Introduction to

Hydroprocessing

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Presentation Outline

• The hydrotreating process

• Different oil fractions

• Hydroprocessing drivers

• Hydrotreating reactions

• Process variables and impact

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 The Hydrotreating Process
Oil Reacts with Hydrogen
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The Hydrotreating Unit PFD

Recycle gas

Quench gas

Heater

Reactor Gas purification

H2S

Feedstock – high sulfur

Separator
Product – low sulfur
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The Hydrotreating Reactor

Distribution
Inert Topping Layer
Grading material – large size particles

Grading material – small size particles

Main Bed Catalyst
Quench, Mixer and Re-distribution
Inert Topping Layer

Main Bed Catalyst

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Hydrotreating Catalyst
Reactor Catalyst Porous Active Site
Carrier

The porous carrier is Alumina (Aluminum Oxide).

Dispersed on the Alumina surface, are metals:

• Ni Mo
• Co Mo
• Ni W
• Pt Pd
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Hydrotreating Kinetics

• Factors influencing the reaction kinetics given a fixed feedstock

➢ Catalyst type / activity

➢ Temperature
➢ Pressure (H2)
➢ Feed flow rate and residence time (LHSV)
➢ Hydrogen flow rate
➢ H2S

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 Different Oil Fractions

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Refinery Process Overview

Fuel Gas
Amine Treating Refinery Fuel
H2S Claus Sulfur Plant Sulfur
Other Gases
LPG
Gas Processing Merox Treater Butanes
Gas
Light Naphtha
Naphtha HT Isomerization Plant
Isomerate
Gasoline
Heavy Naphtha Blending
Reformate
Naphtha HT Catalytic Reformer Pool
Crude Oil
Jet / Kero
Kerosene HT Jet/Kerosene

Diesel Oil Diesel Product

Atmospheric Diesel HT i-Butane

Distillation HDC Gasoline

AGO Hydrocracker
Alkylate
UCO / Bleed Alkylation
ATB Butenes / Pentenes
Naphtha FCC
LVGO Gasoline
Cat-Cracker Feed HT Fluid Catalytic Cracker Gasoline Post-Treat HT
LCO / HCO
HVGO
Vacuum LCGO / HCGO
Distillation Resid Delayed Coker
/ Visbreaker
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Straight Run Naphtha / Gasoline

• Boiling range: 100°F – 400°F

• 15% – 30% by volume of crude
• Impurities:
➢ 10 to 500 wt ppm sulfur
➢ <1 to 20 wt ppm nitrogen
• Applications:
➢ Gasoline production
➢ Petrochemical applications
➢ Solvent production

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Straight Run Kerosene / Jet fuel

• Boiling range: 350°F – 550°F

• 10% by volume of crude
• Impurities:
➢ 0.05 to 0.3 wt % sulfur
➢ 5 to 100 wt ppm nitrogen
• Applications:
➢ Jet fuel production
➢ Light furnace oil for heating
➢ Blending component in winter diesel
➢ Solvent production

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Diesel

• Boiling range: 450°F – 700°F

• 20% – 30% by volume of crude
• Impurities:
➢ 0.1 to 1.5 wt % sulfur
➢ 50 to 500 wt ppm nitrogen
• Applications:
➢ Diesel production
➢ Furnace oil for house heating
➢ Blending component for heavy fuel oil (cutter stock)

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Vacuum Gas Oil

• Boiling range: 700°F – 1050°F

• 20% - 25% by volume of crude
• Impurities:
➢ 1.3 to 3.0 wt % sulfur
➢ 500 to 3000 wt ppm nitrogen
• Applications:
➢ FCC and hydrocracker feedstock
➢ MHC feedstock
➢ Lube oil and wax production
➢ Heavy fuel oil

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Atmospheric Resid

• Boiling range: 700°F+

• 30% – 40% by volume of crude
• Impurities:
➢ 2.5 to 5.0 wt % sulfur
➢ 2000 to 5000 wt ppm nitrogen
➢ 25 to 1000 wt ppm vanadium and nickel
• Applications:
➢ Heavy fuel oil (for ships and power plants)
➢ Feedstock to crackers
❖ (visbreaker, resid hydrotreater, coker) + vacuum distillation

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Vacuum Resid

• Boiling range: 1050°F+

• 10% – 20% by volume of crude
• Impurities:
➢ 3 to 6 wt % sulfur
➢ 0.3 to 0.6 wt % nitrogen
➢ 50 to 2000 wt ppm vanadium + nickel
• Applications:
➢ Asphalt, tar production
➢ Feedstock to crackers (coker, H-oil, LC-finer)
➢ Refinery fuel (pitch)

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 Feedstock Sulfur Content and Reactivity

Naphtha Kerosene Diesel VGO Resid

1000 8.0

7.0
100

Feedstock Sulfur content, wt%

6.0
Relative Rate Constant

10 5.0

4.0
1 3.0

2.0
0.1
1.0

0.01 0.0
C8 C12 C16 C36 C80
100 - 350°F 350 - 450°F 450 - 680°F 680 - 1020°F 1020+ °F
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Different Crude Sources

The origins of crude oil result in significant differences in the composition of the individual
fractions.
Diesels derived from different crude:

Crude Origin Gravity Sulfur Nitrogen Aromatics

API wt % wt ppm wt %
Ekofisk, North Sea ~37 0.1-0.3 50-100 25
Mid East, Kuwait ~37 0.8-1.2 50-100 30
Boscan, Venezuela ~30 ~2.5 1500 45
REB, Russia ~38 0.6-1.0 50-100 25
Bonny Light, Nigerian ~28 ~0.15 200 30

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 Hydroprocessing
Why?
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Drivers for Hydroprocessing

• Meet environmental standards for sulfur, aromatics etc.

