Author: Warren Averill

waverill@VisPerSol.com
www.VisPerSol.com
“We help your workforce Visualize Solutions for better Performance.” (410) 533-9882
 Generic Full Conversion Petroleum Refinery Refinery Operations Handbook (ROHB) for Operators Foreword

Table of Contents
Chapter 1 Refinery Overview Functional Process Flow Diagrams and Descriptions
Refinery Process Flow Diagram (RPFD Chapter 3 Saturated Hydrocarbon Chapter 5 Sulfur Recovery Complex
Raw Crude Composition vs Market Demand Refining Process Units
G21 Amine Unit (AMNU)
Saturated and Unsaturated Refinery Process Unit G01 Crude Distillation Unit (CDU) G22 Sour Water Stripper (SWS)
Block Flow Diagrams
G03 Hydrocracking Unit (HCU) G23 Sulfur Recovery Unit (SRU)
Gasoline Blending Concepts G05 Saturated Gas Plant (SGP) G24 Tail Gas Unit (TGU)
Sulfur and Nitrogen Removal Processes G10 Hydroprocessing Complex (HPC) Chapter 6 Auxiliary Units
Chapter 2 Common Process Concepts G11a Virgin Naphtha Hydrotreater (VNHT)
G31 Fuel Gas and Flare System (FGFS)
CP1 Mental Simulation Statements G11c Distillate Hydrotreater (DHT)
G32 Wastewater Treatment Plant (WWTP)
CP2 Hydrocarbon Characteristics G12 Light Naphtha Isomerization Unit (ISOM)
CP3 Basic Distillation G13 Reformer (RFMR)
CP4 Atmospheric Fractionation G14 Hydrogen Plant No. 1 (H2P#1)
CP5 Heat-Driven Stripping G15 Jet Caustic Treating Unit (JCTU)
CP6 Steam-Driven Stripping Chapter 4 Unsaturated Hydrocarbon
Refining Process Units
CP7 Hydrocarbon Absorption
CP8 Hydrocarbon Cracking G02 Delayed Coking Unit (DCKU)
CP9 Amine Absorption and Regeneration G04 Fluid Catalytic Cracking Unit (FCCU)
CP10 Hydrotreating G06 Unsaturated Gas Plant (USGP)
CP11 Caustic Scrubbing and Mercaptan Extraction G11b Cracked Naphtha Hydrotreater (CNHT)
CP13 Heavy Oil Process Heaters G16 Sulfuric Acid Alkylation Unit (ALKY)

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 Generic Full Conversion Petroleum Refinery Refinery Operations Handbook (ROHB) for Operators Foreword

Purpose Chapter 1 Refinery Overview

This Refinery Operation Handbook (ROHB) was designed to enlighten Refinery Process Flow Diagram (RPFD). This is the centerpiece training aid for Operator’s.
anyone interested in how petroleum refineries convert raw crude oil into It illustrates the comprehensive layout of the full conversion refinery and how each process
valuable hydrocarbon fuel products that satisfy market demand and unit contributes to the transformation of raw crude oil into refinery finished products. A high-
environmental standards. The polished writing style accompanied by resolution version of the RPFD is provided in acrobat PDF format on page 2 of chapter 1.
numerous detailed graphics and process diagrams make this an easy read for While the full size of this diagram is 27” X 38”, it is readable when printed on A3 or Super B
Operators, Interns, new Process Engineers, Supervisors, and Managers. paper sizes. After reading each incremental component of the handbook, Operators are
encouraged to refer to the RPFD to add what they just read to their understanding of overall
Over the last 30 years, the ROHB design evolved as we implemented multiple refining operation.
customized versions for operational teams at Exxon, Mobil, ExxonMobil,
Chevron, BP, Phillip 66, Calumet, ParPacific, and Marathon refineries. In this Raw Crude Composition vs. Market Demand. Raw crude oil, after being distilled in the
evolution, we worked with the most experienced Console Operators and Crude Distillation Unit, requires a significant amount of processing to satisfy the refinery’s
Process Engineers in the refining industry to validate the many technical product slate based on market demand. The biggest difference is that over 50% of raw crude
concepts and overall presentation strategy. oil components comprise very large gas oil and residuum (tar) molecules; yet 95% of finished
fuel products comprise very much smaller molecules. The full-conversion refinery employs
Process Flow Diagram Design Concepts three hydrocarbon cracking process units to address this difference.
User-Friendly Layout with Logical Flow. For each process diagram, flow is Refinery Block Flow Diagrams and Overview Descriptions. The hydrocarbon fuel refining
depicted going from left to right and top to bottom starting with feed sources process units are segregated into two groups: Saturated Hydrocarbon Refining Process Units
and progressing to product dispositions. Heat integration is subordinated in that refine saturated hydrocarbons; and Unsaturated Hydrocarbon Refining Process Units that
this layout strategy by showing each process-to-process heat exchanger twice refine unsaturated hydrocarbons.
on all diagrams -- once for tube-side flow and another for shell-side flow.
Gasoline Blending Concepts. The refinery block flow diagrams also depict the gasoline
Detailed Equipment Internals. Each major piece of equipment is depicted blending system. The description content defines the key characteristics (octane and Reid
iconically with sufficient detail to convey the internal operation and basic vapor pressure); lists typical characteristic values for each gasoline blending component; and
function. how the mixture of these components results in gasoline products that satisfy specifications.
Customized Color Palette. This is a human-factored collection of colors that The description also addresses how refinery operation must be adjusted for summer and
facilitate the Operators’ comprehension of process material flow patterns winter blending seasons to comply with EPA-mandated gasoline RVP specifications.
throughout the refinery. The palette comprises nineteen separate color Sulfur and Nitrogen Removal. A separate block flow diagram illustrates how key
specifications. environmental standards for sulfur and nitrogen content in fuel products are satisfied with
removal processes integrated into multiple refinery process units.

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 Generic Full Conversion Petroleum Refinery Refinery Operations Handbook (ROHB) for Operators Foreword

Chapter 2 Common Process Concepts Gestalt Learning Theory

These concepts are common among multiple refinery process units. These same concepts are relevant The RPFD and FPFD content is presented in a form that embodies
to other petroleum refineries. Each description includes: Gestalt theory which can be simply stated as: ‘In a learning endeavor,
the natural desire of adults is to first understand each body of
• Purpose – how the common process contributes to refinery objectives. knowledge at an overview level and then develop a logical
• Process Functional Flow – general description of flow through the common process. understanding of how all the pieces fit into the overall system.”
• Principles of Operation – general description of applicable chemistry concepts. Most people have heard the phrase “A picture is worth a thousand
• Applications – which process units within the Generic Full Conversion Petroleum Refinery employ words.” To leverage this concept, this handbook includes descriptions
each common process. of the RPFD and FPFDs. After Operators read each description with the
Chapters 3 through 6 -- Functional Process Flow applicable diagram content in view, they can typically recall the written
content from memory simply by interpreting the composition of each
Separate chapters are focused on process units within four operational groups: iconic image and how all of these are interconnected on the diagram.
Over a brief period of time, the Operators embrace the RPFD and each
• Chapter 3 Saturated Hydrocarbon Refining Process Units
FPFD as common mental models that, as a system, facilitates a
• Chapter 4 Unsaturated Hydrocarbon Refining Process Units contextual understanding of overall refinery operation.
• Chapter 5 Sulfur Recovery Complex
Handbook Viewing Considerations
• Chapter 6 Auxiliary Units
The handbook design is optimized for viewing as an eBook on a PC or
Each chapter provides the following content for each process unit.
as a printed textbook. It includes 169 high-resolution process diagrams
Functional Process Flow Diagram (FPFD). Each FPFD is similar in layout to what is presented in the and other graphics integrated into a 133-page presentation.
RPFD. The FPFD, though, includes additional content to include all ancillary equipment – pumps,
The PDF page size is 11” X 17” with all descriptive text in 14 pt font.
exchangers, filters, etc. – with equipment numbers. As an eBook, this results in an aspect ratio to fill standard computer and
Functional Process Flow Description. This describes functional flow through the process unit. The monitor screens and provides highly readable description content. As
description is parallel to the layout of the FPFD. provided in textbook delivery, when printed on letter-size paper,
readability is equivalent to or better than most hardback textbooks.
Principles of Operation Description. These are based on fundamental chemistry concepts. The content
is sufficient to provide a fundamental understanding of major equipment internal operation. These
same concepts are relevant to similar process units at other petroleum refineries. For process units that
incorporate common processes, this includes a reference to the applicable chapter 2 content.

