Hydroprocessing: Hydrotreating & Hydrocracking: Chapters 7 & 9

Hydroprocessing: Hydrotreating & Hydrocracking
Chapters 7 & 9
Updated: August 11, 2016

Copyright © 2016 John Jechura (jjechura@mines.edu)
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

2
U.S. Refinery Implementation of Hydrotreating
EIA, Jan. 1, 2016 database, published June 2016

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

3
U.S. Refinery Implementation of Hydrocracking
EIA, Jan. 1, 2016 database, published June 2016

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

4
Purpose
• Hydrotreating • Hydrocracking
 Remove hetero atoms & saturate carbon-  Severe form of hydroprocessing
carbon bonds
• Break carbon-carbon bonds
• Sulfur, nitrogen, oxygen, & metals
• Drastic reduction of molecular weight
removed
 Reduce average molecular weight & produce
• Olefinic & aromatic bonds saturated
higher yields of fuel products
 Minimal cracking
 50%+ conversion
 Minimal conversion – 10% to 20% typical
 Products more appropriate for diesel than
 Products suitable for further processing or gasoline
final blending
• Reforming, catalytic cracking,
hydrocracking
http://www.kbr.com/Newsroom/Publications/Brochures/Hydropr
ocessing-Technology.pdf

5
Typical Hydrogen Usage
Refining Overview – Petroleum Processes & Products,

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

6
Characteristics of Petroleum Products
Hydrotreating: just enough conversion to remove undesirable atoms;

hydrogen addition for atom removal


7
Characteristics of Petroleum Products
Hydrocracking: hydrogen addition to minimize coke formation


8
Hydroprocessing Trends
• Hydrogen is ubiquitous in refinery & expected to increase
 Produces higher yields & upgrade the quality of fuels
• The typical refinery runs at a hydrogen deficit
 As hydroprocessing becomes more prevalent, this deficit will increase
 As hydroprocessing progresses in severity, the hydrogen demands increase dramatically
• Driven by several factors
 Increased use of hydrodesulfurization for low sulfur fuels
 Heavier & higher sulfur crudes
 Reduction in demand for heavy fuel oil
 More complete protection of FCCU catalysts
 Demand for high quality coke
 Increased production of diesel

9
Sources of Hydrogen in a Refinery
By-product from other processes Manufactured
• Catalytic Reformer • Steam-Methane Reforming (SMR)
 Most important source of hydrogen for the
refiner  Most common method of manufacturing
hydrogen
 Continuously regenerated reformer: 90 vol%
 Semi-continuously regenerated reformer: 80 vol%  90 – 95 vol% typical purity
• FCCU Offgas • Gasification / Partial Oxidation

 5 vol% hydrogen with methane, ethane &  Produce synthesis gas (syngas)
propane
 Hydrogen recovery
 Several recovery methods (can be combined)
• Cryogenic • Pressure swing adsorption (PSA)
• Pressure swing adsorption (PSA) • Membrane separation
• Membrane separation  More expensive than steam reforming but can
use low quality by-product streams

10
Hydroprocessing Catalysts
• Hydrotreating • Hydrocracking
 Desired function  Crystalline silica alumina base with rare earth
• Cobalt molybdenum – sulfur removal & olefin metals deposited in the lattice
saturation
• Nickel molybdenum – nitrogen removal & • Platinum, palladium, tungsten, and/or nickel
aromatic saturation • Rare earth metals typically mixture of lanthanum,
 Reactor configuration cerium, and other minor quantities
• Downflow fixed bed – temperature to control • Acid function promotes the cracking
final sulfur content
• First bed may guard bed for nickel & vanadium  Feed stock must first be hydrotreated
o Cheaper catalysts  Catalysts deactivate & coke forms even with
hydrogen present
o Most removal of hetereo atoms in
subsequent beds • Hydrocrackers require periodic regeneration of
 Selective catalysts for sulfur removal without the fixed bed catalyst systems
olefin saturation • Channeling caused by coke accumulation a major
• Maintaining high octane rating concern
• Can create hot spots that can lead to temperature
runaways
 Reactor configuration
• Fixed bed – typical for gas oil hydrocracking
• Expanded circulating bed or slurry – proposed for
resid hydrocracking

