Generic Full Conversion Petroleum Refinery Refinery Operations Handbook (ROHB) for Operators Chapter 1 - Refinery Operation Overview

ROHB-2CH1 Refinery OperationOverview

Chapter 1
Refinery Overview
Excerpted from Refinery Operations Handbook
with Addendum CP2 Three Key Hydrocarbon Characteristics

Topics Page
Refinery Process Flow Diagram (RPFD) 2
Raw Crude Composition vs. Market Demand 3
Saturated and Unsaturated Hydrocarbon Refining Processes 5
Gasoline Blending Concepts 8
Sulfur and Nitrogen Removal Processes 9

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 Saturated Hydrocarbon Refining Process Units
Light Naphtha

Full Conversion Petroleum Refinery G05 Saturated Gas Plant (SGP)

D-25 99% purity
Isomerization Unit (ISOM)
R-2 & R-3 P
Relief
G10 Hydroprocessing Complex
1300 psig
1600 psig
Header

Refinery Process Flow Diagram 1300 psig 1600 psig 150 psig
(C1-C2)
HP FG
lean
Propane 150 psig C-101
ISOM Reactor
System
350 psig 400 psig
Header
Header

P
Header 95% purity P

Header Header Header Sales 99% purity Header Hydrocracking Unit

(RPFD) amine P
T-1 D-24 (HCU)
T-3 AMNU Hydrogen
C-105 A/B/C Deethanizer Caustic Scrubber/ first stage
rich Plant #1
Makeup T-6 Virgin Naphtha Hydrotreater Distillate Hydrotreater
AGO Mercaptan (H2P #1) R-31 HDT
makeup Compressors D-22 amine Depropanizer (VNHT) makeup (DHT) makeup
LVGO D-21 lean Extractor &
hydrogen D-23 makeup
T-1 LCCO CDU absorbent 99% purity R-32 HDC
light ends R-37
R-35 Reactors
Generic Refinery light ends LCGO F-41
(C1-C4) DHT T-2 steam (nC4 & iC4)
Hydrogen
Plant #2
Reactor
Reactor System
(C1-C4) wild Sponge System
VNHT ALKY (H2P #2) P F System P
Revision 3, 2/2024 FG bleed gas CNHT
naphtha Oil Absorber T-4 (T-1 Relief
F recycle
350 psig HP recycle P Relief
F recycle
hydrogen
1500 psig
makeup hydrogen Fuel Gas bleed gas 1100 psig
(H2 + C1-C2)
hydrogen RFMR Debutanizer caustic Deisobutanizer) Header bleed gas hydrogen Header bleed gas
D-22 Relief G03 Hydrocracking Unit ISOM
(C3-C12) (H2, C1, & C2) (H2,C1, & C2) (H2,C1, & C2)
T-2 R-31 Header
Atmospheric Hydrotreating
(HCU) light ends unstabilized
T-5 lean 84% purity Cat Naphtha Hydrotreater
(CNHT) C-105 A/B/C
second stage
Amine amine Reformer makeup
makeup

1500 psig recycle hydrogen

Crude Tower SWS Reactor (C1-C4) naphtha 3 Stage Makeup Hydrogen Compressors
Contactor AMNU Unit (RFMR) R-33
(C5-C12) R-36 Capacities: 2,500 scfh each
F-42 CDU HDC Reactor
naphtha SGP rich Reactor Loading Steps: System
LPG amine System
(C5-C12) steam P 50%, 60%,70%, 80%, 90%, 100% recycle P
bleed gas T-10 unstabilized (C3-C4) Relief
G01 Crude Distillation Unit T-4 (H2 + C1-C2) Fractionator light naphtha F recycle
P
Relief
F
hydrogen 1500 psig

