Hydroprocessing:

Hydrotreating &
Hydrocracking
Chapters 7 & 9
 Gases

Polymer- Sulfur
ization Plant
Sulfur

LPG
Sat Gas
Gas Plant

Butanes Fuel Gas

Alkyl
Feed LPG
Alkylation

Gas Polymerization
Separation & Naphtha
Stabilizer Isom-
erization
Light Naphtha
Alkylate
Aviation
Isomerate
Gasoline
Automotive
Gasoline
Reformate
Naphtha Solvents
Heavy Naphtha
Hydro-
Naphtha Reforming
treating Naphtha
Atmospheric
Distillation

Jet Fuels
Kerosene
Crude
Desalter Kerosene
Oil
Distillate Cat Solvents
AGO Hydro-
Naphtha Distillate
cracking Treating &
Hydro-
Blending
Heating Oils
treating
Gas Oil Fluidized
Cat Diesel
LVGO Hydro- Catalytic
treating Cracking Distillates
Vacuum
Distillation
Fuel Oil
HVGO
Cycle Oils
Residual
Fuel Oils
DAO
Solvent
Deasphalting SDA
Coker Asphalts
Bottoms
Naphtha Naphtha

Visbreaking Heavy Distillates

Fuel Oil
Coker Bottoms
Vacuum Gas
Lube Oil Lubricant
Residuum Oil
Solvent Greases
Dewaxing
Waxes
Waxes
Coking Light Coker
Gas Oil

Coke

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U.S. Refinery Implementation of Hydrotreating

EIA, Jan. 1, 2018 database, published June 2018

http://www.eia.gov/petroleum/refinerycapacity/

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U.S. Refinery Implementation of Hydrocracking

EIA, Jan. 1, 2018 database, published June 2018

http://www.eia.gov/petroleum/refinerycapacity/

Updated: July 12, 2018

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Purpose

Hydrotreating Hydrocracking
 Remove hetero atoms & saturate  Severe form of hydroprocessing
carbon‐carbon bonds • Break carbon‐carbon bonds
• Sulfur, nitrogen, oxygen, & metals • Drastic reduction of molecular weight
removed  Reduce average molecular weight &
• Olefinic & aromatic bonds saturated produce higher yields of fuel
 Minimal cracking products
 Minimal conversion – 10% to 20%  50%+ conversion
typical  Products more appropriate for diesel
 Products suitable for further than gasoline
processing or final blending
• Reforming, catalytic cracking,
hydrocracking

http://www.kbr.com/Newsroom/Publications/Brochures/Hydroprocessing‐Technology.pdf

Updated: July 12, 2018

5
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Example Hydrogen Usage

Refining Overview – Petroleum Processes & Products,

by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD‐ROM, 2000

Updated: July 12, 2018

6
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 Characteristics of Petroleum Products

Hydrocracking: hydrogen addition to minimize coke formation

Refining Overview – Petroleum Processes & Products,

by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD‐ROM, 2000

Updated: July 12, 2018

7
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 Characteristics of Petroleum Products

Hydrotreating: just enough conversion to remove undesirable

atoms; hydrogen addition for atom removal
Refining Overview – Petroleum Processes & Products,
by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD‐ROM, 2000

Updated: July 12, 2018

8
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Hydroprocessing Trends

Hydrogen is ubiquitous in Driven by several factors

refinery & expected to  Increased use of
increase hydrodesulfurization for low
 Produces higher yields & sulfur fuels
upgrade the quality of fuels  Heavier & higher sulfur crudes
 Reduction in demand for heavy
The typical refinery runs at a fuel oil
hydrogen deficit  More complete protection of
 As hydroprocessing becomes FCCU catalysts
more prevalent, this deficit will  Demand for high quality coke
increase  Increased production of diesel
 As hydroprocessing progresses in
severity, the hydrogen demands
increase dramatically

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9
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Sources of Hydrogen in a Refinery

