Refining processes handbook

REFINING PROCESSES
HANDBOOK

Surinder Parkash

AMSTERDAM BOSTON HEIDELBERG LONDON
NEWYORK OXFORD PARIS SANDIEGO
SANFRANCISCO SINGAPORE SYDNEY TOKYO
Gulf Professional Publishing is an imprint of Elsevier


Gulf Professional Publishing is an imprint of Elsevier.
Copyright © 2003 by Elsevier. All rights reserved.
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ISBN: 0-7506-7721-X
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Cover Photo by Mieko Mahi, energyimages.com


To My Wife
RITA


Preface
Petroleum refineries have grown rapidly in complexity and so, too, the
refinery operations. However, the published information on the refinery
processes and operation is scant and mostly confined to licensor's data,
which reveal little beyond what is absolutely necessary for process sale,
even when these processes have been in operation for a number of years
and in many refineries. This book is an overview of the processes and
operations concerned with refining of crude oil into products. The streams
coming from processing units are not finished products; they must be
blended to yield finished products. The refining operations presented here
are those concerned with blending products in an optimum manner with
the twin objectives of meeting product demand and maximizing refinery
profit. The objective here is to provide basic instructions in refinery
practices employing the methods and language of the industry.

Presented in the book are refinery processes, such as crude desalting and
atmospheric and vacuum distillation; gasoline manufacturing processes,
such as catalytic reforming, catalytic cracking, alkylation, and isomerization; hydrodesulfurization processes for naphtha, kerosene, diesel, and
reduced crude; conversion processes such as distillate and resid hydrocracking; resid conversion processes such as delayed coking, visbreaking, solvent
deasphalting, and bitumen manufacture; pollution control processes such as
sulfur manufacture, sulfur plant tail gas treatment, and stack gas desulfurization. Also presented here are operations performed in refinery off-site
facilities, such as product storage and blending, refinery steam and fuel
systems, refinery boiler feedwater treatment, and wastewater treatment.
The process details include processflowsheets,process description, chemistry involved, detailed operating conditions, process yields and utilities.
Among the refinery operations and practices presented are product blending,
refinery inventory forecasts, spreadsheet and LP modeling of refineries, and
methods for pricing crude oil, petroleum products, and intermediate stocks.
It must be recognized, however, that many variants of the same process
are found in the industry, and the operating conditions can be quite


diverse, depending on the type of catalyst used and feedstock processed.
We have insufficient space for bibliographic comparison and evaluations
of identical basic processes from different licensors. The data presented
here represent typical industrial operations practiced in refineries today.
Where no mention is made of recent contributions to the literature, no
slight is intended. The few references quoted are those where an industrial
practice is known to have originated.
Another important subject presented in this volume is concerned with
the operation of joint ownership refineries. Building a grassroots refinery
requires large capital investment. It is feasible for two companies to own
and operate a refinery as if it were build of two independent refineries.
Each company may operate its share of the refinery virtually independent
of other; that is, each company may bring in its own feedstock and
produce product slate independent of the other with no need to build

separate product storage facilities for the two companies.
The basic rules of operations of joint ownership refineries is discussed in
this book. A typical pro-forma processing agreement between the participants
is presented in the Appendix of this book. This covers detailed procedures for
refinery production planning, product allocation, inventory management, and
allocation of refinery operating cost to participants. Product allocation is the
split of total refinery production among the participants on the basis of the
feedstock processed by each. Keeping in view that the participants do not
process identical feedstocks or produce identical product grades, product
allocation for establishing the ownership of stock, must be done at the end
of every month. This is a complex exercise and a detailed procedure for this is
presented in a separate chapter.
The methods for preparing inventory forecasts and tracking refinery
operating expenses in a joint ownership refinery scenario are presented as
well. Even though such practices—product allocation, inventory and
ullage allocation, operating costs allocation—exist in refining industry,
there is no known literature examining them.

CHAPTER BREAKDOWN
Chapter 1 covers atmospheric and vacuum distillation and crude
desalting. Chapter 2 covers the refinery hydrotreating processes: naphtha
hydrotreating, kerosene hydrotreating, gas oil hydrodesulfurization
and atmospheric resid desulfurization. Chapter 3 presents the distillate
hydrocracking, mild hydrocracking, and resid hydrocracking processes.


