HYDROTREATING

Oil Refining Processes

TKP-4150 - Group A
April 8th, 2013

Background & Basics

Definition of Hydrotreating

Use of hydrogen for:

Removal of heteroatoms (S, N, O).

Removal of heavy metals (V, Ni).
Saturation of olefins and aromatics.

No significant reduction of molecular

weight.

Driving forces:

Process requirements.
Environmental policies.
Product specifications.

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Background & Basics

The Role of Hydrotreating in a Refinery

Simplified processing scheme of an oil refinery

4

(I. Chorkendorff and J. W. Niemantsverdriet, 2003)

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Chemistry of Hydrotreating

Hydrodesulfurization (HDS)

Sulfur: most abundant heteroatom.

Removed as H2S.

Simple removal reactions:

Mercaptanes

RSH + H2 RH + H2S

Sulfides

R2S + 2H2 2RH + H2S

Disulfides

(RS)2 + 3H2 2RH + 2H2S

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Chemistry of Hydrotreating

Hydrodesulfurization (HDS)

Thiophenes are more difficult to treat:

Global reaction mechanism for hydrodesulfurization of thiophene

7

(I. Chorkendorff and J. W. Niemantsverdriet, 200

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Chemistry of Hydrotreating

Hydrodesulfurization (HDS)

Sulfur is commonly present as thiophene:

Example of sulfur types distribution as a function of distillation temperature (fraction)

in Arab medium distillate (Stanislaus et al, 2010)
8

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Chemistry of Hydrotreating

Hydrodenitrogenation (HDN)

Mostly found in heavy fractions.

Nitrogen removed as NH3.

Amines
Pyrrole

Pyridine

Quinoline
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Chemistry of Hydrotreating

Hydrodeoxygenation (HDO)

Low and medium boiling point fractions.

Non-conventional sources.
Oxygen removed as water.
Phenols
Peroxides

Naphtenic
acids

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Chemistry of Hydrotreating

Hydrodemetallization and halides removal

Most common: nickel and vanadium.

Removed as metal sulfides.

Chloride and bromide present at trace

levels.

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Chemistry of Hydrotreating

Hydrodearomatization & olefin saturation

Aromatics: naphtha to gasoil boiling range.

Olefins and diolefins: formed in thermal and
catalytic units.

Toluene

Naphthalene

Phenanthrene
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Chemistry of Hydrotreating

Hydrotreating Catalysts

Most common: -alumina base, promoted

MoS2

Co-Mo:

Ni-Mo:

13

Preferred for HDS.

Lowest hydrogenation activity.
Low sensitivity to H2 consumption and operating
pressure.
Better HDN and hydrogenation performance.
Higher sensitivity to H2 partial pressure.

Topse catalysts for hydroprocessing of petroleum fractions (Brochure, 2009)

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Chemistry of Hydrotreating

Deactivation of Hydrotreating Catalysts

Temporary:

Coke formation:

Defines when to regenerate

catalyst.

Deposition of nitrogen and

sulfur compounds.

Irreversible:

Metal deposition:

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V, Ni, Pb, Fe, As, among others.

Example of coke buildup on

catalystand the agglomeration
from unstable dienesin feed.

Catalyst support sintering.

Hydrotreating

(Sanghavi, K. & Schmidt, J., 2011.)

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Thermodynamics of Hydrotreating

Equilibrium & Heat of Reaction

Hydrotreating reactions are

exothermic.

Increasing temperature:

But:

Kinetic rates.
Metal removal.

Equilibrium conversion.
Coke formation.
Aromatic saturation maximum
activity at 385C.

Other parameters to favor

reaction:

H2 partial pressure.
LHSV.

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A
B

C
Equilibrium data of selected HDS
reactions.
(Fahim
et al, 2010)
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Hydrotreating Processes

General Process Description

Liquid feedstock is mixed with hydrogen.

Furnace preheat the mix.

Naphtha (vapor).
Heavier residues: gas oil or residue (mixedphase).

Catalytic reactor.
Cooling and
separation steps:
Liquids to
fractionator
Gases to
treatment.
Main elements of Hydrotreating Processes.

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(Fahim et al, 2010)

Hydrotreating Processes

Naphtha Hydrotreating

Naphta Hydrotreating Process.

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(Fahim et al, 2010)

Hydrotreating Processes

Middle Distillates Hydrotreating

Feedstock: kerosene, jet fuel oil, and diesel.