• Convert the heavier fractions to lighter and more valuable fractions

• Improve properties of the oil to meet product specifications (Cetane, VI, etc.)

• Protect downstream catalysts from poisoning and deactivation

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Sulfur Specification for Diesel

10000

1000
wtppm Sulfur

100

10

1
1995 2000 2005 Now
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Diesel Sulfur Specifications in ppm S

Japan
EU 25 2008
North America
2010 10
2006
10 Rest Asia
15
Towards 50 South Korea
Mexico Africa 2006
In cities
2016
Towards 50 30
15
South America In cities
Towards 50 / 15 Oceania
In cities S. Africa 2009
2017 10
10

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Gasoline Sulfur Specifications in ppm S

Russia
2016 Japan
EU 27 2008
North America 10
2009 10
2017
10 China
10
2017
10

Rest of
Brazil Asia
2014 Towards 50
50 S. Africa
In cities
2017
10

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Product Specifications

• Why do they exist?

➢ Safety / Handling: Flash Point, Cloud/Pour Point + CFPP (Cold Filter Plugging Point)

➢ Environmental: Sulfur, Aromatics, Distillation

➢ Performance / Reliability: Cetane Number / Index, Density, Viscosity, CFPP, Distillation

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 Hydroprocessing Reactions

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Hydroprocessing Reactions

• Sulfur removal (hydro-desulfurization - HDS)

• Nitrogen removal (hydro-denitrogenation - HDN)
• Metals removal (hydro-demetallation - HDM)
• Oxygen removal (hydro-deoxygenation - HDO)
• Hydrogenation / Saturation of:
➢ Aromatics (hydro-dearomatization - HDA)
➢ Olefins (HYD)
• Hydrocracking (HDC)

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HDS Reactions

• Sulfur-containing hydrocarbons reacting with H2 to remove sulfur and form H2S

Examples:
Mercaptans : R-SH + H2 → R-H + H2S

Thiophenes : + 4 H2 → C4H10 + H2S

s
Dibenzothiophenes: + 2 H2 → + H2S
(DBT) s

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HDN Reactions

• Nitrogen-containing hydrocarbons reacting with H2 to remove nitrogen and form NH3

Examples:
Non-basic nitrogen-containing hydrocarbons:
N
Pyrrole N
H
Indole
H

Basic nitrogen-containing hydrocarbons :

N Pyridine N Quinoline
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HYD and HDA Reactions

Unsaturated hydrocarbons reacting with H2 to form saturated hydrocarbons

Two groups of unsaturated hydrocarbons exist:

• Olefins
➢ Formed in cracking processes
➢ Can, sometimes, be present in crude oil
• Aromatics
➢ Present in the crude oil
➢ Formed in cracking processes - especially FCC

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HDA Reactions

Types of aromatics:

Mono Di Tri

Reactivity: Mono < Di < Tri

Tri- and Di- aromatics are relatively easy to saturate forming Mono-aromatics in typical HDS
reactors.

Saturation of mono-aromatics requires higher pressure and/or longer residence time.

Alternatively noble metal catalysts can be used.

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HDM Reactions

Metal-containing hydrocarbons react with H2 to form metal-sulfides and metal-free

hydrocarbons. The metal-sulfides are deposited on catalyst.

Types of metals:
• Vanadium (V) and Nickel (Ni), present in the crude
• Iron (Fe), either found in the crudes or originating from corrosion products
• Silicon (Si), present in crude and several additives – mainly introduced in coker units (anti-foaming
agent)

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HDC Reactions

Large hydrocarbons are broken down and the fragments are hydrogenated

• Both thermal and catalytic cracking

• Larger hydrocarbons easier to crack
• Cracking reactions are sequential:

-C-C-C-C-C-C-C-C-C-C-C-C- → -C-C-C-C-C-C- + -C-C-C-C-C-C-

→ -C-C-C-C-C-C- + -C-C-C- + -C-C-C-
→ -C-C-C-C- + -C-C- + -C-C-C- + -C-C- + -C-

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 Process Variables

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Process Variables

• Reactor temperature (WABT)

• Hydrogen partial pressure

• Liquid hourly space velocity (LHSV)

• Hydrogen gas rate and hydrogen purity

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Effect of Process Variables on Hydrotreating
Performance
Process
Catalytic Variable Increasing Increasing Hydrogen Increasing Increasing
Function Temperature Partial Pressure Feedrate Hydrogen Rate

HDS

HDN

Aromatic
Then
Saturation

Olefin
Saturation
_
CCR
Reduction

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Effect of Process Variables on Hydrotreating
Performance

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Operating Temperature vs. Product Sulfur

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Feed SR Diesel
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Delta Operating Temperature (ºF)

Gravity = 35° API

15 Feed Sulfur = 1.5 wt%

LHSV = 1.0 hr-1

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Pressure (H2) = 650 psig
5

-5

-10
3 5 7 9 11 13 15
Product S (wppm)

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LHSV and Operating Temperature

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Delta Operating Temperature
15

5
Feed SR Diesel
(ºF)

-5 Gravity = 32° API

Feed Sulfur = 1.5 wt%

-15
Product S = 10 wtppm

-25 Pressure (H2) = 650 psig

-35
0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4
LHSV (hr-1)

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Summary

• A number of different oil fractions can be hydrotreated to meet product specifications (sulfur,
etc.) and to protect downstream processes (e.g. FCC)

• The process variables that impact reaction kinetics are temperature, LHSV, hydrogen partial
pressure and hydrogen flow rate

• Kinetics are also impacted by the reactivity of the feed and the activity of the catalyst

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