Chapter 4 covers gasoline manufacturing processes: catalytic reforming,
alkylation, isomerization, catalytic cracking, and MTBE manufacture.
Chapter 5 looks at the manufacture of hydrogen for hydrotreating
and hydrocracking process and its recovery from some of the hydrogenbearing streams coming from these units. Chapter 6 presents refinery

residuum processing units, on delayed coking, visbreaking, solvent
deasphalting, and bitumen blowing.
Chapter 7 examines treating processes for catalytic cracker light and
heavy naphthas and kerosene-type jet fuels. Chapter 8 presents sulfur
manufacture and pollution control processes, such as sulfur plant, sulfur
tail gas treatment, and stack gas desulfurization.
Chapter 9 examines the refinery water system. This includes treatment
of cooling and boiler feed water, the refinery's oily waste water, and stripping the refinery's sour water.
Chapter 10 looks at the off-site and utility systems of a refinery. The
topics include the tankage requirements for product export and product
blending; batch and in-line product blending systems; refinery flare
system, including principals of flare system design; the refinery steam
system; and liquid and gaseous fuel systems.
Chapter 11 describes the procedures for product blending. Chapter 12
presents the procedure for preparing a refinery material balance using
a spreadsheet program. Chapter 13 describes the general principles
of building a refinery LP model. Chapter 14 discusses the mechanism
of pricing petroleum products, including intermediate streams and products. Chapter 15 describes the concept of a definitive operating plan for
the refinery during an operating period.
Chapter 16 shows the methodology behind product allocation in jointownership refineries. Chapter 17 explains methods of estimating available tankage capacity as a part of an inventory forecast system in both
single- and joint-ownership refineries. Chapter 18 explains how these
inventory forecasts are prepared for planning shipment of product in both
single-ownership and joint-ownership refineries. Chapter 19 presents
procedures for estimating the operating costs of the refinery and, in case
of joint-ownership refineries, the allocation of refinery operating costs to
the participants.
An appendix explains the organizational structure of joint-ownership
refineries and presents an example of a processing agreement among the
participants required for operating such a refinery.
We hope this book will serve as a useful tool for both practicing engineers

concerned with refinery operational planning as well as for academics.


Index

Index terms

Links

A
Alkylation
feed, product properties

138

operating conditions

136

process description

131

process variables

129

reactions

129

utility consumption

137

yields

137

Amine treating
amine properties

241

chemical reactions

236

feed and product composition

241

operating conditions

240

process (description)

238

utility consumption

240

239

Atmospheric resid desulfurization
catalyst

54

catalyst addition onstream

55

feed and product qualities

57

operating conditions

56

process description

50

process yields

57

utility consumption

58

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709


710

Index terms

Links

B
Bitumen Blowing
bitumen grades properties

207

feed and product properties

206

operating conditions

205

process description

205

utility consumption

206

C
Catalytic reforming
chemical reactions

110

feed and product properties

115

process description (semi-regenerative)