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

Full Conversion Petroleum Refinery Table of Contents

Refinery Process Flow Diagram (RPFD)…………………….2
Refinery Operation Handbook (ROHB) Raw Crude Composition vs. Market Demand……………….3
for Operators Saturated and Unsaturated Hydrocarbon Refining Processes..5
Gasoline Blending Concepts………………………………….8
Chapter 1
Sulfur and Nitrogen Removal Processes………………………9
Refinery Operation Overview CP2 Three Key Hydrocarbon Characteristics……….Addendum

While reading this chapter and all chapters to follow, 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 includes terminology associated with hydrocarbon characteristics. If you are unfamiliar with these
terms, refer to the last 2 pages of this document CP2 Three Key Hydrocarbon Characteristics excerpted from
Chapter 2 Common Process Concepts.

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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
rich pilot sour water acid gas (SWAG) R-31A combustion air Quench
D-23 Waste Heat Filters (PBFs)
Feel free to distribute this diagram on paper or FGRU amine
steam
Refinery Sour CW (NH3 & H2S) Boiler
R-3 Tower
Station
bleed gas from S-2 Tail Gas PBF
electronically within your organization and/or hydroprocessing KO Drum
Refinery
Water Sources
F-41 2H2S + SO2 NG
Reactor Sump outfall river
CW refinery slop D-21
technology network. Please do not employ this complex seal Refinery Flare System Flare sour
Reaction waste activated sludge (WAS)
Offsite
molten

oil system
combustion air

sulfur

water E-21 P-81 Furnace CO2, H2S, H2O, Dissolved Air

in any for-profit endeavor without permission off gas from SWS water T-2 Sulfer
Condensers & inerts
coagulant
Flotation Tank
M Disposal
foam polymer
sulfur

auger
sulfur

sulfur
Sour Water
from Mr Averill. process units D-22 D-20
Stripper (SWS) ball valve Recycle M
D-21 Liquid Seal atm SWS
Refinery Relief KO Drum liquid seal steam H2O purge recycle activated sludge (RAS) Sump
Drum
Header slop oil gravity flow plant air
steam stripped
(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

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 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.

Figure CH1-1. Refinery Typical Product Slate based on Market Demand

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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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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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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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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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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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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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Table of Contents
Full Conversion Petroleum Refinery CP1 Mental Simulation Statements ........................................... 2
Refinery Operation Handbook (ROHB) CP2 Three Key Hydrocarbon Characteristics ........................... 3
CP3 Basic Distillation Concepts ............................................... 5
for Operators
CP4 Atmospheric Fractionation ................................................ 9
CP5 Heat-Driven Hydrocarbon Stripping ............................... 13
Chapter 2 CP6 Steam-Driven Stripping ................................................... 14
Common Process Concepts CP7 Hydrocarbon Absorption ................................................. 15
CP8 Hydrocarbon Molecule Cracking Concepts .................... 16
CP9 Amine Absorption and Regeneration .............................. 21
This chapter describes fundamental analysis concepts (CP1 and CP2) and the
common processes that are integrated in multiple refinery process units (CP3 CP10 Hydrotreating ................................................................. 23
through CP13). CP11 Caustic Scrubbing and Mercaptan Extraction ............... 26

Each of the CP3 through CP13 common process descriptions include a listing CP13 Heavy Oil Process Heater .............................................. 28
of all specific Refinery Process Units where the common process is integrated
into the refinery.

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CP1 Mental Simulation Statements

Purpose Example CP1-1: What if the Operator increased FC21.SP (flow of feed to D-2 degassing surge
drum)? (Focus on the flow controller response.)
Mental simulation statements are integrated into principles of operation descriptions throughout this
ROHB. They provide the means to concisely describe cause and effects associated with chemistry- ANSWER:  FC21.SP  FC21.PV is greater than/less than/equal to FC21.SP  FC21.OP 
based relationships, control adjustments, and operational malfunctions. The capability to mentally  FC21.PV  to SP
simulate how process systems respond to changes is the basis for development of systematic
The above shorthand mental simulation statement can be translated as follows:
troubleshooting and optimization skills. Establishing mental simulation statements, as a standard
form of communication, facilitates collaboration among the operations team members when ANSWER:  FC21.SP [an increase in FC21 inlet flow setpoint]
resolving operational issues.  [causes] FC21.PV less than SP [FC21 inlet flow process variable
to be less than FC21 setpoint value]
Table CP1-1. Mental Simulation Shorthand Abreviations and Symbols  [causes] FC21.OP  [FC21 output signal to the control valve to increase]
 [causes] FC21.PV  to SP [FC21 process variable to increase to a value
Symbol Meaning
equal to the setpoint value]
Parameter Value
.PV
(Indication)
.SP Control Setpoint
 Increase(s)
 Decrease(s)
Ө No change
 Causes/which causes

The primary advantages of using symbols rather than words are that:

• Symbols provide maximum information in a minimum space.

• Symbols are more visual than words and therefore improve comprehension.
• Symbols make it easier and quicker to document cause-and-effects
Figure CP1-1. D-2 Degassing Surge Drum Process Flow

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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.
As the C number increases from one size hydrocarbon molecule to another, the atmospheric C2s ethane (C2) N/A ethylene (C2=)
boiling point temperature increases. BP = -128F BP = -155F

Species. There are five hydrocarbon species, one for each letter in the PIANO acronym:

• P for paraffin C3s propane (C3) N/A propylene (C3=)

BP = -44F BP = -54F
• I for isoparaffin
• A for aromatic
• N for naphthene C4s butane (C4) isobutane (iC4) butylene (C4=)
• O for olefin BP = 31F BP = 11F BP = 21 to 34F

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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
BP = 121F
isopentane BP = 82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.
BP = 214F BP = 231F • There is a large boiling point temperature gap between C3s and C4s.
isoheptane = 194F
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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CP3 Basic Distillation Concepts

Purpose Functional Process Flow
The simple debutanizer of figure CP3-1 is the vehicle to demonstrate basic distillation concepts. The Tower Tray Operation. Distillation takes place by establishing vapor-liquid interaction in the
objective of this debutanizer is to separate the C3-C12 feed into relatively pure overhead LPG tower trays. The sources of liquid flowing through the tower are reflux from the overhead circuit
(lights) product and pure bottom naphtha product (heavies). Distillation is imperfect; there is a small and feed. Vapor flow is produced by the reboiler at the tower bottom.
amount of C5s in the LPG product and a small amount of C4s in the bottom product.
As illustrated in figure CP3-2, the liquid flows across each tray and then through a downcomer to
the tray below it. Vapor rises through holes in the trays and bubbles up through the liquid flowing
across the trays. This results in vapor-liquid interaction. Moving down the tower the temperature
of the contents in each tray increases.