1500 psig recycle hydrogen

steam jet Relief FG Header 150 psig Relief 250 psig A
D-22 Header
(CDU) (C3-C12)
(C11-C13) Header (C5-C6) G11a Virgin Naphtha Hydrotreater Header bleed gas
hydrogen bleed gas
(H2,C1, & C2)
(H2,C1, & C2) B
virgin makeup 400 psig (VNHT) 95% purity
R-32 stabilized
distillate JCTU SWS Header off gas C
1st Stage R-33 naphtha CW
(absorbent) T-5 virgin (C1-C2) Relief
Hydrocracking 2nd Stage Regular
T-1
pumparounds distillate
Reactor Hydrocracking
(C5-C12) recycle hydrogen
bleed gas Header
D-1 G12 Light Naphtha Isomerization Unit (ISOM) iC5 product
87 octane
(C13-C20) T-4 (H2 + C1-C2) (90% purity)
Preflash D-23
Reactor jet and diesel steam heavy naphtha F-41 Relief
to hydrogen
Tower pumparounds (C7-C12) (C5-C12) Header SWS
T-6 T-1 circulation (nC5 & iC5; 34% iC5) (H2, C1, & C2) Relief
F-41 lean wild naphtha
T-5 350 psig T-1 Header
overflash Jet FG amine (small flow) T-1 chloride D-22
atmospheric gas oil AMNU T-2 SGP isomerate
steam jet Blender wash Deisopentanizer Caustic High Test
D-21 (AGO) High Pressure (C11-C13) R-37 rich Stripper F-1 (iC5 & iC6)
hot crude oil D-21 D-22 water steam Scrubber 93 octane
Desalter FG (C15-C30) Separators HDT amine
water light ends T-6 T-4 CW caustic
steam diesel Reactor steam CW
condensate steam injection (C1-C4) (nC5, nC6, 300 oF (87 RON
(C13-C17) D-21 WWTP D-41
F-43 light naphtha & iC6) D-21 14 RVP)
wash water P FG
from brine D-23 overflash Diesel
D-23 WWTP pressure (nC5, iC5, nC6, & iC6) SWS
Low Pressure FG steam Blender SWS let down wild naphtha
Separator heavy naphtha
Pipeline
steam Refinery steam
(C7-C12)
CW (small flow)
polynuclear aromatics SGP
Oils Manifold (PNAs) purge flow
heavy diesel
D-11 R-2 R-3 T-4
Docks SWS D-10 T-2 Depentanizer
Relief 350 Isom RX Isom RX
Sulfur Feed
demulsifier Header
G11c Distillate Hydrotreater (DHT) (C20+)
Diesel G14 Hydrogen Plant #1 (H2P #1) Guard Bed Dryers psig
Stabilizer
natural gas (NG)
Blender 600#
1300 psig NG Hydrogen steam steam iC6 product
D-23 off gas Steam D-12 A/B
Hydrogen G15 Jet Caustic Treating Unit (JCTU) super Plant #1 (80% purity)
Slop Oil makeup (C1-C2) Relief D-1 A/B wet wet H2 Makeup
T-7 Header bleed gas heated C-101
System Header D-22 Desulfurizers steam steam Gas Driers (nC5, iC5,nC6 & iC6
Vacuum wash water
H2 + (C1-C2)
D-23 steam makeup Hydrogen
D-21 Water Wash D-9
atmospheric Tower Desalter F-41
recycle H2 HP FG
pressure wild naphtha
dry jet
BFW
Boiler
Feedwater
Compressor G13 Reformer (RFMR) 84% purity 150 psig
residuum light vacuum gas oil D-23 (small flow) fresh water D-24 A/B Hydrogen
let down SWS fuel gas (FG) System recycle hydrogen (H2, C1, & C2)
(C25-C50 +) hydrogen Clay Filters NG Header

Gasoline Blender
(LVGO) (C25-C35) lean SGP
LVGO & HVGO circulation FG BFW
amine T-2 CDU D-21 (C11-C13) FG H2P#2 Reforming Reactors hydrogen off gas Relief
pumparounds heavy vacuum gas oil FG 1100 psig T-1 T-3 Jet Caustic PSA 150 psig F-41 F-42 F-43 F-44
(C30-C50) jet AMNU Stripper
off gas D-2 air S-1 99% purity Hydrogen circulation Header
D-22
(HVGO)

vir
Wash D-23 A/B
virgin distillate rich steam (C11-C13) Blender Jet catalyst Exhaust Header

gi
water/ Salt Driers D-21

n
AGO amine Blender tubes Stack D-8 A-D

je t
F-42 caustic FG FG FG FG wild naphtha
overflash HCGO D-22 dry and clean jet F-52 Pressure Swing
F-42 caustic with purge B-32 (small flow)
HCCO Low Temp (no surfactants) Steam-Methane Adsorber (PSA)
Separator Ultra Low mercaptides regenerated SGP
R-35 Reformer
Sulfur Diesel Caustic caustic PSA T-1
FG HDT (SMR) D-3
steam FG (ULSD) (C13-C17) Diesel Regenerator off gas F-45 Stabilizer
Vacuum Reactor SWS High Temp to R-31 R-32
D-21 40 Cetane Blender (mercaptides CDU R-33
Resid High Temp wash oil to disulfides wash oil Shift Converter D-6 F-52 Reactor Reactor Reactor R-34
Quench (solvent) conversion) D-5 produced Reformate
Separator with Reactor FG
pressure heating oil Heating water (C7-C12)
(C50 +) disulfides
let down production mode Oil Sales (103 RON; 0.6 RVP)
(C13-C20)

