The Refinery of the Future

643 Pages·2020·11.411 MB·English

by  James G. Speight

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Contents
Preface ix
1 Feedstocktypesandproperties 1
1.1 Introduction 1
1.2 Terminology 3
1.3 Occurrence andreserves 17
1.4 Ultimate(elemental)composition 20
1.5 Chemicalcomposition 21
1.6 Fractional composition 23
1.7 Crudeoilproducts 35
1.8 Petrochemicals 38
References 39
2 Introductiontorefiningprocesses 43
2.1 Introduction 43
2.2 Refineryconfigurations 45
2.3 Refineryprocesses 48
2.4 Thefuture 82
References 83
3 Refiningchemistry 85
3.1 Introduction 85
3.2 Cracking 86
3.3 Hydroprocesses 99
3.4 Otherreactions 105
3.5 Instabilityandincompatibility 109
3.6 Thefuture 119
References 121
4 Distillation 125
4.1 Introduction 125
4.2 Currentprocessesandequipment 126
4.3 Otherprocesses 139
4.4 Thefuture 147
References 158
5 Thermalcracking 161
5.1 Introduction 161
vi Contents
5.2 Earlyprocesses 163
5.3 Commercialprocesses 166
5.4 Processoptionsforheavyfeedstocks 180
5.5 Thefuture 188
References 194
6 Catalyticcracking 197
6.1 Introduction 197
6.2 Earlyprocesses 200
6.3 Commercialprocesses 200
6.4 Catalysts 212
6.5 Processoptionsforheavyfeedstocks 215
6.6 Thefuture 221
References 225
7 Deasphaltinganddewaxing 227
7.1 Introduction 227
7.2 Commercialdeasphaltingprocesses 228
7.3 Commercialdewaxingprocesses 243
7.4 Thefuture 248
References 254
8 Desulfurization,denitrogenation,anddemetalization 257
8.1 Introduction 257
8.2 Rationaleforhydroprocesses 260
8.3 Processoptions 261
8.4 Processparameters 267
8.5 Reactors 270
8.6 Commercialprocesses 273
8.7 Processoptionsforheavyfeedstocks 279
8.8 Catalysts 282
8.9 Bioprocesses 287
8.10 Thefuture 292
References 298
9 Hydrocracking 303
9.1 Introduction 303
9.2 Commercialprocesses 306
9.3 Catalysts 311
9.4 Processoptionsforheavyfeedstocks 320
9.5 Thefuture 337
References 341
10 Non(cid:1)fossilfuelfeedstocks 343
10.1 Introduction 343
Contents vii
10.2 Biomass 344
10.3 Waste 381
References 387
11 Productionoffuelsfromnonfossilfuelfeedstocks 391
11.1 Introduction 391
11.2 Typesoffuels 394
11.3 Fuelproduction 397
References 426
12 SynthesisgasandtheFischer(cid:1)Tropschprocess 427
12.1 Introduction 427
12.2 Gasificationofcoal 428
12.3 Gasificationofcrudeoilfractions 434
12.4 Gasificationofotherfeedstocks 446
12.5 TheFischer(cid:1)Tropschprocess 448
12.6 Fuelsandpetrochemicals 451
12.7 Thefuture 461
References 467
13 Typesandpropertiesoffuelsfromnonfossilfuelsources 469
13.1 Introduction 469
13.2 Gaseousfuels 470
13.3 Liquidfuels 480
13.4 Solidfuels 496
13.5 Fuelquality 508
References 513
14 Abiorefinery 515
14.1 Introduction 515
14.2 Thebiorefinery 517
14.3 Processoptions 521
14.4 Benefits 541
References 544
15 Therefineryofthefutureandtechnologyintegration 549
15.1 Introduction 549
15.2 Refineryconfigurations 550
15.3 Thefuturerefinery 566
References 576
Conversionfactors 579
Glossary 589
Index 627
Preface
The petroleum refining industry includes integrated process operations that are
engagedin refining crude petroleum intorefined petroleum products,especially liq-
uidfuelssuchasgasolineanddieselaswellasprocessesthatproducerawmaterials
forthepetrochemicalindustry.