Figure CP3-2. Tower Tray Operation

Figure CP3-1. Simple Debutanizer

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Naphtha Circulation in the Tower Bottom. As illustrated in figure CP3-3, naphtha circulates Reflux Circulation in the Tower Overhead. As illustrated in figure CP3-4, LPG circulates
through the bottom subsystem of the tower and the reboiler. A portion of this naphtha flows through through the the overhead system of the tower and condenser. All vapor entering the overhead
the reboiler and vaporizes as it absorbs heat from the condensing steam (heat in). The remainder of condenses as heat is absorbed by the cooling water (heat removed). A portion of the LPG flows
the naphtha flows out as bottom product. into the tower as reflux. The remainder of the LPG flows out as overhead product.

As the naphtha vapor bubbles up through each tray, the vapor components with boiling point As the reflux (LPG) flows down and across each tray, the liquid components with boiling point
temperatures less than the tray liquid temperature condense and produce heat of condensation. As temperatures less than the tray liquid temperature, vaporize and absorb heat-of-vaporization. As
the liquid in the tray absorbs heat it causes LPG components with boiling point temperatures less the liquid in the tray cools, it causes hydrocarbon components with boiling point temperatures
than the tray temperature to vaporize. Going from top to bottom of the tower, there is a greater than the tray temperature to condense. Going from bottom to top of the tower, there is a
progressively greater concentration of the naphtha and less LPG in the trays. progressively greater concentration of LPG and less naphtha in the trays.

Figure CP3-3. Naphtha Vapor Circulation in Bottom Subsystem

Figure CP3-4. Reflux Circulation in Overhead System.

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CP3 Principles of Operation Product Distillation Curves Definitions

Heat and Material Balance. For all distillation processes, highly competent Operators predict how Crossover Point Temperature. This is the temperature where the two product curves intersect. If
control adjustments impact product quality and constraint variables; for the simple debutanizer, the this temperature increases, it infers that product curves shift to the right. If this temperature
focus is on how control adjustments to reflux and steam flows impact product quality. decreases, it infers that the product curves shift to the left.

Product Distillation Curves. Figure CP3-5 provides a useful representation to visualize the results Initial Boiling Point Temperature (IBP). In a lab test of a hydrocarbon product sample, the sample
of heat and material balance analysis. The solid-colored lines represent the actual composition of is slowly heated at atmospheric pressure. The initial boiling point is the temperature value when
material entering the tower if the components could be perfectly separated. The colored dashed lines the first bubble of vapor is formed in the liquid mixture.
represent the results of distillation.
Final Boiling Point Temperature (FBP). In the same lab test, the final boiling point is the
temperature value when a product sample is completely vaporized.

Refinery Applications
In G05 Saturated Gas Plant (SGP), T-4 Debutanizer separates feed into LPG (C3-C4) and virgin
naphtha; T-6 Depropanizer separates feed into propane and butane.

In G06 Unsaturated Gas Plant (USGP), T-4 Debutanizer separates feed into olefin-rich C3s and
C4s in overhead product and cracked virgin naphtha in bottom product; T-6 Depropanizer
separates feed into propylene-rich overhead product and butylene rich bottom product; T-9
Cracked Naphtha Splitter separates feed into light cracked naphtha in overhead product and heavy
cracked naphtha in bottom product.

In G12 ISOM, T-1 Deisopentanizer separate the feed into iC5-rich overhead product, the bottom
Figure CP3-5. Product Distillation Curves for a Simple Debutanizer. product consists of nC5, iC6, and nC6 to be upgraded in the Isom Reactors to an isomerate-rich
The distillation is imperfect; the green dashed line encompasses the components in the overhead product intermediate product; T-4 Depentanizer separates isomerate reactor effluent into C5s in
product; it contains all the C3s, most of the C4s, and a very small amount of naphtha (C5s). The red the overhead product and iC6 blending component bottom product.
dashed line encompasses the components in the bottom product; it consists of naphtha and a small
In G16 ALKY, T-1 Deisobutanizer separates alkylate effluent into recycle iC4 in the overhead
amount of C4s.
product and iC8 rich bottom product; T-2 Debutanizer separates the bottom product of T-1 into
nC4 overhead product and alkylate blending component bottom product.

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Quality of Distillation. An increase in vapor-liquid contact in the tower trays improves the quality Shift in Crossover Point. An increase of steam to the reboiler and no change in reflux, increases
of distillation. This is accomplished by a proportional increase of steam to the reboiler and increase crossover point. The result is illustrated in figure CP3-7. There is an increase in the quality of the
of overhead reflux flow. The result is illustrated by the change in product curves in figure CP3-6. naphtha and decrease in the quality of the LPG.
There are less C5s in the overhead product and less C4s in the bottom product.
Heat and Material Balance
Heat and Material Balance  FC2.SP steam to reboiler  hydrocarbon vapor load to the overhead 
 FC2.SP steam to reboiler  liquid produced in the overhead condenser 
 proportional  vapor up the tower  vapor into the overhead 
 liquid condensed   overhead liquid produced and Ө FC6.SP reflux
 FI8 LPG product  material balance in the overhead
Proportional  FC6.SP  reflux equal to the additional liquid condensed in the overhead
 material balance  FI8 and FI4 flow rates are approximately equal to the product flow rates Ө feed rate and  FI8 LPG product  FI4 naphtha product 
before the changes  crossover point temperature Ө and vapor-liquid contact   crossover point temperature 

Products Quality Products Quality

Ө crossover point temperature and  in vapor-liquid contact  crossover point temperature 
 FBP of the LPG  C5s in LPG   LPG quality   FBP of the LPG  C5s in LPG   LPG quality 
 IBP of the naphtha   C4s in naphtha   naphtha quality   IBP of the naphtha   C4s in naphtha   naphtha quality 

Figure CP3-6. Product Curves for Increase in Quality of Distillation Figure CP3-7. Product Curves for a Shift in Crossover Point

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CP4 Atmospheric Fractionation

Purpose Functional Process Flow
The simple fractionator of figure CP4-1 is a vehicle to demonstrate basic fractionation concepts. The Flash Zone Vaporization. Feed is typically preheated to approximately 650 F. As illustrated
objective is to fractionate a feed containing a broad range of hydrocarbon components into a relatively in figure CP4-1, as the heated multi-component oil enters the fractionator flash zone, most
pure overhead product, multiple sidestream products, and a bottom product. These towers operate at hydrocarbon components with boiling point temperatures less than 650 F (light components)
pressures slightly above atmospheric. vaporize and rise through a chimney tray into the tower trays. Heavy components with boiling
point temperatures greater than 650F (heavy components) accumulate in the bottom of the
tower. The separation of light and heavy components is facilitated with an overflash flow from
the bottom chimney tray and steam rising through the flash zone. The overflash is a reflux
flow into the flash zone; as the reflux vaporizes, it cools and condenses the small amounts of
entrained heavy components in the flashed vapor. The stripping steam entering the bottom of
the tower promotes the vaporization of the small amount of light components entrained in the
heavy oil.

Tower Tray Operation. Distillation takes place by establishing vapor-liquid interaction in the
tower trays. The sources of liquid flow down through the tower include condensation in the
pumparound regions and reflux from the overhead circuit. Vapor flow is produced in the flash
zone.