By‐product from other processes Manufactured

 Catalytic Reformer  Steam‐Methane Reforming (SMR)
• Most important source of hydrogen • Most common method of
for the refiner manufacturing hydrogen
• Continuously regenerated reformer: • 90 – 95 vol% typical purity
90 vol%  Gasification / Partial Oxidation
• Semi‐continuously regenerated • Produce synthesis gas (syngas)
reformer: 80 vol%
• Hydrogen recovery
 FCCU Offgas o Pressure swing adsorption (PSA)
• 5 vol% hydrogen with methane,
o Membrane separation
ethane & propane
• More expensive than steam
• Several recovery methods (can be
reforming but can use low quality by‐
combined)
product streams
o Cryogenic
o Pressure swing adsorption (PSA)
o Membrane separation

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Hydroprocessing Catalysts

Hydrotreating Hydrocracking
 Desired function  Crystalline silica alumina base with rare earth metals
• Cobalt molybdenum – sulfur removal & olefin deposited in the lattice
saturation • Platinum, palladium, tungsten, and/or nickel
• Nickel molybdenum – nitrogen removal & aromatic • Rare earth metals typically mixture of lanthanum,
saturation cerium, and other minor quantities
 Reactor configuration • Acid function promotes the cracking
• Downflow fixed bed – temperature to control final  Feed stock must first be hydrotreated
sulfur content
 Catalysts deactivate & coke forms even with hydrogen
• First bed may guard bed for nickel & vanadium present
o Cheaper catalysts • Hydrocrackers require periodic regeneration of the
o Most removal of hetereo atoms in subsequent fixed bed catalyst systems
beds • Channeling caused by coke accumulation a major
 Selective catalysts for sulfur removal without olefin concern
saturation • Can create hot spots that can lead to temperature
• Maintaining high octane rating runaways
 Reactor configuration
• Fixed bed – typical for gas oil hydrocracking
• Expanded circulating bed or slurry – proposed for resid
hydrocracking
Hydroprocessing catalysts
https://grace.com/catalysts‐and‐fuels/en‐us/art‐
hydroprocessing‐catalysts

Updated: July 12, 2018

11
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Reactor Bed Configurations

Petroleum Refining Processes

J.G. Speight & B. Özüm
Marcel Dekker, Inc., 2002, pg. 452

Sample packing of catalyst on top of supports

Model prepared by Enterprise Products

Updated: July 12, 2018

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 Gases

Polymer- Sulfur
ization Plant
Sulfur

LPG
Sat Gas
Gas Plant

Butanes Fuel Gas

Alkyl
Feed LPG
Alkylation

Gas Polymerization
Separation & Naphtha
Stabilizer Isom-
erization
Light Naphtha
Alkylate
Aviation
Isomerate
Gasoline
Automotive
Gasoline
Reformate
Naphtha Solvents
Heavy Naphtha
Hydro-
Naphtha Reforming
treating Naphtha
Atmospheric
Distillation

Jet Fuels
Kerosene
Crude
Desalter Kerosene
Oil
Distillate Cat Solvents
AGO Hydro-
Naphtha Distillate
cracking Treating &
Hydro-
Blending
Heating Oils
treating
Gas Oil Fluidized
Cat Diesel
LVGO Hydro- Catalytic
treating Cracking Distillates
Vacuum
Distillation
Fuel Oil
HVGO
Cycle Oils
Residual
Fuel Oils
DAO
Solvent
Deasphalting SDA
Coker Asphalts
Bottoms
Naphtha Naphtha

Visbreaking Heavy Distillates

Fuel Oil
Coker Bottoms
Vacuum Gas
Lube Oil Lubricant
Residuum Oil
Solvent Greases
Dewaxing
Waxes
Waxes
Coking Light Coker
Gas Oil