G02 Delayed Coking Unit

F-42
CO Boiler steam Unsaturated Hydrocarbon Refining Process Units D-24
D-22 system G06 Unsaturated Gas Plant Distillation Section
Coker (DCKU) fuel gas atm
G16 Sulfuric Acid Alkylation Unit D-24
Wet Gas (C1-C2) G04 Fluid Catalytic Cracking Unit Steam Drum
BFW
HP FG (USGP) propylene-rich D-25
Compressor USGP (FCCU) Expander FG
lean
100 ppm H2S (C3= & nC3) (ALKY) T-1 (nC4)
Deaerator absorbent
Turbine lean Chemical Deisobutanizer
D-22 Coker (C1-C2) (naphtha) 0 ppm mercaptans Reaction Section Butane
coker LPG & reactor vapor V-33 S-4 T-3 amine Plant SGP
D-21 Wet Gas C7-C12 C-81 Sales
naphtha Third Stage iC4 refrigerant T-6 (nC4 & iC4) (iC4)
LPG Compressor AMNU regenerated T-8
(C3-C12) Separator T-7 Depropanizer to (90 RON; 52 RVP)
naphtha Refinery D-23 rich caustic Depropanizer D-21
USGP atmos Cat Wet Gas from Mercaptan R-31 Rx
Mud Drum T-2 amine during winter
Oils Manifold Compressor (C1-C2) Reactor feed
SWS air T-9 Extractor Caustic pressure T-2
D-21 Sponge Oil M M M
Regeneration let down Debutanizer
R-31 Cat D-25 Absorber 0 ppm H2S
T-1 System
Coker Main Reactor Fines LPG (iC4 & C4=) Treating Section
T-1
T-2 Column SWS (C3-C4) T-1 D-22 D-23 spent caustic
reactants steam
light cat cycle oil flue FCCU Main caustic
steam naphtha Absorber steam (iC8) alkylate
LCGO & HCGO light coker gas oil (LCCO) gas Column with mercaptides D-22 D-23 (92 RON; 4 RVP)
pumparounds (LCGO) (C13-C20) cat LPG and cat naphtha 100 ppm H2S
D-25 spent acid
heavy cat cycle oil
FCCU
T-2
(C3-C12) lean (nC4, C4= & iC4) from fresh acid condensate
Main Column T-6 amine (60% C4=) Storage fresh
(HCCO) steam Refinery Oils recycle iC4 D-24 caustic
light cracked naphtha (LCN)
(C5-C6)
LCCO & HCCO AMNU
light cat cycle oil Manifold (C3s-C4s)
T-3 heavy coker gas oil (86 RON; 7 RVP)
steam pumparounds (C13-C20) rich
(LCCO) D-21
HCGO
(HCGO)
T-5
amine absorbent to G11b Cracked Naphtha Hydrotreater (CNHT)
T-9 T-2 400 psig
spray (C15-C35) T-3 rich Debutanizer Cracked
Catalyst steam absorbent Naphtha makeup Hydrogen bleed gas off gas Relief
vacuum Circulation T-4 Header (H2 + C1-C2)
cutting water overflash heavy cat cycle oil Stripper steam Splitter Relief Header
residuum Circuit steam recycle hydrogen D-22
R-32 (HCCO) (C15-C35) F-42 Header
atomizing heavy cracked naphtha (HCN) lean
Regenerator
steam (C5-C12) (C7-C12) (80 RON) hydrogen T-8
cold F-41 steam coker LPG & naphtha amine SWS
LVGO circulation wild naphtha
CSO (C3-C12) (C3-C12) AMNU
D-24 HVGO DCKU FG 250 psig (small flow)
D-25 atmos PA rich SGP
hot gas oil combustion amine
Coke Drum Coke Drum wash
feed air T-3
online offline water
CSO
FCCU
coking
operation
decoking
operation
atmos Expander DCKU cat slurry oil (CSO)
Feed (C30+)
sweet hydrogen
sweet fuel gas
G21 Amine Unit (AMNU) recycle H2S
CW
G20 Sulfur Recovery Complex
Steam atmos R-36
pressure
let down steam
Stripper
HCN