As illustrated in figure CP4-2, the liquid flows across each tray and then through a downcomer
to the tray below it. Vapor rises through holes in the trays and bubbles up through the liquid
flowing across the trays. This results in vapor-liquid interaction.

Figure CP4-1. T-1 Simple Fractionator

Figure CP4-2. Fractionator Tray Operation

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Pumparound Operation. The volume of vapor rising through the tower decreases in each of the In summary, there is continuous circulation of naphtha through the overhead system. It
fractionator pumparound regions. As illustrated in figure CP4-3, each pumparound system includes the absorbs heat-of-vaporization as it cools liquid in the upper fractionator trays and transfers
external pumparound loop and the pumparound region within the tower between the pumparound draw heat-of-condensation to cooling water in the overhead condenser. The warmed cooling
point and the return point. Heat is absorbed from the hydrocarbon in the pumparound steam generator; the water removes heat from the system.
cooled liquid returning to the tower absorbs heat in the pumparound region causing condensation of vapor.

Figure CP4-3. Simple Fractionator Top Pumparound Operation

Overhead Operation. As illustrated in figure CP4-4, the vapor leaving the top pumparound rises into the
overhead system. The overhead system includes the overhead condensing circuit above the tower and the
upper trays in the tower.

As the vapor passes through the cooling water condenser, almost all naphtha in the vapor condenses; the
heat-of-condensation is transferred to the cooling water. The condensed naphtha settles into the accumulator
drum. The naphtha is pumped from the bottom of the accumulator back to the tower as reflux and as a
product to the gas plant. Figure CP4-4. Simple Fractionator Overhead Operation

As the naphtha reflux flows down through the upper tower trays, it encounters the vapor rising from the Sidestream Products. Separation of hydrocarbons based on boiling point temperatures
distillate pumparound region. The vapor components, with boiling point temperatures greater than tray takes place as described in tower tray operation description. The hydrocarbons in the
liquid temperature, condense; heat-of-condensation transfers to the tray liquid (heating effect). The reflux boiling point range of the distillate product are condensed in the top pumparound region of
naphtha components, with boiling point temperatures less than the tray liquid temperatures, vaporize; heat- the tower and in all the trays above the draw point. The hydrocarbons in the boiling point
of-vaporization is absorbed from the tray liquid (cooling effect). The volume of heavier components range of gas oil product are condensed in the bottom pumparound region of the tower and
condensed in the upper trays is proportional to the volume of naphtha reflux vaporized. in all the trays below the top pumparound region.

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CP4 Principles of Operation Increase in Distillate Flow. A change in distillate flow results in changes in compositions of
distillate, gas oil, and residue products.
Heat and Material Balance. For all distillation processes, highly competent Operators predict how
control adjustments impact product quality; this requires a fundamental understanding of heat and  FC27.SP distillate flow  gas oil type materials in distillate product 
material balance concepts. Each product is a fraction of the feed composition. For the simple
 gas oil type materials in distillate product and Ө FC28.SP gas oil product
fractionator, the focus is on how control adjustments to pumparounds and sidestream products impact
 residue type material in gas oil product 
product quality.

Fractionation Product Curves. Figure CP4-5 is a useful representation to visualize product

characteristics.

Figure C4-5. Product Fractionation Curves for Normal Operation

Initial Boiling Point (IBP). In a lab test of a hydrocarbon product sample, the sample is slowly heated
at atmospheric pressure. The initial boiling point is the temperature value when the first bubble of
vapor is formed in the liquid mixture.

Final Boiling Point (FBP). In the same lab test, the final boiling point is the temperature value when a
product sample is completely vaporized.

Cut Point Temperature. This is the temperature where the two product curves intersect. There is an
overlap of boiling point range between each fraction and the adjacent fractions because distillation is
imperfect. In the case of a naphtha-distillate cut point, there are equal amounts of naphtha-type
material in the distillate and distillate-type material in the naphtha.

As illustrated in figure CP4-6, the product curves are useful representations to visualize the results of
heat and material balance. The dashed black lines illustrate the initial product characteristics before an
adjustment. The colored solid lines illustrate how the characteristics change after a control adjustment. Figure CP4-6. Increase of Distillate Flow in T-1 Simple Fractionator

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Quality of Distillation. As illustrated in figure CP4-7, an increase in vapor-liquid contact in the tower
trays improves the quality of distillation which increases the quality of the fractionator products.

 FC23.SP or  TI33 in the BPA  condensation in the tower BPA region 

 vapor traffic above the region   temperature at TC10.PV (overhead)   TC10.OP 
 proportional  FI4 overhead reflux approximately equal to the decrease in liquid condensed in the
BPA region

 vapor flow and  internal reflux flow in the region above gas oil product draw
 vapor-liquid contact   quality of distillation  quality of naphtha, distillate, and gasoil
products   naphtha material in the distillate product ; distillate material in the naphtha and gas
oil product ; and gas oil material in distillate product 

Refinery Applications
In G02 Crude Distillation Unit, T-2 Atmospheric Crude Tower fractionates crude oil into intermediate
products that include fuel gas, LPG, naphtha, jet, distillate, atmospheric gas oil, and atmospheric
residuum.

In G04 Fluid Catalytic Cracking Unit, T-1 FCCU Main Column fractionates the cracked vapor
flowing out of the reactor.

In G02 Delayed Coker, T-1 Coker Main Column fractionates the cracked vapor flowing out of the
coke drums.

In G03 Hydrocracking Unit, T-10 Fractionator fractionates the cracked vapor flowing from 1st stage
and 2nd stage hydrocracking reactors.

Figure CP4-7. Increase in Quality of Distillation in T-1 Simple Fractionator

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CP5 Heat-Driven Hydrocarbon Stripping

Purpose Case 1:  concentration of the stripping medium in the vapor phase
 partial pressure of the impurities in the vapor phase 
To remove trace amounts of light materials from a heavier hydrocarbon stream with stripping vapor  impurities vaporized from the liquid phase into the vapor phase 
produced by an external heat source at the bottom of the tower. This process is employed when there is  stripping efficiency 
a very small amount of light hydrocarbons in the feed as compared to the amount of heavy hydrocarbons
in the bottom product. In most cases, the stripped content in the overhead gas product is primarily Case 2:  total pressure in all points in the tower
noncondensable hydrocarbons (C1 and C2) that were dissolved in the unstabilized product flowing from  partial pressure of the impurities in vapor phase 
an upstream process. Even trace amounts of these light noncondensable components in the stabilizer  impurities vaporized from liquid phase 
bottom product can result in pressure upset conditions in downstream processes and storage facilities.  stripping efficiency 

Functional Process Flow

T-1 Stabilizer. The configuration is similar to a basic distillation tower; it depends on the same vapor-
liquid interaction on multiple trays. The vapor traffic is created in the reboiler which vaporizes a portion
of the bottom product material. Most of this vaporized stripping material is ultimately condensed in the
tower and in the overhead condenser.

The stabilizer overhead product is referred to as wild naphtha, it consists of material that contains small
amounts of LPG, light naphtha components, and entrained noncondensables. The wild naphtha is recycled
to the front end of the Saturated Gas Plant.

Principles of Operation
Partial Pressure Concept. The following is focused on the stabilizer operation. In this case the objective is
to eliminate impurities which are noncondensable hydrocarbons and other light hydrocarbons to improve
quality of the bottom product. The same partial pressure concepts apply to all stripping processes.