11
Reactor Bed Configurations
“Slurry-phase hydrocracking—possible solution to refining

margins”, M. Motaghi & A. Subramanian, Hydrocarbon
Petroleum Refining Processes Processing, February 2011
J.G. Speight & B. Özüm
Marcel Dekker, Inc., 2002, pg. 452

12
Gases
Polymer- Sulfur
ization Plant
Sulfur
LPG
Sat Gas
Gas Plant
Butanes Fuel Gas

Alkyl
Feed LPG
Alkylation
Gas Polymerization
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
AGO Hydro-
Naphtha Distillate
cracking Treating &
Hydro-
Blending
Heating Oils
treating
Gas Oil Fluidized
Cat Diesel
Vacuum
Distillation
Fuel Oil
HVGO
Cycle Oils
Residual
Fuel Oils
DAO
Solvent
Deasphalting SDA
Coker Asphalts
Bottoms
Naphtha Naphtha

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

13
Hydrodesulfurization
• Sulfur
 Sulfur converted to hydrogen sulfide (H2S)
• Added hydrogen breaks carbon-sulfur bonds & saturates remaining hydrocarbon chains
 Form of sulfur bonds
• Sulfur in naphtha generally mercaptans (thiols) & sulfides
• In heavier feeds, more sulfur as disulphides & thiophenes
 Light ends
• Heavier distillates make more light ends from breaking more complex sulfur molecules
• Unsaturated carbon-carbon bonds
 Olefins saturated – one hydrogen molecule added for each double bond
• Olefins prevalent in cracked streams – coker or visbreaker naphtha, catalytic cracker cycle oil, catalytic cracker
gasoline
 Aromatic rings hydrogenated to cycloparaffins (naphthenes)
• Severe operation
• Hydrogen consumption strong function of complexity of the aromatics
• prevalent in heavy distillate hydrotreating, gas oil hydrotreating, hydrocracking
• Selective catalysts available for hydrotreating cat gasoline for sulfur removal but not saturate olefins
 Maintain high octane ratings

14
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: August 11, 2016 Page 15

Yield Estimates
• Difficult partly because conversion of feedstock is relatively low
• Liquid products generally have gravity +1API
 Overall volume typically increases
• General relationship of hydrogen required vs. sulfur content
360
320
280
240
SCFB of Hydrogen
200
160
120
80
40
0
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
Weight Percent Sulfur in Feed
Petroleum Refining Processes,

by James Speight & Baki Ozum, Marcel Dekker, 2002

16
Typical Process Parameters
Refining Overview – Petroleum Processes & Products, 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

17
Sulfur Distribution vs. Boiling Point LCO Feedstock

18
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

19
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

20
Naphtha Hydrotreating Process
• Reactor typically at 200 psig &
700F
 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
• Product fractionation
 Pentane/hexane overhead either to
blending or isomerization Haldo Topsøe process flow
2011 Refining Processes Handbook
 Bottoms to reformer Hydrocarbon Processing, 2011

21
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
producing the naphtha which is http://www.totalpetrochemicalsusa.com/press_room/press_releases_dc
recycled to motor gasoline pphotos.asp
processing

22
Distillate Hydrotreating Process
• Reactor typically at 800F
• 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
number improvement
• over 800 scf/bbl hydrogen
• up to 1,000 psig
Haldo Topsøe process flow
Hydrocarbon Processing, 2011

23
Boiling Point Ranges for Products
Kaes's Example Distillate Hydrotreating Problem
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]

24
Gas Oil Hydrotreating
• Catalytic cracker feedstocks (atmospheric gas oil, light vacuum gas oil, solvent deasphalting
gas oil) hydrotreated severely
 Sulfur removal
 Opening of aromatic rings
 Removal of heavy metals
• Desulfurization of gas oil can be achieved with a relatively modest decomposition of
structures
• Gas oils can be contaminated with resins & asphaltenes
 Deposited in hydrotreater
 Require catalyst replacement with a shorter run length than determined by deactivation
 Guard chamber may be installed to prolong bed life
• Nickel molybdenum catalyst system for severe hydrotreating
• Gas oil units more expensive because of more intensive hydrogenation
 Quench
 Multi-stage flash
 More complex strippers