3 Coke Drum Modules A/B/C,

CW
H2S
G24 Tail Gas Unit (TGU) System HDT Reactor
(C7-C12)
(70 RON; 3 RVP)
F-41 sweet LPG CO2 & inerts D-26
Each module consists of Fuel Gas System D-11 rich amine B-9
Fuel Tk-1 incinerator
charge pump, heater, and
pair of drums. G31 Fuel Gas and Flare High Pressure Fuel natural gas
(C1)
Gas CW rich D-13
T-3
Amine
Tk-2 Incinerator
outlet gas API Separator Bays
sulfidic Inline
FG Gas Collection Header Users amine NG process Tk-121
Module A is shown here. Coke Pit
Systems high Fuel Gas
Lean
Amine
T-1
Amine
Regenerator
steam T-8
E-91 Refinery wastewater
M
caustic Mixer
M M M
Equalization

air
pressure Gas LPG Waste Heat Boiler Process Diversion
Distribution Regenerator amine acid gas Amine S-91 oil Tank
Header
Author: Warren P. Averill fuel gas D-24 Header
Plants
FG Absorber Incinerator
Sewers Sump Skim
Crude sludge
producers Fuel Gas FGRU D-10 (AAG) H2S, CO2
Tk-120 M M M sewer
waverill@vispersol.com steam lean amine Stack Pit
Mix Drum (94% H2S) & inerts Slop Tank Offsite
HDTs Storm Water TK-115 Tk-114
Fuel Gas Recovery Unit (FGRU) hydrogen Rich Retention Tank Sludge Tank Disposal
©Copyright 2023 slop oil lean amine B-4 Slop Tank
C-81
T-1 22 lean system Refinery Amine Amine 1/3 2/3 G23 Sulfur Recovery Unit Tail Gas Burner Tk-123
Visual Performance Solutions, Inc. FGRU Compressor slop oil Tk-121 Lagoons w/ Aerators filter
(liquid ring compressor) Fuel Gas Amine amine Absorbers and Contactors Header system of AAG of AAG Steam SMR CO2, H2, H2S, Backwash Tank backwash
www.VisPerSol.com from pressure Claus Reactors
CO2, CH4, H2S, Equalization (biological oxidation) TOC/BOD
condensate Absorber AMNU System SO2, H2O & inerts reaction SO2, H2O,
Permit
relief valves (C1-C2) 1 natural gas
G22 Sour Water Stripper Unit (SWS) E-51 reheater R-31B R-31C & inerts T-6 Tank
M M M
M M M M M Clarifier M foam Post Biox Monitoring
R-31A combustion air Quench
VPS authorizes distribution on paper or D-23 rich
steam
pilot
CW
sour water acid gas (SWAG) Waste Heat R-3 Tower
Filters (PBFs) Station
FGRU amine Refinery Sour (NH3 & H2S) Boiler
electronically within your organization and/or bleed gas from
KO Drum
S-2 Water Sources NG
Tail Gas PBF
outfall river
hydroprocessing Refinery F-41 2H2S + SO2 Reactor Sump
technology network for reference purposes complex seal
CW refinery slop Refinery Flare System Flare
D-21
Reaction waste activated sludge (WAS)
sour Offsite
molten

oil system
combustion air

only. Educators and students may distribute

sulfur

water E-21 P-81 Furnace Sulfer CO2, H2S, H2O, Dissolved Air Disposal
SWS water T-2 coagulant M
off gas from & inerts Flotation Tank
this freely among their peers. Not to be Condensers foam polymer
sulfur

auger
sulfur

sulfur
process units D-22 Sour Water
D-20 ball valve M
Stripper (SWS) Recycle
employed in any for-profit endeavor without Refinery Relief
D-21 Liquid Seal atm
liquid seal
SWS
H2O purge recycle activated sludge (RAS) Sump
KO Drum Drum steam
permission from Mr Averill. Header slop oil
steam stripped
gravity flow plant air
(low pressure) system slop oil G32 Wastewater Treatment Plant air
CH1 Page 2 of 11 P-82 water
system water
WWTP
condensate
D-39 Sulfur Pit (WWTP) air-saturated water
 Generic Full Conversion Petroleum Refinery Refinery Operations Handbook (ROHB) for Operators Chapter 1 - Refinery Operation Overview

While reading this chapter, refer frequently to the Refinery Process Flow
Diagram (RPFD). The RPFD illustrates the layout of a modern full
conversion refinery which employs many process units to refine raw crude
into products that satisfy market demand and environmental standards. A full
conversion refinery configuration provides a great deal of flexibility to
support a wide range of production optimization strategies; molecule
management is a common term for these strategies.

This chapter employs terminology associated with hydrocarbon

characteristics. If you are unfamiliar with the terms, refer to the last 2 pages
of this document CP2 Three Key Hydrocarbon Characteristics excerpted
from Chapter 2 Common Process Concepts.