Basics. The total pressure at any point in a stripping tower is equal to:
Figure CP5-1. Stabilizer (heat-driven stripper)
• Partial pressure of the impurities in the vapor phase
Refinery Applications
• Plus, partial pressure of stripping medium (hydrocarbons) in the vapor phase
In G05 SGP T-1 Deethanizer; In G06 USGP T-4 Stripper; In G11a VNHT T-2 Stripper
In this process, the stripping medium is hydrocarbon vapor generated by the reboiler.
In G12 ISOM T-2 Stabilizer; In G13 RFMR T-1 Stabilizer; In G11b CNHT T-3 Stripper

In G11C DHT T-2 Stripper

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CP6 Steam-Driven Stripping

Purpose
To remove trace amounts of light materials from a heavier hydrocarbon with steam as the stripping
medium. This process is employed when there are light hydrocarbons in the feed flowing into a
tower. In most cases, the stripped content in the overhead gas product is primarily noncondensable
hydrocarbons (C1 and C2) that were entrained in the feed. Even trace amounts of these light
noncondensable components in the bottom and sidedraw products can result in pressure upset
conditions in downstream processes and storage facilities.

Functional Process Flow

Sidestream Stripper Operation. Almost all fractionators incorporate steam strippers in side-draw
product circuits. Figure CP6-1 includes a stripper for the distillate sidestream product. Stripping
steam enters the bottom of the stripper to establish low partial pressure of the light hydrocarbons in
the vapor phase. This results in vaporization of the light hydrocarbon; and then, the steam sweeps
them up through the stripper and into the fractionator.

Bottom Stripping Operation. The same stripping process takes place in the bottom of the
Figure CP6-1. Simple Fractionator with Sidestream Stripper
fractionator to eliminate noncondensables and recover distillate from the bottom residue.

Principles of Operation
Hydrocarbon Partial Pressure. Stripping steam vaporizes light hydrocarbons by lowering partial
pressure of those hydrocarbons in the vapor phase. The light hydrocarbons are those with boiling
point temperatures below the temperature of the hydrocarbon liquid flowing into the stripper or
bottom of a fractionator.

Definition. In a mixture of gases, each gas component has a partial pressure; this is the hypothetical
pressure of that gas if it alone occupied the entire volume of the original mixture at the same total Figure CP6-2. Steam Stripping in Product Stripper and Fractionator Bottom
pressure. The following equation applies to steam entering the bottom of a fractionator and side
stream stripper. Refinery Applications
 stripping steam  percentage of light hydrocarbons in the vapor flowing through the tower  In G01 CDU T-2 Atmospheric Crude Tower; In G02 DCKU T-1 Coker Main Column
 partial pressure of light hydrocarbons in the vapor 
 vaporization of light hydrocarbons   stripping efficiency  In G03 HCU T-10 Fractionator; In G04 FCCU T-1 FCCU Main Column

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CP7 Hydrocarbon Absorption

Purpose Principles of Operation
Basics. The absorbent is a heavy hydrocarbon with a boiling point temperature much greater than
To capture condensable hydrocarbons from a vapor stream flowing from the bottom of the tower the boiling point temperature of targeted light condensables.
employing an absorbent flowing down from the top of the tower.
The temperature of the absorbent is much less than the boiling point temperature of the targeted
Functional Process Flow condensables.
Absorber Operation. The absorber operates similar to a basic distillation tower and depends on Mass Transfer. This takes place as the condensable gas components condense when they
the same vapor-liquid interaction on multiple trays. The liquid traffic is established with cool lean encounter the absorbent. The primary drivers in the process are absorbent temperature and
absorbent flowing into the top of the tower and gas feed with light condensables entering the absorbent-to-gas flow ratio.
bottom of the tower. As the gas bubbles up through the trays, the condensable molecules in the
gas bubbles encounter the absorbent, they condense and pass into the liquid phase. The rich Case 1:  lean absorbent temperature  condensation of condensables 
absorbent leaves the bottom of the tower.  mass transfer of condensables from gas phase to the liquid phase 

In this absorber: Case 2:  lean absorbent flow  absorbent-to-gas ratio 

 contact between condensables and absorbent 
• Noncondensables are C1 and C2 hydrocarbons
 condensation of condensables 
• Light condensables are C3s, C4s, C5s, and C6s  mass transfer of condensables from gas phase to the liquid phase 
• Cool Lean absorbent consists of C7s through C12s
Refinery Applications
In G01 Crude Distillation Unit, T-1 Preflash Tower employs stripped virgin distillate to absorb
heavy components entrained in the vapor rising out of the tower overhead.

In G05 Saturated Gas Plant, two absorption stages are needed. T-1 Deethanizer employs rich
sponge oil from T-2 Sponge Oil Absorber to capture the majority of the entrained condensables
from the fuel gas. T-2 Sponge Oil Absorber employs stabilized HCN as lean sponge oil to absorb
the remaining trace amounts of condensable components.

In G06 Unsaturated Gas Plant, two stages of absorption are needed. T-1 Absorber employs
unstabilized cat naphtha as absorbent to capture the majority of the entrained condensables content
from the fuel gas. T-2 Sponge Oil Absorber employs HCN as lean sponge oil to absorb remaining
trace amounts of condensable components.
Figure CP7-1. Hydrocarbon Absorber

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CP8 Hydrocarbon Molecule Cracking Concepts

Raw Crude vs. Market Demand
Raw crude oil is fractionated in the crude unit. As illustrated in figure
CP8-1, the resulting intermediate products require a significant amount of
processing to satisfy the refinery’s product slate based on market demand.
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 flowing out of the Crude Distillation
Unit. The barrel on the right illustrates the volumes in each barrel of
finished liquid product groups based on market demand. Key points:

• Over 50% of a medium crude oil is composed of very large molecules

in the gas oils and residuum groups; these have 17 or more carbon
atoms per molecule (C17+); but 95% of the refinery final product slate
comprises 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 crude
contains only 20% virgin naphtha (raw gasoline) per barrel with an
octane rating of less than 60.
Full Conversion Refinery
Hydrocarbon Cracking Process Units
The refinery front end includes three hydrocarbon cracking process units
-- Delayed Coking Unit, Hydrocracking Unit, and Fluid Catalytic
Cracking Unit. These crack low-value excess distillates, large gas oil, and
Figure CP8-1 Crude Oil Composition vs Market Demand vacuum residuum molecules into a full range of smaller molecules that
can be processed into high-value fuel products.

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G02 Delayed Coking Unit (DCKU) - Functional Process Flow DCKU - Principles of Operation
The DCKU employs, high temperature (typically 900 F) and extensive residence time (an average As illustrated in figure CP8-3, thermal cracking process is non-selective and produces large
of 30 minutes per molecule) to thermally crack very large vacuum residuum molecules with boiling volumes of all intermediate product groups that include coker gas oil, coker distillates, coker
point temperatures over 1050F; these contain 50 or more carbon atoms. The reaction takes place in naphtha, LPG and fuel gas. As illustrated in figure CP8-2, coke comprises very large aromatic
a hydrogen poor environment; this results in production of unsaturated hydrocarbon products and a molecules such as the C47 dense aromatic and free carbon molecules. The dense aromatics are
large volume of coke as a biproduct. The coke accumulates in the coke drum. tightly bound and very hard to crack. The hydrocarbon liquid product yield is typically 65% of
feed volume.
The vacuum residuum flows through the bottom of the Coker Main Column, through a fired heater,
enters the bottom of the coke drum, rises through coke bed channels, and accumulates on top of the
bed. The cracked products rise out of the drum into the sheds within the Coker Main Column.