Over the past four decades, the refining industry has experienced significant
changes in oil market dynamics, resource availability, and technological advance-
ments. Advancements made in exploration, production, and refining technologies
allow utilization of resources such as heavy oil and tar sand bitumen that were con-
sidered economically and technically unsuitable in the middle decades of the past
century. Along with the many challenges, it is imperative for refiners to raise their
operations to new levels of performance. Merely extending today’s performance
incrementallywillfailtomeetmostcompany’sperformancegoals.
Petroleum refining in the 21st century may continue to be shaped by the factors
suchasconsolidationofoilcompanies,dramaticchangesinmarketdemand,customi-
zation of products, and a decrease in the API gravity and sulfur content of the petro-
leum feedstocks. In fact, in addition to a (hopeful but unlikely) plentiful supply of
petroleum, the future of the refining industry will base on the following factors such
as (1) increased operating costs or investments due to stringent environmental
requirements for facilities and products and (2) accelerating globalization resulting in
stronger international petroleum price scenarios. The effect of these factors is likely
to reduce refinery profit margins further, and petroleum companies worldwide will
need to make significant changes in their operation and structure to be competitive
on global basis. Development and incorporation of novel technologies to cope with
thefuturechallengesareessentialtoremaincompetitiveinthebusiness.
As global petroleum consumption increases and resources are depleted, it is
expected that conventional oil production will decline within the next two to three
decades, and the production of oil from residua, heavy oil, and tar sand bitumen
will increase significantly. In fact, over the next decade, refineries will need to
adapt to receiving heavier oils as well as a range of biofeedstocks. It is conceivable
that current refineries could not handle such a diverse slate of feedstocks without
experiencingshutdownsandrelatedproblems.
As feedstocks to refineries change, there must be an accompanying change in
refinery technology as petroleum feedstocks are becoming highly variable. At the
same time, more stringent antipollution regulations are forcing greater restrictions
on fuel specifications. There are fundamental limitations on how far current pro-
cesses can go in achieving proper control over feedstock behavior. This means a
movement from conventional means of refining heavy feedstocks by using
x Preface
(typically) a cooking process to more development and use of more innovative pro-
cesses that will produce the maximum yields of liquid fuels (or other desired pro-
ducts)fuelsfromthefeedstock.
With the changing face of refining, the use of tailor-made technologies will pro-
vide the edge tomove ahead.This is more sowhenthe refining marginsare shrink-
ing day to day due to several emerging factors such as stringent product qualities,
strict environmental regulations, changing feedstock properties, and high prices for
petroleumfeedstocks.
Thus the need for the development of upgrading processes continues in order to
fulfill the product market demand as well as to satisfy environmental regulations.
One area, in particular, the need for residuum conversion, technology has emerged
as result of declining residual fuel oil market and the necessity to upgrade crude oil
residua beyondthe capabilitiesofthevisbreaking,cooking,andlow-severityhydro-
desulfurizationprocesses.
With the arrival of the 21st century, the refining industry has entered a signifi-
cant transition period, and it is not surprising that refinery operations have evolved
to include a range of next-generation processes as the demand for transportation
fuels, and fuel oil has shown a steady growth. These processes are different from
one another in terms of the method and product slates and will find employment in
refineriesaccordingtotheirrespectivefeatures.Theprimarygoaloftheseprocesses
is to convert heavy feedstocks, such as residua, to lower boiling products, and such
processesarenotedinthisbook.
This book will present to the reader the evolution of refinery processes during
the last century and develop as well as the means by which refinery processes will
evolveduringthenextthree-to-fivedecades.Chapterswillcontainmaterialrelevant
to (1) comparisons of current feedstocks with heavy oil and biofeedstocks, (2) evo-
lution of refineries since the 1950s, (3) properties and refinability of heavy oil and
biofeedstocks, (4) thermal processes versus hydroprocesses, and (5) evolution of
productstomatchtheenvironmentalmarket.