Raw Crude Composition vs. Market Demand

Raw crude oil, after being distilled in the Crude Distillation Unit at the front
of the refinery, requires a significant amount of processing to satisfy the
refinery’s product slate based on market demand. As illustrated in figure
CH1-1, the biggest differences are related to groups of hydrocarbon materials
based on molecular size and the volume of each group. The left barrel
illustrates the composition of the crude oil entering the refinery as percentages
of virgin product groups. The barrel on the right illustrates the volumes of
finished hydrocarbon product groups in each barrel based on market demand.
Key points:

• Over 50% of a medium crude oil is composed of very large molecules in Figure CH1-1. Refinery Typical Product Slate based on Market Demand
the gas oils and residuum groups; these have more than 17 carbon atoms
per molecule (C17+); but 95% of the refinery final product slate is
comprised of finished product fuel groups that have 17 or fewer carbon
atoms per molecule.
• To satisfy market demand, the refinery must produce gasoline with an
octane rating of 87 or 93 at a volume rate of 50% per barrel; but medium
grade crude oil contains only 20% virgin naphtha (raw gasoline) per barrel
with an octane rating of less than 60.

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 Generic Full Conversion Petroleum Refinery Refinery Operations Handbook (ROHB) for Operators Chapter 1 - Refinery Operation Overview

Molecule Cracking Concepts. The refinery front end employs process units that crack low-value
large gas oil and vacuum residuum molecules into a full range of smaller molecules that can be
processed into high-value fuel products. These cracking units provide the initial alignment between
crude oil and market demand as it impacts the volumes of finished fuel product groups per barrel
shipped.

As an example, figure CH1-2 illustrates the results of hydrocarbon cracking in a Fluid Catalytic
Cracking Unit. (FCCU). The FCCU cracks multiple bonds within gas oil molecules containing many
carbon atoms and thereby produces a variety of smaller molecules containing fewer carbon atoms.
One of these smaller molecules in the example shown is a 10-carbon molecule that belongs to the
heavy cat naphtha intermediate product group; after undergoing additional refining processes, it
becomes a high-octane gasoline blending component.

Figure CH1-2. FCCU Cracks Large Gas Oil Molecules

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 Generic Full Conversion Petroleum Refinery Refinery Operations Handbook (ROHB) for Operators Chapter 1 - Refinery Operation Overview

Saturated and Unsaturated Hydrocarbon Refining Processes

As illustrated in figure CH1-3, refineries typically employ two separate refining
process sequences to produce fuel products. The process units listed in the upper
block diagram refine saturated fuel molecules; all carbon atoms are interconnected
with 4 single bonds – the molecules are fully saturated with hydrogen atoms. The
process units listed in the lower block diagram refine unsaturated fuel and chemical
molecules; a large percentage of these have double bonds between carbon atoms –
they are unsaturated with hydrogen atoms.

Saturated Molecules Unsaturated Molecules

Figure CH1-3. Saturated and Unsaturated Refinery Process Units

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 Generic Full Conversion Petroleum Refinery Refinery Operations Handbook (ROHB) for Operators Chapter 1 - Refinery Operation Overview

G05 Saturated Gas Plant (SGP). This receives light ends (C1-C4) from CDU and
HCU; virgin naphtha (C5-C12) from the CDU; and light naphtha (C5-C6) from
HCU. SGP separates the feed stream content into fuel gas, propane, butane, and
virgin naphtha. The virgin naphtha has a relatively low octane rating that is
typically less than 60.

G11a Virgin Naphtha Hydrotreater (VNHT). This employs hydrotreating

catalyst, moderately high temperature, and hydrogen-rich environment to remove
organic sulfur and organic nitrogen from virgin naphtha. The term organic implies
that sulfur and nitrogen are bound within hydrocarbon molecules. If not removed,
these would otherwise poison the catalyst in the downstream ISOM and RFMR
units. The hydrotreating reaction removes sulfur and nitrogen atoms from the
naphtha in the form of hydrogen sulfide (H2S) and ammonia (NH3). These
impurities are ultimately processed at the Sulfur Recovery Complex to produce pure
sulfur and nitrogen.