Figure CP8-3. Thermal Cracking Reaction

Figure CP8-2 Delayed Coking Module

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G03 Hydrocracking Unit (HCU) - Functional Process Flow HCU – Principles of Operation
As illustrated in figure CP8-4, the HCU employs fixed catalyst beds, high temperature (typically 700F), and a high- In the example reaction illustrated in figure CP8-5, the catalyst is formulated
pressure (typically 1500 psig) hydrogen-rich environment to crack gas oil and/or excess distillates in the boiling range of to produce large volumes of cracked naphtha. The hydrogen-rich environment
315F to 850F. Hydrocracking takes place in two stages. In each stage the hydrocarbon feed passes through a fired results in production of saturated hydrocarbons; it also prevents coke
heater, mixes with circulating high-pressure hydrogen, and enters the top of the reactor. Each reactor comprises multiple accumulation on the catalyst. The expansion of liquid product yield is
catalyst beds. The reaction is highly exothermic; hydrogen is injected between the beds to control temperatures. typically 125% of feed volume. Catalyst can be formulated to produce large
volumes of gasoline or diesel blending components.

Figure CP8-5. Hydrocracking of a Gas Oil Molecule

Figure CP8-4. Hydrocracking in Fixed Bed Reactors

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G04 Fluid Catalytic Cracking Unit (FCCU) – Functional Process Flow FCCU – Principles of Operation
As illustrated in figure CP8-6, the FCCU employs fluidized catalyst and high temperature to crack Figure CP8-7 illustrates cracking in the FCCU. In this example, it cracks multiple bonds within
light and heavy vacuum gas oils in the boiling range of 650F to 1050F. Atomizing steam and a gas oil molecule containing 38 carbon atoms to produce a variety of smaller molecules
gas oils flow through feed nozzles into the mixing zone at the base of the reactor riser. As the oil containing fewer carbon atoms. One of the smaller molecules in the example shown is a 6-
encounters the very hot regenerated catalyst (typically 1300 F) the cracking process takes place carbon molecule that belongs to the light cat naphtha group (a high-octane gasoline blending
very rapidly (in seconds). The hydrogen-poor environment results in production of unsaturated component). The cracking process is selective; the catalyst is formulated to produce large
hydrocarbon products and coke (a carbon-rich biproduct). The coke accumulates on the fluidized volumes of cat naphtha or large volumes of light olefins (such as propylene and butylene). The
catalyst. The coke-bearing spent catalyst circulates through a regenerator where coke is removed expansion of liquid product yield results in an increase of liquid volume that is typically 108%
by spontaneous combustion with controlled volumes of air. This converts coke to carbon dioxide of feed volume.
and provides heat needed for molecule cracking taking place in the reactor riser.

Figure CP8-7. Fluid Catalytic Cracking Reaction

Figure CP8-6. Fluid Catalytic Cracking in Reactor Riser

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Cracking Severity – Principles of Operation

Severity is a general term that implies the degree to which cracking reactions are driven in
hydrocarbon processing. The hammer and anvil in figure CP8-8 serves as a useful physical
analogy. Breaking a chain link requires force applied by a hammer against an anvil. The
larger the chain link or the stronger the metal, the greater the force required to break the link.
The key contributing factors of breaking force in this domain are the speed and weight of the
hammer head.

The molecular graphic in the figure illustrates how cracking molecular bonds takes place in
refinery processes. This is similar to breaking metal chain links with force. Groups of atoms
are held together by molecular bonds in large gas oil molecules. The cracking reaction breaks
molecular bonds to create smaller molecules. The term severity refers to the molecular-bond-
breaking force. For larger molecules or stronger molecular bonds, greater severity is required
to crack them.

Severity Factors:
In the case of Fluid Catalytic Cracking Unit, the key factors are:

• Catalyst-to-oil ratio
• Riser top temperature
In the case of Hydrocracking Unit, the key factors are:

• Hydrogen partial pressure

• Temperature
• Catalyst activity
In the case of Delayed Coking Unit, the key factors are:

• Temperature
• Residence time

Figure CP8-8. Cracking Severity

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CP9 Amine Absorption and Regeneration

Purpose The amine solution includes process water; as the lean amine solution flows from the bottom of the amine regenerator
through the reboiler, it vaporizes a portion of the water content. This water vapor is the stripping medium that rises
To remove H2S from noncondensable gas (C1, C2, and H2) in amine through the regenerator trays and establishes a low partial pressure of H2S throughout the tower; this promotes stripping
absorbers and from LPG (C3-C4) liquid streams in amine contactors. As of the H2S from the liquid phase to the vapor phase and then sweeps the H2S into the tower overhead. Vapor leaving the
illustrated in figure CP9-1, in a cyclic sequence, Amine Absorbers and regenerator passes through a condenser where all but a very small amount of the water component condenses. H2S gas
Contactors capture the majority of H2S from gas and LPG liquid to produce and water separate in D-7 Reflux Drum. The concentrated H2S gas flows to the Sulfur Recovery Unit. The condensed
sweet overhead gas and liquid products. The Amine Regenerator strips the water flows back into the tower as reflux. The regenerated amine flows from the bottom of the reboiler up through E-3.
H2S molecules from the rich amine to regenerate the amine molecules to The lean amine temperature decreases as it transfers heat to the rich amine in E-3 and in E-2 (cooling water exchanger).
produce lean amine and H2S-rich amine acid gas. This establishes the optimum temperature needed to drive absorption in the amine absorber and contactor.

Functional Process Flow

Amine Absorber. Absorption takes place by establishing vapor-amine
interaction in the tower trays at a cool temperature. Lean amine solution is
cooled and then enters the top of the tower. Sour gas enters the bottom of the
tower and rises through the trays. When H2S molecules encounter the amine
molecules, ionic bonds form to absorb H2S into the liquid phase. The amine
solution leaving the bottom of the tower is ‘rich’ with H2S content. Sour gas
entering the bottom of the absorber may contain up to 3,000 ppm of H2S. At
the tower outlet, the product will typically contain less than 100 ppm of H2S.

Amine Contactor. This operates similar to the absorber. The difference is

that an amine contactor removes H2S molecules from a liquid LPG stream.
The LPG density is greater than the amine density; this results in a gravity-
driven downward flow of LPG against the upward counter flow of amine.
The packed bed contains irregular metal objects to promote interaction
between the sour LPG and the amine.

Amine Regenerator. The rich amine flows from the amine absorber and
contactor towers through E-3 (lean-rich heat exchanger). The heat transfer is
sufficient to raise the rich amine temperature needed to break the ionic bonds Figure CP9-1. Amine Absorption and Regeneration Chemistry
between amine and H2S molecules. Upon entering the top of the regenerator,
the H2S molecules in the rich amine do not readily pass into the gas phase.

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Principles of Operation As illustrated on the right side of figure CP9-1, the primary drivers for amine regeneration are rich amine
temperature at the E-3 shell-side outlet and steam-to-amine flow ratio in the regenerator.
Amine Composition. An amine molecule is a derivative of ammonia (NH3) formed
by replacing two hydrogen atoms with two hydrocarbon groups. The following is a Case 3: As it applies to amine regeneration  steam to reboiler  steam-to-amine flow ratio 
chemical representation of a simple amine molecule. As a standard in most amine  water vapor produced in the reboiler  H2S partial pressure throughout the tower 
chemistry literature, an amine molecule is represented by RNR where the two R's  stripping of H2S in liquid phase into the vapor phase 
represent the hydrocarbon groups on both sides of the nitrogen atom. The specific  H2S in the lean amine returning to the amine absorber and contactor 
type of amine used throughout this refinery is diethanolamine (DEA).