Diesel Fuel Hydrotreating

Unit. (Fahim et al, 2010)
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Hydrotreating Processes

Atmospheric Residue Hydrotreating

Reduce metal content:

Reduce sulfur content:

Ni and V, from 75-90 ppmw.

From 5 to 0.5 wt%.

Process temperature is 370C.

To avoid coke formation, steam is fed to the
heater.
Guard reactor contains 8 % of the total catalyst.
(retains 30% of V).
Produces: Naphtha, Diesel, and Low Sulfur Oil.

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Hydrotreating Processes

Atmospheric Residue Hydrotreating

Atmospheric Hydrotreating Process.

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(Fahim et al, 2010)

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Hydrotreating Processes

Operating Conditions

Vary due to the broad variety of applications.

The most important operating conditions are:
Typical Process Parameters for Hydrotreating of Different Feedstocks.
(Fahim et al, 2010; Speight et al, 2011)

Feedstock

Naphth
a

Temperature

Hydrogen

VGO*
360380

Residu
e
360380
120160

260-300

pressure

bar

5-10

15-30

15-40

40-70

partial
pressure

bar

10-20

20-31

26-41

50-90

90-200

0.050.10

0.1-0.2

0.3-0.5

0.4-0.7

1.5-2.0

4-10

2-4

1-3

1-2

36-48
3-10

36-48
-

36-48
-

36-48
-

consumption wt%
LHSV
H
/HC ratio
* 2VGO
= Vacuum gas oil
Catalyst life
23

Kerosen
Gas oil
e
320300-340
350

hr-1
std m3/m3
years

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0.150.3
12-24
0.5-1

Hydrotreating Processes

Fixed-Bed Reactor

Adiabatic reactor:

Works as a plug-ow reactor:

To control temperature, the outflow is

quenched between reactors.

Pressure drop and reaction rate must be

balanced.

Mechanical
catalyst.

over

Reactivity is favored.
Pressure drop is increased.

(Ullmanns Encyclopedia of Industrial Chemistry,

1992)

24

the

Attrition decreases catalyst particle size:

Fixed Bed Reactor

work

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Hydrotreating Processes

Trickle-Bed Reactor (TBRs)

Preferred for two-phase

uids.
Multiple
randomly
fixedbeds in the same body.
Quenching points to control
temperature.
Distributor design is a
very important issue.

Trickle Bed Reactor and Examples of Distributors

(Lee , 2006; Renade et al. 2011)

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Safety & Environmental Issues

Byproducts, Emissions, Catalyst Handling

Closed process.
Hydrotreating reduces SOx and NOx emissions.

Possible risk during inspections, maintenance,

regeneraton/loading/ unloading of catalyst.

Catalyst may be regenerated several times to

remove coke and sulfur.

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CO2 and CO are produced.

Sulfur reacts to form SO2.
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Hydrotreating

Selected References

M. A. Fahim, T. A. Al- Sahhaf and A. S. Elkilani, Fundamentals of Petroleum Refining,

Elsevier, 2010.

I. Chorkendorff and J. W. Niemantsverdriet, Concepts of Modern Catalysis and

Kinetics, Weinheim: WILEY-VCH Verlag GmbH & Co., 2003.

Topse catalysts for hydroprocessing of petroleum fractions,

http://www.topsoe.com/business_areas/refining/~/media/PDF
%20files/Refining/topsoe_hydroprocessing_catalysts_aug09.ashx; Brochure, 2009.
Visited: March 26th, 2013.

A. Stanislaus, A. Marafi and M. S. Rana, "Recent advances in the science and

technology of ultra low sulfur diesel (ULSD) production," Catalysis Today, no. 153, p.
168, 2010.

Sanghavi, K. & Schmidt, J., 2011.

http://www.hydrocarbonprocessing.com/Article/2892145/Achieve-success-in-gasolinehydrotreating.html Visited : March 26th, 2013

J. G. Speight, "Chapter 8 Hydrotreating and Desulfurization," in The Refinery of the

Future, Elsevier, 2011, p. 237273.

S. Lee, Ed., Encyclopedia of Chemical Processing, New York: Taylor & Francis Group,
LLC, 2006.

V. Ranade, R. Chaudhari and P. R. Gunjal, Reactor Engineering and Applications, Elsevier, 2011.

Ullmann's Encyclopedia of Industrial Chemistry, vol. B4, VCH Publishers, 1992.

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Thank you for your attention!

Questions?

HYDROTREATING
Oil Refining Processes
TKP-4150 - Group A
April 8th, 2013