Coke

Updated: July 12, 2018

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Hydrodesulfurization

Sulfur Unsaturated carbon‐carbon bonds

 Sulfur converted to hydrogen sulfide  Olefins saturated – one hydrogen
(H2S) molecule added for each double bond
• Added hydrogen breaks carbon‐sulfur • Olefins prevalent in cracked streams –
bonds & saturates remaining hydrocarbon coker or visbreaker naphtha, catalytic
chains cracker cycle oil, catalytic cracker gasoline
 Form of sulfur bonds  Aromatic rings hydrogenated to
• Sulfur in naphtha generally mercaptans cycloparaffins (naphthenes)
(thiols) & sulfides • Severe operation
• In heavier feeds, more sulfur as • Hydrogen consumption strong function of
disulphides & thiophenes complexity of the aromatics
 Light ends • prevalent in heavy distillate hydrotreating,
• Heavier distillates make more light ends gas oil hydrotreating, hydrocracking
from breaking more complex sulfur
molecules Selective catalysts for hydrotreating cat
gasoline for sulfur removal but not
saturate olefins
 Maintain high octane ratings

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Hydrodesulfurization Chemistry

H2 required & final hydrocarbon products dependent on position of sulfur in molecule

CH3CH2CH2CH2CH2CH2CH2CH2‐SH + H2 → CH3CH2CH2CH2CH2CH2CH2CH3 + H2S

CH3CH2CH2CH2CH2 ‐S‐CH2CH2CH3 + 2 H2 → CH3CH2CH2CH2CH3 + CH3CH2CH3 + H2S

Saturation of molecules possible because of high H2 concentrations
CH3CH2CH2CH=CHCH2CH2CH3 + H2 → CH3CH2CH2CH2CH2CH2CH2CH3
Ultra low sulfur levels difficult
 Complex structures
+ 4 H2 → CH3CH2CH2CH3 + H2S

 Mercaptan reversion
CH3CH2CH2CH2CH2CH2CH=CH2 + H2S → CH3CH2CH2CH2CH2CH2CH2CH2‐SH

Updated: July 12, 2018

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Yield Estimates

Difficult to generalize because conversion of feedstock is relatively low

Liquid products generally have volume & gravity increase – typically +1oAPI
General relationship of hydrogen required vs. sulfur content
 Naphtha: (scf/bbl H2) = 191  (wt% sulfur) – 30.7
 Middle distillates: (scf/bbl H2) = 110.7  (wt% sulfur) + 10.2  (% desulfurized) – 659.0

Petroleum Refinery Process Economics, 2nd ed., Fundamentals of Petroleum Refining,

Robert E. Maples, 2000 by Fahim, Al‐Sahhaf, & Elkilani , Elsevier, 2010

Updated: July 12, 2018

16
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Typical Process Parameters

http://www.eia.doe.gov/oiaf/servicerpt/ulsd/figd3.html

Petroleum Refining Processes,

by James G. Speight & Baki Özüm, Marcel Dekker, Inc., 2002 LHSV = Reactant Liquid Hourly Space Velocity
Supplemented by personal conversation with Bart Carpenter = Liquid volumetric flow  volume catalyst

Updated: July 12, 2018

17
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Sulfur Distribution vs. Boiling Point LCO Feedstock

Updated: July 12, 2018

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Copyright © 2017 John Jechura (jjechura@mines.edu)
General Effects of Process Variables

Reactor inlet temperature & pressure

 Increasing temperature increases hydrogenation but decreases the number of active catalyst
sites
 Temperature control is used to offset the decline in catalyst activity
 Increasing pressure increases hydrogen partial pressure & increases the severity of
hydrogenation

Recycle hydrogen
 Require high concentration of hydrogen at reactor outlet
 Hydrogen amount is much more than stoichiometric
 High concentrations required to prevent coke laydown & poisoning of catalyst
• Particularly true for the heavier distillates containing resins and asphaltenes

Purge hydrogen
 Removes light ends & helps maintain high hydrogen concentration

Updated: July 12, 2018

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Naphtha Hydrotreating

Naphtha hydrotreated primarily for sulfur removal

 Mostly mercaptans (R‐SH) & sulfides (R‐S‐R')
 Some disulfides (R‐S‐S‐R'), & thiophenes (ring structures)
Most common catalyst cobalt‐molybdenum on alumina
Chemical hydrogen consumption typically 50 to 250 scf/bbl
 For desulfurization containing up to 1 wt% sulfur — 70 to 100 scf/bbl
 Significant nitrogen & sulfur removal — 250 scf/bbl
Ultra low sulfur levels difficult because of