G12 Isomerization Unit (ISOM). This converts low-octane-straight-chain

paraffins in light naphtha (C5 and C6) into high-octane branched-chain isoparaffin
molecules (iC5) and iC6). The isomerate is a valuable gasoline blending component
with a typical octane rating of 87.G13 Reformer (RFMR). This converts the low-
octane straight-chain paraffins and circular naphthenes molecules in heavy naphtha
(C7-C12) into high-octane isoparaffins and aromatic-ring molecules; the product is
Figure CH1-4. Saturated Refining Process Units
reformate gasoline blending component with a typical octane rating of 103.
G01 Crude Distillation Unit (CDU). All crude oil enters the refinery through the CDU. The atmospheric tower
provides the first stage of fractionation to produce intermediate products that are ultimately upgraded in G11c Diesel Hydrotreater (DHT). This employs the same hydrotreating process as
downstream refining processes. These intermediate products include light ends, virgin naphtha, jet, distillate, described for VNHT. The difference is that DHT employs multiple hydrotreating
atmospheric gas oil (AGO), and atmospheric residuum (feed to vacuum tower). The vacuum tower employs a catalyst beds, operates at very high-temperature very high-pressure, in a hydrogen-
vacuum environment to decrease the boiling point temperatures of the atmospheric residuum components. This rich environment to remove organic sulfur and nitrogen from a wide range of gas oil
makes it possible to vaporize and recover light vacuum gas oil (LVGO) and heavy vacuum gas oil (HVGO) that and distillate streams. The principal products are low sulfur jet fuel and ultra-low-
have atmospheric boiling points up to 1050F while operating at vacuum tower inlet temperature less than 700F. sulfur diesel (ULSD). Added value is that DHT also saturates aromatic molecules
which improves diesel cetane value.
G03 Hydrocracking Unit (HCU). This employs hydrotreating and hydrocracking catalyst beds, high temperature
(over 700F), and a high-pressure (1500 psig) hydrogen-rich environment to crack atmospheric gas oil (AGO) and G15 Jet Caustic Treating Unit (JCTU). This employs caustic to remove sulfur
other distillates into an array of intermediate and finished products. The hydrocracking reaction is selective; the from jet fuel. When JCTU is shut down for any reason, jet fuel production is
catalyst is formulated to produce a large volume of naphtha or a large volume of diesel. In a hydrogen-rich diverted to the DHT.
environment, the reactors saturate the cracked products (eliminate double bonds).

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 Generic Full Conversion Petroleum Refinery Refinery Operations Handbook (ROHB) for Operators Chapter 1 - Refinery Operation Overview

G06 Unsaturated Gas Plant (USGP). This receives unsaturated light olefins and
naphtha from FCCU and DCKU. The term “unsaturated” implies that most of the
straight-chain and branched-chain molecules are “unsaturated” with hydrogen; the
cracking processes in the FCCU and DCKU units occur in hydrogen-poor
environments. The cracked naphtha products have a high-octane rating. The
cracked LPG is rich in high-value very-reactive olefins including propylene (C3=)
and butylene (C4=). Propylene is a valuable feed to the chemical plant as the basic
ingredient for plastics production. The butylene is a valuable feed to ALKY as a
primary reactant in the production of alkylate.

G16 Alkylation Unit (ALKY). This employs sulfuric acid as a catalyst in a

reaction that combines isobutane (iC4) and butylene (C4=) to produce alkylate
(iC8). This is a high-octane low-RVP gasoline blending component. An added
benefit of this unit is that it provides the means to maintain C4 balance in the
refinery. The C4s (iC4 and nC4) from the SGP and USGP processes far exceed
market demand for commercial butane sales. ALKY consumes large volumes of iC4
Figure CH1-5. Unsaturated Naphtha and Light Olefins Process Units from the refinery butane pool.
G02 Delayed Coking Unit (DCKU). This employs high temperatures (over 900F) and extensive residence time G11b Cracked Naphtha Hydrotreater (CNHT). This operates similar to VNHT.
(typically over 30 minutes) in a coke drum to thermally crack the very large vacuum residuum molecules (more A side effect is that CNHT also infuses hydrogen into double bonds in some of the
than 50 carbon atoms per molecule) coming from the Crude Distillation Unit (CDU). The term “coker” implies aromatic ring molecules, this results in a decrease of octane up to 10 in hydrotreated
that a byproduct of thermal cracking is a large volume of solid coke consisting primarily of carbon atoms. The HCN.
term “delayed” implies a long delay between the time the average molecule is first exposed to high temperature
and when it cracks.

G04 Fluid Catalytic Cracking Unit (FCCU). FCCU employs circulating fluid catalyst and high temperatures
(over 1100F) to crack the large molecules (C25-C50) in light and heavy vacuum gas oils (LVGO and HVGO).
The process is selective; the catalyst is formulated to produce large volumes of cat naphtha or light olefins
(primarily propylene and butylene). The cracking takes place in a hydrogen-poor environment; this results in a
high volume of unsaturated molecules and accumulation of coke on the catalyst. The fluidized catalyst
continuously circulates through a regenerator where the coke is removed in a combustion process at a
temperature over 1300F with controlled air flow into the regenerator catalyst bed.

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 Generic Full Conversion Petroleum Refinery Refinery Operations Handbook (ROHB) for Operators Chapter 1 - Refinery Operation Overview

Gasoline Blending Concepts

As illustrated in figure CH1-3, the gasoline blender combines multiple components to deliver
two gasoline products with octan values of 87 and 93; these are produced in volumes that
satisfy gasoline product market demands and specifications.