112

reforming yields

116

unit operating conditions

114

utility consumption

117

113

Claus tail gas treatment
catalyst

225

operating conditions

229

process description

226

process yields

230

system chemistry

223

utility consumption

230

229
227

D
Definitive operating program (DOP)
fixed and balancing grade products

505

input data

493

joint-ownership refineries

498

refinery DOP

499

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711

Index terms

Links

Delayed coking
coke properties and end uses

184

coke specifications

187

coking process description

176

177

feed and product qualities

185

186

operating conditions

182

process yields

184

utility consumption

184

Distillate treating
FCCU light gasoline treating

211

212

feed and product properties

213

218

general principles

210

jet fuel sweetening

214

operating conditions

217

215

F
Flue gas desulfurization
chemical reactions

231

feed and product properties

237

operating conditions

236

process description

232

utility consumption

237

232

233

Fluid catalytic cracking
catalyst

117

feed and product qualities

123

operating conditions

118

product yields

119

refinery FCCU unit

124

resid processing in

124

utility consumption

122

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179

712

Index terms

Links

H
Hydrocracking, distillates
catalyst

66

catalyst average temperature

81

catalyst fouling rate

82

catalyst regeneration

92

catalyst sulfiding and unit start up

88

feed and product qualities

77

feed specifications

64

operating conditions

75

process configuration

66

process flow scheme

69

process yields

80

reactions

62

shutdown procedure

90

utility consumption

81

76

Hydrocracking, mild
operating conditions

81

process yields

96

Hydrocracking, residuum
catalyst characteristics, metal deposited on

96

feed and product qualities

106

operating conditions

105

process yields

107

reactions

97

resid hydrocracker reactor

96

resid hydrocracker units

100

utility consumption

108

97

101

Hydrodesulfurization, gas oil
feed and product properties

48

operating conditions

47

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104


713

Index terms

Links

Hydrodesulfurization, gas oil (Continued)
process description

43

process yields

48

typical specifications

49

ultra low sulfur diesels

46

utility consumption

48

45

Hydrodesulfurization, naphtha
basic reactions

30

catalyst

34

feed and product properties

37

naphtha HDS process

34

operating conditions

36

operating variables

31

process yields

37

utility consumption

38

35

Hydrogen (partial oxidation process)
operating conditions

165

process yields

165

synthesis gas generation

166

utility consumption

166

167

Hydrogen production (steam reforming)
chemical reactions

163

feed and product qualities

160

natural gas desulfurization

153

operating conditions
HT shift reactor

156

LT shift reactor

157

methanation reactor

158

primary reformer

154

process description

156

process yields

159

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714

Index terms

Links

Hydrogen production (steam reforming) (Continued)
PSA route, H2 manufacture

162

utility consumption

159

Hydrogen recovery
feed and product properties

173

feed treatment

170

operating conditions

172

process yields

174

PSA system

173

utility consumption

174

Hydrotreating, kerosene
feed and product properties

42

kero (DPK) fuel specifications

44

operating conditions

41

process description

38

process utilities

43

process yields

43

39

I
Inventory (for shipping) forecasts
allocation of deltas

641

forecasting system; inventory and ullage

646

refinery estimate schedule

639

weekly production estimates

638

671

Isomerization (C5/C6) normal paraffins
catalyst

140

feed and product properties

145

hydrocarbon contaminants

140

isomerization process

141

operating conditions

143

properties of C5/C6 paraffins

138

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715

Index terms

Links

Isomerization (C5/C6) normal paraffins (Continued)
unit yields

144

utility consumption

144

J
Joint-ownership refineries
processing agreement

691

refinery DOP

499

L
LP modeling (refinery)
assay table

447

capacities, process units

424

CDU and VDU models

447

CDU submodel structure

460

delta based modeling

443

distributive recursion

436

feed availability

418

interpreting solution

440

LP model structure

417

objective function

439

process yields

420

product blending

426

product demand

419

property propagation to other tables

430

report writer program

443

row and column names

417

single product LP blender

471

stream pooling

431

user defined rows

423

utility, catalyst and chemical consumption

423

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716

Index terms

Links

LP modeling (refinery) (Continued)
vacuum distillation unit modeling

468

M
MTBE manufacture
chemical reactions

147

feed and product properties

152

operating condition

150

process description

146

process variables

150

process yields

151

utility consumption

151

148

O
Operating cost (refinery)
cost allocation per actual usage

684

leasing, tankage capacity

687

operating cost allocation

682

operating cost elements

681

system costing method

682

TSRV method

682

unused capacity charge

684

P
Pricing (refinery streams)
assigned crude yield and pricing

488

energy

487

formula pricing of crude

480

fuel oil cutters

486

netback pricing of crudes

476

products and intermediate stocks

481

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717

Index terms

Links

Pricing (refinery streams) (Continued)
vacuum gas oils

485

Product allocation
balancing grades

536

crude changes

534

DOP loss adjustment

535

examination of allocation LP results

551

final allocation

542

final allocation example

560

forecaster changes rules

521

forecaster compensating changes

532

input data for allocation

521

LP’s (final allocation)

545

preliminary allocation example

537

559

556

problems in allocation
allocation of refinery fuel consumption

613

allocation of sulfur production in refinery

612

dumping kerosene in diesel

567

elimination of negative inventories

616

‘intank’ sale and purchase between participants

611

reblending of finished products

612

simulation of reduction in a conversion unit severity

614

product prices for allocation LP's

548

retrospective OOP

536

reverse allocation

537

spreadsheet program (allocation)

561

unit capacities in allocation LP’s

545

557

Product blending

aniline point

341

ASTM distillation

314

flashpoint

331

336

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718

Index terms

Links

Product blending (Continued)
fluidity of fuel oils

369

gasoline octane

308

pour, cloud and freeze

330

RVP of gasoline, naphtha

339

viscosity

326

340

Product blending systems
blending, batch

278

280

blending, continuous in-line

283

284

blending, partial in-line

282

Product equivalencies
calculation

514

crude oil, equivalency of

518

slop, equivalency of

519

Properties (narrow cuts) estimation
aromaticity factor

369

ASTM distillation from TBP

359

bureau of mines correlation index

368

cetane index of diesels

368

characterization from API and viscosity

363

diesel index

368

flash point

366

heating value (lower)