Updated: July 12, 2018

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Naphtha Hydrotreating Process

Reactor typically at 200 psig & 700oF

 Temperature increases to
compensate for decrease in catalyst
activity

Liquid space velocity ~ 2 per hour

Hydrogen recycle ~ 2,000 scf/bbl
Acid gas removal may not be directly
incorporated into recycle gas loop
 Overhead vapor from fractionator to
saturates gas plant to recover light
hydrocarbons & remove H2S
Haldo Topsøe process flow
2011 Refining Processes Handbook
Product fractionation Hydrocarbon Processing, 2011

 Pentane/hexane overhead either to

blending or isomerization
 Bottoms to reformer

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Distillate Hydrotreating

In general, all liquid distillate streams

contain sulfur compounds that must
be removed
Saturate olefins in diesel to improve
the cetane number
Hydrogenation at the high pressure
produces small amounts of naphtha
from hydrocracking
 Required to get at the embedded
sulfur
 Diesel hydrotreater stabilizer will
have an upper sidestream draw Total Distillate Hydrotreater
http://www.totalpetrochemicalsusa.com/press_room/press_releases_dcpphotos.asp
producing the naphtha which is
recycled to motor gasoline processing

Updated: July 12, 2018

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Distillate Hydrotreating Process

Reactor typically at 800oF

Hydrogen recycle starts at 2,000
scf/bbl; consumption 100 to 400
scf/bbl
Conditions highly dependent upon
feedstock
 Distillate (jet fuel & diesel) with 85% ‐
95% sulfur removal
• 300 psig
• hydrogen consumption 200 ‐ 300
scf/bbl
 Saturation of diesel for cetane Haldo Topsøe process flow
2011 Refining Processes Handbook
number improvement Hydrocarbon Processing, 2011
• over 800 scf/bbl hydrogen
• up to 1,000 psig

Updated: July 12, 2018

23
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Boiling Point Ranges for Products
19,145 bpd Sour Distillate Feed
18,292 bpd Treated Distillate
3,000

35-Treated.Distillate
31-Liquids
2,500
27-Off.Gas
1-fresh.charge
Incremental Yield [bpd]

2,000

1,500

1,000

500

-
0 100 200 300 400 500 600 700 800
BPT [°F]
Based on example problem in:
Refinery Process Modeling, A Practical Guide to Steady State Modeling of Petroleum Processes, 1st ed.
Gerald Kaes, Athens Printing Company, 02004

Updated: July 12, 2018

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Gas Oil Hydrotreating

Catalytic cracker feedstocks (atmospheric Gas oils can be contaminated with resins
gas oil, light vacuum gas oil, solvent & asphaltenes
deasphalting gas oil) hydrotreated  Deposited in hydrotreater
severely  Require catalyst replacement with a
 Sulfur removal shorter run length than determined by
 Opening of aromatic rings deactivation
 Removal of heavy metals  Guard chamber may be installed to
prolong bed life
Desulfurization of gas oil can be achieved
with a relatively modest decomposition Nickel molybdenum catalyst system for
of structures severe hydrotreating
Gas oil units more expensive because of
more intensive hydrogenation
 Quench
 Multi‐stage flash
 More complex strippers

Updated: July 12, 2018

25
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Gas Oil Hydrotreating Process

Normally two reactor beds – control

temperature rise
Hydrogen partial pressure related to ring
saturation & amount of sulfur
 For low ring saturation 300 psig may be
sufficient
 1,200 psig will convert 25% ring
saturation & somewhat less than 95%
sulfur removal
 Pressures as high as 1,500 psig can
saturate 30% of aromatic rings

Hydrogen absorption of 300 scf/bbl

Chevron Lummus Global LLC process flow
could give about 80% sulfur removal & 2011 Refining Processes Handbook
Hydrocarbon Processing, 2011
only require 300 psig
 No ring saturation at these mild
conditions

Updated: July 12, 2018

26
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Saturation of Benzene in Gasoline