Gasoline Specifications. The most important specifications are octane and Reid vapor pressure
(RVP).
Octane rating is a standard measure of gasoline quality that contributes to high automobile
motor performance. Octane at the gas station pump is based on a Research Octane Number
(RON) and Motor Octane Number (MON) calculation. These are determined by employing
different laboratory test methods using test engines. RON is used within the refinery for quality
control of gasoline blending components.
Reid vapor pressure (RVP) of a gasoline blend is measured in units of pounds per square inch
(PSI). If blended gasoline RVP is higher than specification this results in an unacceptable level
of emissions during transportation and loading. Typical values for RON and RVP for gasoline
blending components are listed in figure CH1-3.
Summer vs Winter Blending Seasons. EPA-mandated gasoline RVP specification is the
major driver for shifts in refinery operations during summer and winter seasons.

In the winter, RVP specification for blended gasoline can be as high as 14.7 psi. This provides
an opportunity to maximize percentage of butane into the gasoline blend and thereby contribute
to C4 balance in the refinery – C4 production equals C4 consumption. Normal butane is a low-
cost-high-octane component with a RON of 90 and an RVP of 52; to compensate for an
increase in butane, the blend must be adjusted to include a larger percentage of components
with very low RVP. For example, an increase in percentage of reformate flow (with an RVP of
0.6) makes it possible to incrementally increase percentage of butane flow into the blender.

In the summer, the maximum RVP can be as low as 8 psi; this compensates for higher average
environmental temperatures that promote gasoline vaporization. In a shift from winter to
summer, the refinery adjustments may include:
• Increase production of alkylate production to consume iC4s.
• Store excess butane with a plan to consume the C4s during the winter gasoline blending
season.

Figure CH1-3. Refinery Block Flow Diagrams (copy)

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Sulfur and Nitrogen Removal Processes

Concerns. Crude oil contains a significant amount of hydrogen sulfide (H2S), organic sulfur (S) and
organic nitrogen (N) within virgin light ends, virgin naphtha, distillates, and heavy oils. If not removed,
combustion of sulfur-bearing fuel products results in exhaust that includes sulfur dioxide (SO2). When SO2
encounters water in the atmosphere, it creates acid rain. A significant amount of organic nitrogen (N) is
bound within C7 and larger hydrocarbon molecules. If not removed, combustion of nitrogen-bearing fuel
products results in exhaust that includes nitric oxide which is a harmful greenhouse gas. Organic nitrogen
and sulfur in refinery intermediate products, if not removed, poison catalysts in multiple refinery reactors.

In figure CH1-6, sulfur and nitrogen removal processes are emphasized with yellow-colored borders
within multiple process unit blocks.

Hydrotreating Processes. These remove sulfur bound within hydrocarbon molecules to produce H2S; the
circulation of hydrogen flowing through the hydrotreaters sweeps the H2S out of the hydrotreated product.

Amine absorbers and contactors capture H2S from light ends flowing through Saturated and Unsaturated
Gas Plants (SGP and USGP); from the circulating hydrogen in hydrotreaters (VNHT, CNHT, and DHT);
and from Fuel Gas Recovery System. All rich amine (loaded with H2S) flows into the G21 Amine Unit
(AMNU) within the Sulfur Recovery Complex. AMNU strips the H2S from the rich amine and then the
Sulfur Recovery Unit (SRU) converts H2S into pure sulfur.

Amine absorbers and contactors reduce H2S content in the gas plants down to less than 100 ppm. Caustic
treating reduces H2S down to 0 ppm. Sulfur is also bound within mercaptan molecules; mercaptan
extractors employ caustic to capture the sulfur-bearing mercaptan molecules from the hydrocarbon
streams. Caustic treating and mercaptan extraction in the SGP, USGP, and Jet Caustic Treating Unit
require a continuous supply of fresh caustic and removal of spent caustic.

Hydrotreating processes also remove nitrogen bound within C7 and larger hydrocarbon molecules to
produce NH3 (ammonia). The ammonia leaves the hydrotreating reactors with the treated hydrocarbon
stream flowing into separator drums. Water is injected upstream of these drums to absorb the ammonia and
small amounts of H2S. The sour water with ammonia gravity separates from the hydrocarbon in the drums.
The sour water collection system conveys all sour water to Sour Water Stripper (SWS) located in the
Sulfur Recovery Complex. SWS separates the NH3 and H2S to produce sour water acid gas (SWAG). The
SWAG is incinerated in the SRU reaction furnace to produce pure nitrogen, pure sulfur, and water vapor. Figure CH1-6. Refinery Sulfur and Nitrogen Removal Processes