364

‘K’ Watson; from ASTM distillation

361

luminometer number of kerosenes

367

molecular type composition

375

molecular weight

363

narrow cut properties from assay

343

Ramsbottom from Conradson carbon

365

refractive index

373

smoke point of kerosenes

366

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719

Index terms

Links

Properties (narrow cuts) estimation (Continued)
vapor lock protection temperature

321

vapor pressure

365

viscosity determination from two reference points

379

viscosity kinematic conversion to SUS and SFS

371

wide cut properties from narrow cuts

357

R
Refinery distillation
assay, crude

5

atmospheric distillation unit

18

characterization of unit fractionation

11

desalting (of crude)

22

flash zone conditions

7

operating conditions

23

petroleum fraction properties

14

TBP, ASTM and EFV curves

3

tower, process design

5

utility consumption

24

vacuum distillation; operating conditions

24

vacuum distillation unit

20

19
25

21

Refinery stock balancing
calculation procedure

386

data for model building

385

diesel blending

391

fuel oil blending

390

material balance spreadsheet program

388

unit capacities and operating factors

386

Refinery tankage
allocation of capacity

622

available capacity, estimation of

620

634

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27


720

Index terms

Links

Refinery tankage (Continued)
ceding of refinery capacity

635

LI and HI calculations

621

product groups for

622

shipping terminals and sea lines

272

storage temperature

275

tankage requirements, estimation

273

tanker fleet distribution

277

Refinery utilities
electric system, refinery

300

flare endothermic

295

flare, ground

296

flare, pollution control

293

flare smokeless

293

flare system

286

flare system design

286

home fuel system

303

steam system

298

299

process description

200

201

utility consumption

200

yield and product qualities

199

294

S
Solvent deasphalting of resids

Sulfur recovery
chemical reactions

220

Claus sulfur recovery process

221

operating conditions

224

process yields

225

utility consumption

225

222

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302


721

Index terms

Links

V
Visbreaking process
feed and product properties

194

operating conditions

192

process yields

193

utility consumption

193

visbreaking process

189

190

W
Water systems

API separators

258

cooling towers

246

cooling water system

242

DAF separator

259

liquid effluent; discharge to sea

255

properties, potable water

253

properties, sea water

245

sour water treatment

261

system, fire water

253

system, sea water cooling

243

system, utility water

251

system, wet slop

260

treatment, boiler feed water

247

treatment, sanitary sewage

261

263

treatment, waste/oily water

254

257

244

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245


Contents

Preface ....................................................................................

xii

Chapter Breakdown ...................................................................

xiii

Refinery Distillation ........................................................

1

Process Variables .....................................................................

2

Process Design of a Crude Distillation Tower ...........................

5

Characterization of Unit Fractionation .......................................

11

General Properties of Petroleum Fractions ...............................

14

Atmospheric Distillation Unit ......................................................

18

Vacuum Distillation Unit ............................................................

20

Crude Desalting .........................................................................

22

1.

2.

3.

Distillate Hydrotreating .................................................. 29

Naphtha Hydrodesulfurization Process .....................................

34

Kerosene Hydrotreating ............................................................

38

Gas Oil Hydrodesulfurization .....................................................

41

Atmospheric Residuum Desulfurization .....................................

50

Hydrocracking Processes .............................................. 62
Hydrocracking Reactions ..........................................................

62

Process Configuration ...............................................................

66

Process Flow Scheme ...............................................................

69

Operating Conditions .................................................................

75

Catalyst Sulfiding and Unit Startup ............................................

88

Shutdown Procedure .................................................................

90

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vii


viii

4.

Contents
Catalyst Regeneration ...............................................................

92

Mild Hydrocracking ....................................................................

95

Residuum Hydrocracking ..........................................................

95

Gasoline Manufacturing Processes .............................. 109
Catalytic Reforming ................................................................... 109
Fluid Catalytic Cracking ............................................................. 114
Alkylation ................................................................................... 128
Isomerization of C5/C6 Normal Paraffins .................................... 136
Methyl Tertiary Butyl Ether ........................................................ 143

5.

Hydrogen Production and Recovery ............................. 153
Natural Gas Desulfurization ...................................................... 153
Steam Reforming ...................................................................... 156
Carbon Monoxide Conversion ................................................... 157
Carbon Dioxide Removal .......................................................... 158
Methanation ............................................................................... 162
Pressure Swing Adsorption Route ............................................ 162
Partial Oxidation Process .......................................................... 164
Hydrogen Recovery ................................................................... 170

6.