Strategies for reduction of benzene in gasoline

 Reduce benzene precursors in feed to reformer
 Hydrotreat/saturate benzene in appropriate boiling range fraction

Typical processing strategy

 Separate & hydrotreat narrow‐cut
C6 fraction from rest of feedstock
• Saturate the aromatics & olefins
of the treated stream
• Retain the olefins in the
C5‐ and the aromatics &
olefins of the C7+ fractions

Blend product back into the

stripped feedstock

GTC Benzene Saturation Technology – GT‐BenZap®

http://www.gtctech.com/technology‐licensing/refining/benzyne‐saturation/
Downloaded June 28, 201

Updated: July 12, 2018

27
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Saturation of Benzene in Gasoline

UOP’s BenSatTM process can be used on a

light reformer stream
 Up to 30 vol% benzene in feed
 No recycle gas
• No recycle compressor
• No recycle compression power requirements
 Long catalyst life
 High catalyst selectivity
 Pros & cons
• No increase in RVP
• Mild volumetric swelling, +1 to +6 vol%
• Do lose octane rating

Updated: July 12, 2018

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Catalytic Dewaxing of Middle Distillates

Improve cold flow properties

Clariant Selective Hydrocracking Process
 Selectively cracks normal paraffins due to size
of zeolite pores
 Configurations
Catalytic dewaxing bed within an existing
• Stand alone hydrotreating unit
• Incorporate within existing hydrotreating unit
• Combined hydrotreating & dewaxing

Ref: “Consider catalytic dewaxing as a tool to improve diesel cold‐flow properties”,

Rakoczy & Morse, Hydrocarbon Processing, July 2013 Combined hydrotreating & catalytic dewaxing units

Updated: July 12, 2018

29
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 Gases

Polymer- Sulfur
ization Plant
Sulfur

LPG
Sat Gas
Gas Plant

Butanes Fuel Gas

Alkyl
Feed LPG
Alkylation

Gas Polymerization
Separation & Naphtha
Stabilizer Isom-
erization
Light Naphtha
Alkylate
Aviation
Isomerate
Gasoline
Automotive
Gasoline
Reformate
Naphtha Solvents
Heavy Naphtha
Hydro-
Naphtha Reforming
treating Naphtha
Atmospheric
Distillation

Jet Fuels
Kerosene
Crude
Desalter Kerosene
Oil
Distillate Cat Solvents
AGO Hydro-
Naphtha Distillate
cracking Treating &
Hydro-
Blending
Heating Oils
treating
Gas Oil Fluidized
Cat Diesel
LVGO Hydro- Catalytic
treating Cracking Distillates
Vacuum
Distillation
Fuel Oil
HVGO
Cycle Oils
Residual
Fuel Oils
DAO
Solvent
Deasphalting SDA
Coker Asphalts
Bottoms
Naphtha Naphtha

Visbreaking Heavy Distillates

Fuel Oil
Coker Bottoms
Vacuum Gas
Lube Oil Lubricant
Residuum Oil
Solvent Greases
Dewaxing
Waxes
Waxes
Coking Light Coker
Gas Oil

Coke

Updated: July 12, 2018

30
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Hydrocracking

Purpose: process gas oil to break carbon‐carbon bonds of large

aromatic compounds & remove contaminants
 Hydrogenation (addition of hydrogen)
 Cracking (carbon‐carbon scission) of aromatic bonds
Intent to create middle distillate products, not gasoline range
products

Updated: July 12, 2018

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Hydrocracker Yield Example

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32
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Hydrocracker Yield Trends

Figure 7.4
 Start over‐cracking the heavy naphtha
fraction when the light naphtha yields
gets above 25 vol%.