Technological advancesare on the horizon for alternate sourcesof transportation
fuels. For example, gas-to-liquids and biomass-to-liquids are just two of the con-
cepts currently under development. However, the state of many of these technolo-
gies coupled with the associated infrastructure required to implement them leaves
traditional refining of petroleum hydrocarbons for transportation fuels as the modus
operandi for the foreseeable future, which in this context is seen to be 50 years.
The near future challenge for refiners will be how to harness new technologies to
remainaliveinachangingglobalmarketplace.
It is imperative for refiners to raise their operations to new levels of perfor-
mance. Merely extending current process performance incrementally will fail to
meet most future performance goals. To do this, it will be necessary to reshape
refining technology to be more adaptive to changing feedstocks and product
demand and to explore the means by which the technology and methodology of
refinery operations can be translated not only into increased profitability but also
intosurvivability.
Preface xi
Furthermore, there is considerable uncertainty surrounding the future of uncon-
ventional crude oil production in the United States. Environmental regulations
could either preclude unconventional production or, more likely, raise the cost sig-
nificantly. If future US laws limited and/or taxed greenhouse gas emissions, these
lawswillleadtosubstantialincreaseinthecostsofproductionoffuelsfromuncon-
ventionalsources.Inadditiontoincreases inthe volumes ofcarbondioxide, restric-
tions on access to water also could prove costly, especially in the arid or semiarid
Western States. In addition, environmental restrictions on land use could preclude
unconventional oil production in some areas of the United States. Such policies
could opentoway tothe increased use ofbiomassfeedstocks asameans ofsupple-
mentingproductionofhydrocarbonfuels.
However, the refinery of the future will be more technology focused than
today—a trend that has already commenced. It will make only high-value products,
with one of those products being power. The refinery will be a clean refinery with
a high-value, energy-efficient installation insofar as the refinery environmentally
benign and the carbon footprint of the refinery will be negligible. The refinery will
also be a smart refinery insofar as it will highly to accept a variety of feedstocks
(including biomass) with operations managed around chemical principles and quan-
titativechemicalreactionengineeringconcepts.
Chapter 1, Feedstock Types and Properties, introduces the book by giving an
overview of the properties of various feedstocks, including biomass. Chapter 2,
Introduction to Refining Processes, and Chapter 3, Refining Chemistry, focus on
refining processes and refining chemistry. Chapters 4(cid:1)9 deal with distillation, ther-
mal cracking, catalytic cracking, deasphalting and dewaxing, hydrotreating and
desulfurization, and hydrocracking, respectively, including the introduction of bio-
technology into the refinery (Chapter 8: Desulfurization, Denitrogenation, and
Demetalization). Chapters 10(cid:1)15 are new to this edition and present the potential
for the accommodation of nonfossil fuel feedstocks and the means by which these
feedstockscanbeusedtoprovidevarioustypesoffuels.
By understanding the evolutionary changes that have occurred to date, this book
will satisfy the needs of engineers and scientists at all levels from academia to the
refineryand help them understand the current refining industry and prepare for pro-
cesschangesandevolutionoftheindustry.
The target audience includes engineers, scientists, and students who want an
update on petroleum processing and the direction of the industry over the next 50
years. Nontechnical readers, with help fromthe extensive glossary,will also benefit
fromreadingthebook.
JamesG.Speight
CD&WInc.,Laramie,Wyoming,UnitedStates
March2020
1
Feedstock types and properties
1.1 Introduction
Themoderncrudeoilindustrybeganinthelateryearsofthe1850swiththediscov-
ery and subsequent commercialization of crude oil in Pennsylvania in 1859 (Bell,
1945; Yergin, 1991; Bower, 2009). The modern refining era can be said to have
commenced in 1862 with the first appearance of crude oil distillation. The story of
the discovery of the character of crude oil is somewhat circuitous but worthy of
mention,inthehistoricalsense(Burke,1996).