CP9-2. Amine RNR Composition

Establishing and Breaking Ionic Bonds. As illustrated in figure CP9-1, at low

temperature and high-pressure Amine establishes an ionic bond with H2S.

Primary Drivers. As illustrated on the left side of figure CP9-1, the primary drivers
for amine absorption are temperature, pressure, and amine circulation rate.

Case 1: As it applies to sour gas treatment  temperature

Figure CP9-1. Amine Absorption and Regeneration Chemistry (copy)
or  circulation rate or  pressure
 formation of ionic bonds between H2S and amine molecules (RNR)  Refinery Applications
 H2S absorbed from the vapor phase into the amine liquid phase 
 H2S in the rich amine   H2S in sweet gas In G05 SGP T-3 Amine Absorber and T-5 Amine Contactor

Case 2: As it applies to LPG treatment  temperature or  amine circulation rate In G06 USGP T-3 Amine Absorber and T-6 Amine Contactor
 ionic bonds between H2S and amine molecules 
In G11a VNHT T-1 Amine Absorber; In G11b CNHT T-8 Amine Absorber; In G11c DHT T-1 Amine Absorber
 H2S absorbed from the LPG phase into the amine liquid phase 
 H2S in the rich amine   H2S in sweet LPG  In G21 AMNU T-1 Regenerator; In G24 TGU T-8 Amine Absorber and T-3 Amine Regenerators

In G31 FGFS T-1 Fuel Gas Amine Absorber

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CP10 Hydrotreating
Purpose Hydrotreating Reactions. As illustrated in figure CP10-2, organic sulfur (S) and organic
nitrogen (N) are tightly bound in hydrocarbon molecules. The desulfurization and denitrification
To remove organic sulfur (S) and organic nitrogen (N) from naphtha and heavier hydrocarbon reactions crack the bonds holding the nitrogen and sulfur atoms; this is promoted by a hydrogen-
streams; this is needed to satisfy government-mandated fuel emission standards. Organic sulfur and rich environment, high temperature, high pressure, and specialized catalyst. The free S and N
nitrogen are also catalyst poisons in downstream reactors. Figure CP10-1 illustrates the general atoms then combine with hydrogen to form H2S (hydrogen sulfide) and NH3 (ammonia).
layout of most hydrotreaters.

Functional Process Flow

Feed Preparation. Feed to the reactor is a preheated mix of sour hydrocarbons and hydrogen.

Figure CP10-2. Hydrotreating-Removal of Sulfur and Nitrogen

CP10-1. Simple Hydrotreater

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H2S Processing. The hydrogen circulating from the D-21 Separator sweeps the H2S out of the Mild Hydrocracking. This is a side reaction taking place in all hydrotreating reactors. As
hydrotreated product. The T-1 Amine Absorber captures the H2S from the circulating hydrogen. The illustrated in CP10-3, hydrocracking occurs at the bonds within the central molecule; this
rich amine (loaded with H2S) flows into the Amine Unit (AMNU) located in the Sulfur Recovery produces light hydrocarbons. It is referred to as hydrocracking because it takes place in a
Complex. The central process in AMNU is an amine regenerator; it strips the H2S from the rich hydrogen-rich environment; hydrogen molecules are readily available to stabilize the molecules to
amine to produce amine acid gas (AAG). The acid gas flows into the Sulfur Recovery Unit where prevent release of free carbon molecules that would otherwise lay down as coke residue on the
the H2S is converted to pure sulfur and water. catalyst. A small amount of hydrocracking takes place in the CNHT and VNHT; these operate at
low severity. Hydrocracking in these units typically produces methane and ethane. The DHT
NH3 Processing. The ammonia leaves the hydrotreating reactors with the treated hydrocarbon catalyst is formulated to maximize hydrotreating reactions and minimize hydrocracking reaction.
stream, flows through a finfan cooler, and then into the separator drum. Water is injected upstream
of the cooler to absorb the ammonia and a small amount of hydrogen sulfide resulting in a sour
water solution. In D-21 Separator, the sour water gravity separates from the hydrocarbon and
accumulates in the boot at the bottom of the drum. The sour water flows into the Sour Water
Stripper (SWS) located in the Sulfur Recovery Complex. The SWS separates the NH3 from the
water to produce sour water acid gas (SWAG). The NH3 component of the gas is incinerated in the
front end of the SRU reaction furnace to produce pure nitrogen and water vapor.

Figure CP10-3. Hydrocracking Reaction

CP10-1. Simple Hydrotreater (copy)

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CP10 Principles of Operation Constant Severity Control. Figure CP10-4 illustrates how temperature control adjustments are
required to maintain constant severity in the reactor bed; this is needed to compensate for decrease
Reaction Severity. Severity is a general term to describe how hard the reactions are driven. The in catalyst activity from start of run (SOR) to end of run (EOR). The values shown are typical for a
primary drivers of severity are catalyst activity, reactor bed temperature, and hydrogen partial DHT. The same relationship applies to all other hydrotreaters. In this example, when the inlet
pressure. temperature adjustment to the reactor bed needed to maintain constant severity exceeds 800 F, the
 hydrogen purity or  hydrogen-to-feed ratio or  unit pressure catalyst must be replaced. Catalyst activity is monitored and recorded in units of F.
 hydrogen partial pressure   severity 

 severity  desulfurization  and denitrification  and hydrocracking 

Severity Implications. The DHT operates at much higher severity than VNHT and CNHT. This
is because the sulfur bearing molecules in the distillate and gas oil feed are larger and more
complex; also, the sulfur and nitrogen content is much greater. The impacts include:

• Much more hydrocracking takes place in the DHT than in VNHT and CNHT.
• DHT produces the majority of the H2S and NH3 in the refinery.
• DHT is the second highest consumer of hydrogen in the refinery.
• Hydrotreating and hydrocracking in the DHT are exothermic. The reactor is segregated into
multiple separate beds with an injection of hydrogen to cool the hydrocarbons flowing between Figure CP10-4. Rx Temperature vs Catalyst Activity Relationship
the beds.
Refinery Applications
Constant Hydrogen Partial Pressure Control. Hydrogen partial pressure is a major factor in
maintaining desired severity in the reactors. Hydrogen partial pressure is dependent on three G11a Virgin Naphtha Hydrotreater (VNHT) pretreats naphtha to prepare feeds to Light Naphtha
factors – unit pressure, hydrogen-to-feed ratio, and hydrogen purity. Hydrogen purity is Isomerization Unit and Reformer Unit. Organic nitrogen and sulfur are isomerization and reforming
maintained with a continuous purge of circulating hydrogen to maintain a low concentration of catalyst poisons.
noncondensable impurities, these are primarily C1 (methane) and C2 (ethane). This is the purpose
G11b Cracked Naphtha Hydrotreater (CNHT) treats heavy cracked naphtha produced in the Delayed
of bleed gas to the relief header.
Coker and Fluid Catalytic Cracking Unit to remove nitrogen and sulfur.

G11c Diesel Hydrotreater (DHT) treats atmospheric gas oil and distillates to satisfy government
mandated specifications for ultra low sulfur diesel (ULSD).

G03 Hydrocracking Unit (HCU) employs a hydrotreating reactor upstream of the first stage
hydrocracker.

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CP11 Caustic Scrubbing and Mercaptan Extraction

Purpose Mercaptan Extractor. This employs caustic to extract sulfur-bearing mercaptans from LPG hydrocarbons.
As illustrated in figure CP11-1, the mercaptans react with caustic to produce mercaptides and water. The
To remove H2S and sulfur-bearing mercaptan molecules from LPG (C3s and C4s) mercaptides are soluble in the caustic. The rich caustic (including mercaptides) circulates from the bottom
products employing amine absorption, caustic scrubbing, and mercaptan extraction of the extractor into the regenerator. Lean caustic (without mercaptides) flows from the regenerator into the
processes. top tray of the extractor.