Updated: July 12, 2018

33
Copyright © 2017 John Jechura (jjechura@mines.edu)
Boiling Point Ranges for Hydroprocessing Products

700

14
600 21
20-OffGas
1-oil.feed
500

Incremental Yield [bpd]

400

300

200

100

-
0 100 200 300 400 500 600 700 800 900 1000 1100 1200
BPT [°F]

Based on example problem in:

Refinery Process Modeling, A Practical Guide to Steady State Modeling of Petroleum Processes, 1st ed.
Gerald Kaes, Athens Printing Company, 02004

Updated: July 12, 2018

34
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Hydrocracking Feeds

Typical feeds
 Cat cracker “cycle oil”
• Highly aromatic with sulfur, small ring & polynuclear aromatics, catalyst fines;
usually has high viscosity
• Hydrocracked to form high yields of jet fuel, kerosene, diesel, & heating oil
 Gas oils from visbreaker
• Aromatic
 Gas oil from the delayed coker
• Aromatic, olefinic, with sulfur

Usually more economical to route atmospheric & vacuum gas oils

to the cat cracker to produce primarily gasoline & some diesel

Updated: July 12, 2018

35
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Gas Oil Hydrocracker Feed

Hydrocracking does a better job of processing aromatic rings

without coking than catalytic cracking
 Hydrogen used to hydrogenate polynuclear aromatics (PNAs)
 Reduces frequency of aromatic condensation
Hydrocracking not as attractive as delayed coking for resids high in
resins, asphaltenes & heteroatom compounds
 Heteroatoms & metals prevalent in resins & asphaltenes poison
hydroprocessing catalysts
 High concentrations of resins & asphaltenes will still ultimately coke
Feeds limited to a Conradson Carbon Number (CCR) of 8 wt%
Feeds require high pressures & large amounts of hydrogen

Updated: July 12, 2018

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Gas Oil Hydrocracker Products

Hydrocracking primarily to make distillates

 In US hydrocracking normally a specialized operation used to optimize
catalytic cracker operation
 In US cat cracking preferred to make gasoline from heavier fractions
Hydrocracking capacity is only about 8% of the crude distillation
capacity
 Not all refineries have hydrocrackers
Intent is to minimize the production of heavy fuel oil
 Light ends are approximately 5% of the feed.
 Middle distillates (kerosene, jet fuel, diesel, heating oil) still contain
uncracked polynuclear aromatics
All liquid fractions are low in sulfur & olefins
Updated: July 12, 2018
37
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Hydrocracking Chemistry

Cracking reactions Hydrogenation reactions Isomerization Reactions

 Saturated paraffins cracked  Exothermic giving off heat  Isomerization provides
to form lower molecular  Hydrogen inserted to branching of alkyl groups
weight olefins & paraffins saturate newly formed of paraffins and opening of
 Side chains cracked off molecule from aromatic naphthenic rings
small ring aromatics (SRA) cracking
& cycloparaffins  Olefins are saturated to Condensation Reactions
(naphthenes) form light hydrocarbons,  Suppressed by hydrogen
 Side chains cracked off especially butane
resins & asphaltenes  Aromatic rings
leaving thermally stable hydrogenated to
polynuclear aromatics cycloparaffins
(PNAs) (naphthenes)
• But condensation  Carbon‐carbon bonds
(dehydrogenation) cleaved to open aromatic
also occurs if not & cycloparaffins
limited by (naphthenes) rings
hydrogenation  Heteroatoms form H2S,
NH3, H2O, HCl

Updated: July 12, 2018

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Single Stage Hydrocracking

Feedstock hydrotreated to remove sulfur,

nitrogen, oxygen components
 Guard reactors to remove metals

Temperatures 660 – 800oF

 May raise temperature 0.1 – 0.2oF per day
to offset loss of catalyst activity

Pressures 1,200 – 2,000 psig

 Raising pressure increases conversion

Hydrogen
 High hydrogen recycle to minimize coking
 Consumption
• Low pressure – mild severity – 1,000 – 2,000
scf/bbl
• High pressure – high severity – 2,000 – Haldo Topsøe process flow
2011 Refining Processes Handbook
3,000 scf/bbl Hydrocarbon Processing, 2011

Updated: July 12, 2018

39
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Reactor Configuration

Actual configuration may have multiple vessels and/or catalyst zones

 Dependent on expected
feedstocks
Example shows separate
vessels for removal
of metals, heteroatoms,
& cracking
 Mulitiple zones in the
Pretreat reactor to focus
on sulfur & nitrogen
removal