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 Generic Full Conversion Petroleum Refinery Refinery Operations Handbook (ROHB) for Operators Chapter 1 - Refinery Operation Overview

CP2 Three Key Hydrocarbon Characteristics

Purpose Table CP2-1 illustrates example molecular structures of light ends species and subspecies. Carbon
atoms within paraffin and isoparaffin molecules have single bonds. Carbon atoms within olefin
These characteristics provide insights on the sequential progression of refining processes that molecules have one or more double bonds. For any C number, there can be multiple species and
starts with crude oil feed and ends with the delivery of high-value fuel products. subspecies; each subspecies has a unique atmospheric boiling point temperature.
Hydrocarbon Characteristics. Light Ends (C1-C4). For C1 methane, there is one species and no subspecies. For C3s, there are
two species propane (paraffin) and propylene (olefin). For C4s, there are three species normal
C-Number. This is the number of carbon atoms in each molecule; it provides a sense for the size butane (paraffin), isobutane (isoparaffin) and butylene (olefin); there are multiple subspecies for
of the molecule. Examples: butylene.
• Methane molecule contains only one carbon atom; it is referred to as C1, this is smallest Table CP2-1. Light Ends Molecular Structures
hydrocarbon found in fuel gas and natural gas.
• Naphtha is composed of C5 through C12 molecules. C# Paraffins Isoparaffins Olefins
Atmospheric Boiling Point Temperature. At atmospheric pressure, this is the temperature at C1 methane N/A N/A
which a particular hydrocarbon component: BP = -259F

• Boils as it changes from liquid state to a gas state while being heated.
• Condenses as it changes from gas state to a liquid state while being cooled.
C2s ethane (C2) N/A ethylene (C2=)
As the C number increases from one size hydrocarbon molecule to another, the atmospheric BP = -128F BP = -155F
boiling point temperature increases.

Species. There are five hydrocarbon species, one for each letter in the PIANO acronym:
C3s propane (C3) N/A propylene (C3=)
• P for paraffin BP = -44F BP = -54F
• I for isoparaffin
• A for aromatic
C4s butane (C4) isobutane (iC4) butylene (C4=)
• N for naphthene
BP = 31F BP = 11F BP = 21 to 34F
• O for olefin

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 Generic Full Conversion Petroleum Refinery Refinery Operations Handbook (ROHB) for Operators Chapter 1 - Refinery Operation Overview

Naphtha. All naphtha is a mixture of species and subspecies that are processed to produce Spectrum of Feed Boiling Point Temperatures. Figure CP2-1 is a useful representation of feed
gasoline blending components. As illustrated in table CP2-2, naphtha contains paraffins (also composition at an unsaturated gas plant. The atmospheric boiling points of the feed hydrocarbons
referred to as “normal paraffins” or “n-paraffins”), isoparaffins, olefins, plus two other species -- are between -259F and 370F. Starting with light ends, the yellow lines represent the relative
naphthenes and aromatics. Naphthene molecules are circular with carbon atoms held with single volume of C1 and C2 components that, at normal gas plant pressures, are noncondensables; they
bonds. Aromatic molecules are circular with some carbon atoms held with double bonds. For each always remain in a gas state. The brown lines represent the condensable light ends components
naphtha species listed, there are multiple subspecies; each subspecies has a specific boiling point which include C3s and C4s. The orange curves represent the naphtha component volumes.
temperature. Naphtha is considered a single intermediate product with a multitude of hydrocarbon species and
subspecies with a boiling point range between 68F and 370F.
Table CP2-2. Naphtha Molecular Structures

C# Paraffins Naphthenes Aromatics

Isoparaffins
Olefins
C5s n-pentane BP = 97F cyclopentane None
isopentane BP = 82F BP = 121F
pentylene
BPs = 68 to 101F
Figure CP2-1. Spectrum of Naphtha and Light Ends Hydrocarbons
C6s n-hexane BP = 156F cyclohexane benzene
BP = 177F BP = 176F Key Points. When analyzing separation processes in a gas plant, the following are the key points
isohexane BP = 140F
to be considered:
hexylene
BPs = 106 to 164F • C1 and C2s have very low boiling points and can only be recovered as a liquid at very high
pressures and extremely low temperatures.
• The boiling point range for the different species of C3s is relatively narrow.

C7s n-heptane BP = 209F methylcyclohexane toluene • The boiling point range for the different species of C4s is relatively narrow.

isoheptane = 194F BP = 214F BP = 231F • There is a large boiling point temperature gap between C3s and C4s.
heptylene • There is a large boiling point temperature gap between the highest boiling point temperature
BPs = 172 to 200F component in C4s and the lowest boiling point temperature component in naphtha C5s.

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