hydrocarbon fractions.
In addition, hydrotreating removes Organo-
metallic compounds and saturates olefinic
compounds.
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Feeds and Products for Hydrotreating Unit

Straight Run Naphtha

Off Gas to Amine Treat

Coker Naphtha
LPG to Amine Treat
NAPHTHA
FCC Naphtha
HYDROTREATING Light Naphtha to Isomerization

Hydrocracked Naphtha UNIT

Heavy Naphtha to Platforming
Visbreaking Naphtha
Sour water to Water Stripper
H2 Make up from CRU
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Hydrotreating Process
R.C.Suction Drum Stripper Sour Gas To
Product Condenser 02-
02-V-03 Condenser U-12
E-02
02-E-05
Feed Surge Drum 02-
Reactor
V-01
02-R-01 T=120 oC T=99 oC P=7.1 barg
Charge Heater 02- T=48 oC
P=3.7 barg H-01 P=45.5 barg
T=102 oC T=325 oC
Stripper
T=55 oC 02-K-01 T=50 oC
T=301 oC Receiver 02-
V-04
P=10.4barg

Separator 02- T=154 oC

V-02 Sour water to
Stripper 02-
T-01 U15
HCK

DCU

CDU

HP Stripper
T=343 oC T=201 oC Steam Reboiler
02-E-04
Tank-08-
09 P=52.3 barg Condensat
T=77 oC e
Recycle Gas Unit 03

Combined Feed Exchanger 02-

E-01
Stripper Feed Bottom
Makeup H2 Gas Exchanger 02-E-
from CCR 03
 T=86 oC

Naphtha Splitter Condenser 03-E-

03

P=0.7 barg Naphtha Splitter Receiver 03-V-01

T=72 oC

Naphtha Splitter
03-T-01

Sour Water to U15

P=1.9 barg
Hydrotreated Light Naphtha
T=124 oC

T=159 oC

T=148 oC

Naphtha splitter feed-

Bottom Exchange 03-E- Hydrotreated Heavy Naphtha
01
P=10.3 barg
T=124 oC

Naph. Splitter
OV.HD Cooler 03-
Unit 02 Naph. Splitter E-04
Naph. Splitter. Reboiler Heater 03-
Bottom Cooler 03- H-01
CCR Feed Penex
E-02
51-TK-8 Feed
51-TK-9
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Hydrotreating Process
1. Fixed Bed Reactor

Feed System Recycle Gas

Reactor System Fractionation section
Wash Water System Stripper Section
Separator System Naphtha Splitter Section
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Hydrotreating Process
2. Fluidized Naphtha Hydrotreating

Maintain catalyst in its active form.

Limited Applications due to its complicated design.
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Other Naphtha treating Units

MERCAPTAN OXIDATION MEROX.

Low operating cost and investment requirement.

Ease of operation.
Limited Mercaptan treating not less than 5ppm.
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Objectives of Hydrotreating Processes

Meeting finished product specifications

Kerosene hydrotreating:
a) Reduces mercaptans, sulfur, aromatics,
b) Improves smoke point.
Gas oil hydrotreating:
a) Reduces sulfur, nitrogen, aromatics, olefins,
b) Improves cetane number, thermal stability.
Lube oil hydrofinishing:
a) Reduces sulfur, Conradson carbon (CCR),
b) Improves colour, oxidation stability.
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Objectives of Hydrotreating Processes

Preparing the feed for other refinery processes.

Naphtha hydrotreating : is a pre-treatment for
isomerization and catalytic reforming processes.
The objective is to reduce sulfur, nitrogen (<0.5
ppm wt), and olefins (< 0.1% wt).
Vacuum distillates: such as straight run,
visbreaking, coking and deasphalted oil are
hydrotreated as pre-treatment for FCC and hydro-
crackers. Improves hydrogen content, crack
ability, results increased conversion, reduced
impurities in products, lower SOx and NOx
emissions in gases exiting the regenerator.
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Hydrotreating Process
Distillate hydrotreating processes incorporated in a refinery flow scheme
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Hydrotreating Process
Typical operating conditions, for Distillate and
Residue hydrodesulfurization.

H2 Temperature
Cut Point Space H2/HC ratio
Petroleum Cut Pressure, at Start of
,C velocity,hr-1 , nm3/m3
bar Run

Naphtha 70 -180 1.0 5.0 14 260-300 100

Kerosene 160240 1.0 4.0 28 300-340 150
Gas Oil 230-350 1.0 3.0 35 320-350 150-300
Vacuum Gas
350-550 0.72 2.0 55 360-380 300-500
Oil
Atmospheric
350+ 0.3 - 0.5 100 - 130 360-380 1000
residue
Vacuum
550+ 0.15 - 0.3 120 - 160 360-380 1000
residue
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Hydrotreating Process
Hydrotreating Capacity Worldwide.