25
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
achieve saturation of 30% of
aromatic rings
• Hydrogen absorption of 300
scf/bbl could give about 80%
sulfur removal & only require 300
psig
 No ring saturation at these mild
conditions
Chevron Lummus Global LLC process flow

26
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 Technology process flow


27
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

28
Catalytic Dewaxing of Middle Distillates
• Improve cold flow properties
• Clariant Selective Hydrocracking Process
 Selectively cracks normal paraffins due to size of
zeolite pores
 Configurations
• Stand alone
• Incorporate within existing hydrotreating unit Catalytic dewaxing bed within an 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

29
Gases
Polymer- Sulfur
ization Plant
Sulfur
LPG
Sat Gas
Gas Plant
Butanes Fuel Gas

Alkyl
Feed LPG
Alkylation
Gas Polymerization
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
AGO Hydro-
Naphtha Distillate
cracking Treating &
Hydro-
Blending
Heating Oils
treating
Gas Oil Fluidized
Cat Diesel
Vacuum
Distillation
Fuel Oil
HVGO
Cycle Oils
Residual
Fuel Oils
DAO
Solvent
Deasphalting SDA
Coker Asphalts
Bottoms
Naphtha Naphtha

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

30
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

31
Hydrocracker Yield Example
Example

32
Hydrocracker Yield Trends
• Figure 7.4
 Start over-cracking the heavy naphtha
fraction when the light naphtha yields gets
above 25 vol%.

33
Boiling Point Ranges for Hydroprocessing Products
Kaes's Hydrocracker Example
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]

34
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

35
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

36
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

37
Hydrocracking Chemistry
• Cracking reactions • Hydrogenation reactions • Isomerization Reactions
 Saturated paraffins cracked  Exothermic giving off heat  Isomerization provides
to form lower molecular branching of alkyl groups of
 Hydrogen inserted to
weight olefins & paraffins paraffins and opening of
saturate newly formed
naphthenic rings
 Side chains cracked off small molecule from aromatic
ring aromatics (SRA) & cracking • Condensation Reactions.
cycloparaffins (naphthenes)
 Olefins are saturated to form  Suppressed by hydrogen
 Side chains cracked off resins light hydrocarbons,
& asphaltenes leaving especially butane
thermally stable polynuclear
 Aromatic rings hydrogenated
aromatics (PNAs)
to cycloparaffins
• But condensation (naphthenes)
(dehydrogenation) also
occurs if not limited by  Carbon-carbon bonds
hydrogenation cleaved to open aromatic &
cycloparaffins (naphthenes)
rings
 Heteroatoms form hydrogen
sulfide, ammonia, water,
hydrogen chloride
38
Single Stage Hydrocracking
• Feedstock hydrotreated to remove
sulfur, nitrogen, oxygen components
 Guard reactors to remove metals
• Temperatures 660 – 800F

 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
– 3,000 scf/bbl 2011 Refining Processes Handbook

39
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/

40
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/

41
Summary
Hydrotreating & hydrocracking are opposite extremes of the general
hydroprocessing
Hydrotreating Hydrocracking
• Break only those bonds that allow • Break carbon-carbon bonds to create
removal of undesired atoms (sulfur, smaller molecules
nitrogen, ….) • Products have essentially zero sulfur
• Higher severity required to meet – 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 – good
• Will tend to make some smaller jet & diesel, poor gasoline
molecules due to positon of sulfur in • Good cetane numbers, poor
feedstock molecule octane numbers
• High-severity hydrotreating acts like mild hydrocracking

42
Supplemental Slides
• Installed costs
• Hydroprocessing objectives
• Hydrotreating & hydrocracking technology providers
• Hydrogen consumption in hydrotreating & hydrocracking
• Reactor choice based on severity of operations
• Other hydrocracking configurations

43
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

44
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.
 50,000 bpd @ 2000 scf/bbl – $350 million installed cost Gary, Handwerk, & Kaiser
CRC Press, 2007

45
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

46
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)