Modified Fig. 9
“Unlock next‐level hydrocracker flexibility in today’s turbulent markets”
Baric, Kang, & Orzeszko
Hydrocarbon Processing, September 2016

Updated: July 12, 2018

40
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Value of Hydrocrackers in U.S. Refining

Since 2007 U.S. oil refining focus has been

maximizing distillate production at the expense
of gasoline production
 U.S. gasoline consumption has been decreasing
 U.S. & worldwide diesel consumption continuing
to rise

Value of gas oil hydrocrackers

 Volume expansion through hydrogen saturation & by cracking larger molecules into smaller
ones
 Yield a large amount of distillate products compared to gasoline products
• Have flexibility to shift about 10% between these products
• Further adjustments can be managed by changing fractionation operations Hydrocracker distillate
production good quality for jet & diesel fuel

Products have very low impurities (i.e. sulfur, metals, etc…) – good for blending into
finished product pools or for reprocessing in downstream units (i.e. reformers)
Ref: http://www.refinerlink.com/blog/Value_Hydrocrackers_US_Refining/

Updated: July 12, 2018

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Value of Hydrocrackers in U.S. Refining

Market factors
 Incremental cost of hydrogen decreasing because of the surplus of natural gas in North
America (from shale formations)
 Regional supply & demand balance of gas oils
• In North America gas oils price relative to the incremental disposition to a FCCU
o Better margins to feed hydrocrackers to make distillate vs. feed FCCU to make gasoline
o Used to have margins of $10 per bbl feedstock, now in the $15 to $20 per bbl range

Downsides of hydrocrackers
 High hydrogen consumption
 High energy consumption
 High capital requirements
 High catalyst costs
 High maintenance costs

Ref: http://www.refinerlink.com/blog/Value_Hydrocrackers_US_Refining/

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Summary

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Copyright © 2017 John Jechura (jjechura@mines.edu)
Summary

Hydrotreating & hydrocracking are opposite extremes of the

general hydroprocessing
Hydrotreating Hydrocracking
• Break only those bonds that allow • Break carbon‐carbon bonds to
removal of undesired atoms create smaller molecules
(sulfur, nitrogen, ….) • Products have essentially zero
• Higher severity required to meet sulfur – feed must be severely
ultra low sulfur product specs hydrotreated to protect cracking
• Can also use to control wax catalysts
formation tendencies • Products are highly saturated –
• Will tend to make some smaller good jet & diesel, poor gasoline
molecules due to positon of sulfur • Good cetane numbers, poor
in feedstock molecule octane numbers
• High‐severity hydrotreating acts like mild hydrocracking

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Supplemental Slides

Updated: July 12, 2018

Copyright © 2017 John Jechura (jjechura@mines.edu)
Hydroprocessing Objectives

Feedstocks Desired Products Process Objectives

Naphthas Catalytic reformer feed Removal of S, N, & olefins
LPG Hydrocracking
Atmospheric gas oils Diesel Removal of S, aromatics, & n‐paraffins
Jet Removal of S & aromatics
Ethylene feedstock Removal of aromatics
Naptha Hydrocracking
Vaccum gas oils LSFO Removal of S
FCC feed Removal of S, N, & metals
Diesel Removal of S & aromatics
Hydrocracking
Kerosene/jet Removal of S & aromatics
Hydrocracking
Naptha Hydrocracking
LPG Hydrocracking
Ethylene feedstock Removal of aromatics
Hydrocracking
Lube oil base stock Removal of S, N, & aromatics
Hydrocracking
Residuum LSFO Removal of S
FCC feedstock Removal of S, N, CCR, & metals
Coker feedstock Removal of S, CCR, & metals
Diesel Hydrocracking
Handbook of Petroleum Refining Processes, 3rd ed.
Ed. Robert A. Meyers, McGraw‐Hill, 2004

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Hydrotreating Installed Cost

Includes
 Product fractionation.
 Complete preheat, reaction, and hydrogen
circulation facilities.
 Sufficient heat exchange to cool products to
ambient temperature.
 Central control system.
 Initial catalyst charge.