Regions Capacity (Mt/year)

United States 320
Europe 180
Asia/Pacific 140
Rest of the world 260
Total 900

> 200
200
No. of units

54

23

Naphtha Residuals VGO Distillate

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Hydrotreating Process
Egypt has eight petroleum refining companies distributed
around the country. In Cairo, Alexandria, Suez, Asyut and
Tanta. Six of eight companies have constructed a naphtha
hydrotreating unit.
Barrel/Day

35000

30000

25000

20000

15000

10000

5000

0
Midor Alexandria Suez Ameria Cairo Asyut
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Process Variables

Temperature
Reactor Pressure
Hydrogen to Hydrocarbon Ratio
Space Velocity
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Temperature

The treating severity increases directly with

temperature to decrease the content of
sulfur, nitrogen, oxygen, and metallic compounds
in the treated product.

Factors affect selecting treating temperature:

a) Feed Quality Changes.
b) Changes in Feed Rate.
c) Catalyst End-Of-Run. Maximum temperature
catalyst can withstand , after this temprature , it
will not give the required product quality .
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Temperature

When operating at too high temperature for

maximum sulfur removal. Recombination of
hydrogen sulfide with small amounts of olefins
can result, producing mercaptans in the product
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Reactor Pressure

As the partial pressure of hydrogen increases:

1) Rate of hydrogenation increases, the treating

reactions are brought to a greater degree of
completion.
2) Catalyst is generally effective for a longer time
owing to less formation of carbonaceous
deposits which deactivate the catalyst activity.
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Hydrogen to Hydrocarbon Ratio

Increasing the hydrogen charge rate:

1) Increases the rates of hydrogenation reactions.

2) Reduce the tendency of coke formation on the
catalyst.

Calculation:

Recycle Gas to Reactor (Nm3 /h) x H 2 Purity (Mole Fraction)

H 2 /HC
Naphtha Feed (m3 /h)
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Hydrogen to Hydrocarbon Ratio

Effect of injecting hydrogen between two catalyst
beds
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Space Velocity

The severity of the operation is determined by the

relative volumes of fresh feed and catalyst.
Operating with low S.V. means low capacity of the
unit, which has bad effect on flow distribution of
feed in the catalyst bed with the result of higher
rate of cake formation
High S.V. will require increased temperature for
the same reaction severity with the result of high
coke formation.
Calculation:
volume of charge per hour (m 3 /h)
S.V.
volume of catalyst (m 3 )
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Reactions Kinetics
Relative reaction rates.
Desulfurization 100

Olefin Saturation 80

Denitrification 20

Relative heats of reaction.

Olefin Saturation 100

Desulfurization 20

Denitrification 2
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Reactions Kinetics
Reaction Mechanisms for aliphatic Hydrocarbons.
1) Elimination

2) Substitution
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Reactions Kinetics
Reaction Mechanisms for Aromatic Hydrocarbons.
1) Hydro-desulfurization of dibenzothiophene

2) Denitrogenation of Quinoline
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Catalyst of Naphtha Hydrotreating

Catalyst Protection, Aging and

Poisonous.
Catalyst sulfiding.
Regenerating the Catalyst.
Reactors Technology
weight Average Catalytic Bed
Temperature
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Catalyst of Naphtha Hydrotreating

Typical Composition of Hydrotreating

Catalyst.

Species Range, wt% Typical, wt%

Cobalt Oxide 15 3
Nickel Oxide 1-5 2.5
Molybdenum Oxide 6 25 12
Aluminium Oxide Balance Balance
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Catalyst of Naphtha Hydrotreating

The primary causes of catalyst deactivation are:

1) Rate of carbon deposition on the catalyst.

2) The gradual accumulation of inorganic species

picked up from the charge stock, ex:
arsenic, lead, calcium, sodium, silicon and
phosphorus
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Catalyst of Naphtha Hydrotreating

Catalyst sulfiding
The active phase of hydrotreating catalysts is
produced by sulfurizing the oxide form.

Reactions:
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Catalyst of Naphtha Hydrotreating

Catalyst Regenerating :
Hydrotreating catalysts become deactivated with
time mainly because of coke deposition
Regeneration Reaction:

Lifetime of hydrotreating catalyst.

Petroleum Cut Life time , yrs
Gasoline/Kerosene 4 to 10
Gas Oil, Vacuum Gas Oil 2 to 6
Residue 3 months to 1 year
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Catalyst of Naphtha Hydrotreating

Hydrotreating reactors
and its internals :
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Catalyst of Naphtha Hydrotreating

Weight Average Catalytic

Bed Temperature (WABT) :
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