Functional Process Flow Within the extractor, caustic density is greater than the LPG density resulting in counter flow of caustic and
LPG. Clean LPG (with 0 ppm sulfur) flows out the top of the tower. A key factor is that mercaptan
Amine Contactor. The purpose of the contactor is to remove the vast majority of the extraction reaction takes place very slowly. The tower is designed to provide adequate residence time and
H2S from the LPG. Typical H2S concentration in LPG is over 2000 ppm. The contactor the internals ensure sufficient LPG-caustic interaction needed to produce clean LPG.
employs an amine treating process to decrease H2S content in the LPG to less than
100 ppm.

Caustic Scrubber. The purpose of the caustic scrubber is to remove all remaining H2S
molecules from the LPG; the H2S would otherwise cause the sacrifice of caustic strength
and loss of expensive catalyst in the mercaptan extractor.

Caustic continuously circulates from the bottom of caustic scrubber drum into the LPG
upstream of the mixer. The turbulence within the mixer ensures a thorough mixing of the
LPG and caustic; the H2S molecules immediately react with the caustic to form sodium
sulfide which is soluble in the caustic phase. The LPG-caustic mix flows down a seal leg
into the bottom half of the drum. The LPG gravity separates into the upper half of the
drum and flows into the Mercaptan Extractor.

The H2S-caustic reaction in the caustic scrubber results in the sacrifice of two caustic
molecules for each H2S molecule. The NaOH (sodium sulfide) component is an impurity
in the circulating caustic; periodic replacement of spent caustic with fresh caustic is
necessary to maintain effective circulating caustic strength.

Figure CP11-1. LPG Caustic Scrubbing and Mercaptan Extraction

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CP11 Principles of Operation

Caustic Regeneration. One or more mercaptan extractors can be integrated with a caustic regenerator. This
significantly reduces the cost of hydrocarbon caustic treatment.

As illustrated in figure CP11-2, the caustic regeneration takes place in two major steps:

Step 1: Oxidation of mercaptides produce lean caustic and disulfide oil. A liquid catalyst (such as Merox)
within the circulating caustic promotes the oxidation reaction. NOTE: The catalyst does not have any effect
on mercaptan extraction reaction in the reactor.

Step 2: Separation of disulfide oil from the caustic phase. The caustic plus disulfide oil enters into a mixing
process with circulating wash oil. The disulfide oil components are soluble in the wash oil. The caustic and
wash oil with mercaptides gravity separates in multiple drums, the lean (regenerated) caustic recycles back
into the top of the mercaptan extractor tower. The rich wash oil with disulfide oil is recycled into the crude
distillation unit feed. There is a continuous flow of lean wash oil to replace the rich wash oil.

Table CP11-1. Differences between Caustic Scrubbing and Mercaptan Extraction

Caustic Scrubbing Mercaptan Extraction

Focus is on H2S removal Focus is on mercaptan removal
7 wt % caustic is optimum for the H2S removal 15 wt % caustic is optimum strength
Reaction takes place very rapidly Reaction is slow – requires long residence time
Figure CP11-2. Caustic Regeneration (disulfide oil removal)
Sacrificial process: 2 NaOH molecules are Can be sacrificial process with one NaOH
consumed for each H2S molecule removed consumed for each mercaptan molecule Refinery Applications
Requires continuous replacement of spent caustic With a catalyst, caustic can be regenerated on
with fresh caustic. site

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CP13 Heavy Oil Process Heater

Purpose Balanced Draft Operation. F-41 is a balanced draft heater. It incorporates K-42 (Forced Draft Fan), K-43
(Induced Draft Fan), and E-22. K-42 takes suction from the atmosphere and discharges the air through the tube
To efficiently increase the temperature of heavy oil feed to facilitate a downstream side of E-22 and into the burners. Air flow is controlled by adjusting louvers at the inlet of K-42 to provide
process while minimizing fuel costs and maintaining exhaust gas to the atmosphere target amount of excess O2 in the flue gas flow out of the stack. K‐43 takes suction from the stack below the
within the specification of the operating permit. stack damper, discharges it through the shell side of E-22, and back into the stack above the stack damper. Flue
gas flow is controlled by adjusting the louvers at the inlet of K-43 to maintain draft pressure less than
Functional Process Flow atmospheric pressure.
Heater Configurations. Figure CP13-1 includes two illustrations of F-41 (Heavy Oil
Heater). The diagram on the left depicts functional flow. The diagram on the right is a
detailed illustration of the heater internal operation.

The heat is created by mixing the right amount of air with fuel gas to produce a mixture
that efficiently combusts to generate heat in the burners. The heater is segregated into
two sections. The dominant heat transfer mechanism is different in each section.

Convection Section. Heavy oil enters tubes at the top of the heater convection section;
these direct crude flow back and forth as it works its way down through the structure.
Heat transfer is by convection; heat transfer takes place as the hot flue gas passes over the
outside of the tubes.

Radiant Section. The crude flows out of the convection section through the crossover
piping and enters the radiant section in the bottom region of the furnace. Heat transfer is
by radiation; heat radiates from the flames to the tubes directly and to the heater
refractory. Heat also radiates from the hot refractory to the tubes.

Air Preheat. The E-22 (Air Preheat Exchanger) transfers heat from the hot flue gas
flowing out of the heater stack to the combustion air flowing into the burners. This Figure CP13-1. F-41 Heavy Oil Heater Function Process Flow Diagram
decreases fuel consumption in the burners. By preheating the combustion air from
ambient temperature to over 600F, reduces the amount of fuel that would otherwise be
needed to heat the non-combustible components of the air (mostly nitrogen) up to the
burner temperature.

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CP13 Principles of Operation

Combustion. Feed to the burners consists primarily of methane and ethane; this is
true whether the source is fuel gas produced in the refinery or natural gas from
outside the refinery. Complete combustion of methane is represented by the
following equation:

CH4 + 2O2  CO2 + 2H2O

methane oxygen carbon water
dioxide

Excess oxygen is maintained to prevent incomplete combustion. As illustrated by the

equation below, a bi-product of incomplete combustion is carbon monoxide (CO);
this is an environmental pollutant.

2CH4 + 3O2  2CO + 4H2O

methane oxygen carbon water Figure CP13-1. F-41 Heavy Oil Heater Function Process Flow Diagram (copy)
monoxide
Refinery Applications
In G01 Crude Distillation Unit. F-41 Crude Heater and F-42 Vacuum Heater
Safety Factor--Heater Draft. Draft is the pressure at the top of the firebox; the
draft measurement instrument is located between the radiant and convection In G03 Hydrocracking Unit. F-41 1st Stage Charge Heater and F-42 2nd Stage Charge Heater
section of the heater. The objective is to maintain a draft pressure slightly below
atmospheric pressure; this is necessary to ensure a slight vacuum in the firebox In G02 Delayed Coking Unit. F-41 Coker Charge Furnace
for the following purposes:
In G04 Fluid Catalytic Cracking Unit. F-41 FCCU Feed Heater
• Prevents the outward flow of heat or flame from the firebox through any cracks or
holes in the heater walls. In G11C Distillate Hydrotreater. F-41 DHT Feed Heater
• Minimizes backpressure on the burners and thus prevents a fuel rich condition.

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