47
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

48
Hydrogen Consumption in Hydrotreating
• 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

49
Hydrogen Consumption & Loss
• Heteroatom-carbon bonds • Saturation of carbon-carbon • Cracking of carbon-carbon
broken & saturated bonds bonds
 Creates light ends  Olefins saturated to form light • Severe operation — hydrogen
• Heavier distillates make more hydrocarbons. consumption strong function
light ends from breaking more • Consumption stoichiometric — of complexity of the aromatics
complex molecules one hydrogen molecule added
for each double bond
• Hydrogen mixed with products
 Sulfur converted to H2S
 Aromatic rings hydrogenated • Equilibrium with light gases
 Nitrogen converted to NH3
to cycloparaffins (naphthenes). • Significant — may double
 Oxygen converted to H2O amount required for sulfur
• Severe operation — hydrogen removal
 Organic chlorides converted to consumption strong function of
HCl
complexity of the aromatics • Absorbed in liquid products
• Isomerization reactions • Usually small compared to
hydrogen used for sulfur
generally not present
removal
• Metals deposited directly on • Lost with purge gas
the catalysts
 Excess metals reduce catalyst
activity & promote
dehydrogenation (produces
coke & hydrogen)

50
Severity of operations
“Hydrocracking solutions squeeze more ULSD from heavy ends”

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

51
Single Stage Hydrocracking with HDS 1st Step
Petroleum Refinery Process Economics, 2nd ed.,

Robert E. Maples, Figure 14-1, 2000

52
UOP Two-Stage Unicracking™ Process
http://www.uop.com/hydrocracking-unicracking-stage/

53
UOP’s HyCycle UnicrackingTM Process
http://www.uop.com/objects/Hycycle.pdf

54

Hydroprocessing: Hydrotreating & Hydrocracking: Chapters 7 & 9

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Hydroprocessing: Hydrotreating & Hydrocracking: Chapters 7 & 9

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What are hydrotreating and hydrocracking?

What are hydrotreating and hydrocracking?

What is the difference between hydrotreating and hydrocracking?

What is the difference between hydrotreating and hydrocracking?

Hydroprocessing: Hydrotreating & Hydrocracking

Updated: August 11, 2016

Butanes Fuel Gas

Visbreaking Heavy Distillates

Updated: August 11, 2016

EIA, Jan. 1, 2016 database, published June 2016

Updated: August 11, 2016

EIA, Jan. 1, 2016 database, published June 2016

Updated: August 11, 2016

Updated: August 11, 2016

Refining Overview – Petroleum Processes & Products,

Updated: August 11, 2016

Hydrotreating: just enough conversion to remove undesirable atoms;

Refining Overview – Petroleum Processes & Products,

Updated: August 11, 2016

Hydrocracking: hydrogen addition to minimize coke formation

Refining Overview – Petroleum Processes & Products,

Updated: August 11, 2016

Updated: August 11, 2016

• FCCU Offgas • Gasification / Partial Oxidation

Updated: August 11, 2016

Updated: August 11, 2016

“Slurry-phase hydrocracking—possible solution to refining

Updated: August 11, 2016

Butanes Fuel Gas

Visbreaking Heavy Distillates

Updated: August 11, 2016

Updated: August 11, 2016

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

• Saturation of molecules possible because of high H2 concentrations

• Ultra low sulfur levels difficult

Updated: August 11, 2016 Page 15

Petroleum Refining Processes,

Updated: August 11, 2016

Refining Overview – Petroleum Processes & Products, http://www.eia.doe.gov/oiaf/servicerpt/ulsd/figd3.html

Petroleum Refining Processes,

Updated: August 11, 2016

Updated: August 11, 2016

Updated: August 11, 2016

Updated: August 11, 2016

• Liquid space velocity ~ 2 per hour

Updated: August 11, 2016

Updated: August 11, 2016

Updated: August 11, 2016

Updated: August 11, 2016

Updated: August 11, 2016

Updated: August 11, 2016

• Typical processing strategy

GTC Technology process flow

Updated: August 11, 2016

Updated: August 11, 2016

• Combined hydrotreating & dewaxing

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

Updated: August 11, 2016

Butanes Fuel Gas