Excludes
 Feed fractionation.
 Makeup hydrogen generation.
 Sulfur recovery from off‐gas.
 Cooling water, system, and power supply.

Petroleum Refining Technology & Economics, 5th ed.

Gary, Handwerk, & Kaiser
CRC Press, 2007

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Hydrocracker vs. FCC Installed Cost

Hydrocrackers tend to be more expensive than FCCs

 50,000 bpd distillate FCC – $150 million installed cost Petroleum Refining Technology & Economics, 5th ed.
Gary, Handwerk, & Kaiser
 50,000 bpd @ 2000 scf/bbl – $350 million installed cost CRC Press, 2007

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Hydrotreating Technologies

Provider Features

Axens Hydrotreating: diesel; resid; hydrodearomatization (2 stage HDS/HAD)

CDTECH Hydrotreating: CDHydro & CDHDS

Chevron Lummus Global LLC Hydrotreating: ISOTREATING, RDS/VRDS/UFR/OCR

DuPont Hydrotreating

GTC Technology Hydrotreating, pyrolysis gasoline

Haldor Topsoe A/S Hydrotreating

UOP Hydrotreating; Hydrotreating/desulfurization (SelectFining)

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Hydrocracking Technologies

Provider Features

Axens Hydrocracking; Resid hydrocracking (H‐OilOC)

Chevron Lummus Global LLC Hydrocracking (ISOCRACKING); Resid hydrocracking

DuPont Hydrocracking

ExxonMobil Research & Hydrocracking, moderate pressure (MPHC)

Engineering
Haldor Topsoe A/S Hydrocracking

Shell Global Solutions Hydrocracking

UOP Hydrocracking

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 Hydrotreating Hydrogen Consumption

Chemical consumption due to hydrogenation reactions

 Cracking reactions of carbon‐carbon bonds minimal in hydrotreating, even during
aromatic saturation
 Olefinic bonds easier to saturate than aromatic bonds
• Straight‐run stocks have essentially zero olefins

Hydrogen is lost in equilibrium with light gases

 Amount is significant & may double amount required for sulfur removal
Hydrogen absorbed in liquid products
 Usually small compared to sulfur removal needs – 1 lb/bbl
Hydrogen removed with purge gas
 Used to maintain a high purity of hydrogen — light ends dilute the hydrogen
concentration
 Usually small compared to sulfur removal needs

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 Hydrocracking Hydrogen Consumption & Loss
Heteroatom‐carbon bonds Saturation of carbon‐carbon bonds Cracking of carbon‐carbon
broken & saturated • Olefins saturated to form light bonds
• Creates light ends hydrocarbons. • Severe operation —
• Heavier distillates • Consumption stoichiometric hydrogen consumption
make more light — one hydrogen molecule strong function of
ends from breaking added for each double bond complexity of the aromatics
more complex • Aromatic rings hydrogenated to Hydrogen mixed with products
molecules cycloparaffins (naphthenes). • Equilibrium with light gases
• Sulfur converted to H2S • Severe operation — • Significant — may
• Nitrogen converted to hydrogen consumption double amount
NH3 strong function of required for sulfur
• Oxygen converted to complexity of the aromatics removal
H2O Isomerization reactions generally • Absorbed in liquid products
• Organic chlorides not present • Usually small
converted to HCl Metals deposited directly on the compared to
catalysts hydrogen used for
• Excess metals reduce sulfur removal
catalyst activity & promote • Lost with purge gas
dehydrogenation (produces
coke & hydrogen)

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Severity of operations

“Hydrocracking solutions squeeze more ULSD from heavy ends”

E. Benazzi, J. Bonnardot, F. Morel, Hydrocarbon Processing, November 2009

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Single Stage Hydrocracking with HDS 1st Step

Petroleum Refinery Process Economics, 2nd ed.,

Robert E. Maples, Figure 14‐1, 2000

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UOP Two‐Stage Unicracking™ Process

http://www.uop.com/hydrocracking‐unicracking‐stage/

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UOP’s HyCycle UnicrackingTM Process

http://www.uop.com/objects/Hycycle.pdf

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