Residuum Processing .................................................... 176
Delayed Coking ......................................................................... 176
Visbreaking ................................................................................ 189
Solvent Deasphalting ................................................................ 197
Bitumen Blowing ........................................................................ 203

7.

Treating Processes ......................................................... 210
General Principles ..................................................................... 210
FCCU Light Gasoline ................................................................ 211
Jet Fuel (ATK) Sweetening ........................................................ 214
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Contents
8.

ix

Sulfur Recovery and Pollution Control Processes ...... 220
Sulfur Recovery from Acid Gas ................................................. 220
Claus Tail Gas Treatment ......................................................... 223
Flue Gas Desulfurization ........................................................... 228
Amine Treatment ....................................................................... 235

9.

Refinery Water Systems ................................................. 242
Cooling Water System ............................................................... 242
Sea Water Cooling System ....................................................... 243
Cooling Towers ......................................................................... 246
Boiler Feedwater System .......................................................... 247
Utility Water System .................................................................. 251
Treatment of Oily Water ............................................................ 257
Wet Slop Oil System ................................................................. 260

Treatment of Sanitary Sewage .................................................. 261
Sour Water Treatment ............................................................... 261

10. Refinery Off-site Facilities and Utility Systems ............ 270
Refinery Tankage ...................................................................... 270
Shipping Terminals and Sea Lines ............................................ 272
Refinery Tankage Estimation .................................................... 273
Product Blending System .......................................................... 278
Refinery Flare System ............................................................... 286
Refinery Steam System ............................................................. 298
Refinery Fuel System ................................................................ 303

11. Product Blending ............................................................ 308
Gasoline Octane Blending ......................................................... 308
ASTM Distillation Blending ........................................................ 314
Viscosity Blending ..................................................................... 326

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x

Contents
Pour Point Blending ................................................................... 330
Flash Point Blending ................................................................. 331
Reid Vapor Pressure Blending for Gasolines and Naphthas ..... 339
Aniline Point Blending ............................................................... 341
Crude Oil Assays ....................................................................... 342

12. Refinery Stock Balancing .............................................. 384

Data for Model Building ............................................................. 385
Calculation Procedure ............................................................... 386
Refinery Material Balance Spreadsheet Program ..................... 388

13. Refinery Linear Programming Modeling ....................... 415
Overview ................................................................................... 415
Development of the Refinery LP Model ..................................... 415
The Structure of a Refinery LP Model ....................................... 417
Property Propagation to Other Tables ....................................... 430
Blending Specifications ............................................................. 431
Stream Pooling (Recursion Process) ........................................ 431
Distributive Recursion ............................................................... 436
Objective Function ..................................................................... 439
Optimization Step ...................................................................... 439
Solution Convergence ............................................................... 440
Interpreting the Solution ............................................................ 440
Report Writer Programs ............................................................ 443
Delta-based Modeling ............................................................... 443
Atmospheric Crude Distillation and VDU Modeling ................... 447
Single-product LP Blender ........................................................ 471

14. Pricing Petroleum Products ........................................... 476
Netback and Formula Pricing for Crude Oil ............................... 476
Pricing Petroleum Products and Intermediate Stocks ............... 481
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Contents

xi

Assigned Crude Yields .............................................................. 488

15. Definitive Operating Plan ............................................... 493
DOPs in Joint-ownership Refineries .......................................... 498
Fixed- and Balancing-grade Products ....................................... 505
Product Equivalencies ............................................................... 510
Product Equivalency Determination .......................................... 514
Crude Oil Equivalency ............................................................... 518
Equivalency of Slop ................................................................... 519

16. Product Allocation .......................................................... 520
Input Data .................................................................................. 521
Forecaster Changes .................................................................. 521
Rules for Forecaster Changes ................................................... 521
Crude Oil Changes .................................................................... 534
DOP “Loss” Adjustment ............................................................. 535
Retrospective DOP .................................................................... 536
Allocation of Balancing Grades ................................................. 536
Reverse Allocation .................................................................... 537
Final Allocation .......................................................................... 542
Allocation LPs ............................................................................ 545
Process Unit Capacities ............................................................ 545
Product Prices ........................................................................... 548
Summary of Primary Data Input for LPs .................................... 551
Examination of LP Results ........................................................ 551
Final Allocation Cycle ................................................................ 556
Allocation Spreadsheet Program ............................................... 561
Product Allocation Problems ..................................................... 567

17. Available Tankage Capacity ........................................... 620
Estimation of Total Available Capacity ...................................... 620
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