At a time when the carbonation of water was being investigated, Joseph Priestley
became involved in attemptingto produce such liquid since it was to be used a cure
for scurvy during the second expedition made by Captain Cook in 1771. Priestley
decided to make a contribution to the success of the expedition and set himself to
invent a drink that would cure scurvy. During his experiments at a brewery near his
home in Leeds, he had discovered the properties of the carbon dioxide (he called it
“fixed air”) given off by the fermenting beer vats. One of these properties was that
whenwaterwasplacedinaflatdishforatimeabovethevats,itacquiredapleasant,
aciduloustastethatremindedPriestleyofseltzermineralwaters.
Experiments convinced him that the medicinal qualities of seltzer might be due
to the air dissolved in it. Pouring water from one glass to another for 3minutes in
the fixed air above a beer vat achieved the same effect. By 1772 he had devised a
pumping apparatus that would impregnate water with fixed air, and the system was
set up on board ships Resolution and Adventure in time for the voyage by Cook. It
was a great success. Meanwhile, the politics expounded by Priestley continued to
dog him. His support for the French Revolution was seen as particularly traitorous,
and in 1794 a mob burned down his house and laboratory. As a result, Priestley
(who escaped the wrath of the mob) took ship for Pennsylvania, where he settled in
Northumberland, honored by his American hosts as a major scientific figure. Then
one night, while dining at Yale, he met a young professor of chemistry. The result
oftheirmeetingwouldchangethelifeoftheUnitedStatesinthe20thCentury.
It may have been because the young man at dinner that night, Benjamin Silliman,
was a hypochondriac (rather than the fact that he was a chemist) that subsequent
eventstookthecoursetheydid.Sillimanimaginedthathesufferedfromlethargy,ver-
tigo, nervous disorders, and whatever else he could think of. In common with other
invalids, he regularly visited health spas such as Saratoga Springs, New York (at the
expense of his mother), and he knew that such places were only for the rich. The
meeting with Priestley apparently moved Silliman to decide to make the mineral-
watercureavailabletothecommonpeople(alsoattheexpenseofhismother).
TheRefineryoftheFuture.DOI:https://doi.org/10.1016/B978-0-12-816994-0.00001-4
©2020ElsevierInc.Allrightsreserved.
2 TheRefineryoftheFuture
In1809SillimansetupinbusinesswithanapothecarynamedDarling,assembled
apparatus to impregnate 50 bottles of water a day and opened two soda-water foun-
tains in New YorkCity, one at the Tontine Coffee House and one at the City Hotel.
The decor was hugely expensive (a lot of gilt), and they only sold 70 glasses on
opening day. But Darling was optimistic. A friend of Priestley visited and declared
that drinking the waters would prevent yellow fever but in spite of Silliman’s hopes
that the business would make him rich, by the end of the summer the endeavor was
adisastrousflop.Itwouldbemanymoredecadesbeforethesodafountainbecamea
culturaliconinAmerica!
Silliman cast around for some other way to make money. Two years earlier, he
had analyzed the contents of a meteor that had fallen on Weston, Connecticut, and
this research had enhanced his scientific reputation. So he decided to offer his ser-
vices (as a geologist) to mining companies. His degree had been in law: he was as
qualifiedforgeologyashewastobeYaleprofessorofchemistry.Thegeologyven-
ture prospered, and by 1820 Silliman was in great demand for field trips, on which
he took his son, Benjamin, Jr. When he retired in 1853, his son took up where he
had left off, as professor of General and Applied chemistry at Yale (this time, with
a degree in the subject). After writing a number of chemistry books and being
elected to the National Academy of Sciences, Benjamin, Jr. took up lucrative con-
sulting posts,ashis father had done,withthe Boston City Water Company andvar-
iousminingenterprises.
In 1855 one of these asked him to research and report on some mineral samples
from the new Pennsylvania Rock Oil Company. After several-month work,
Benjamin, Jr. announced that approximately 50% of the black tar-like substance
could be distilled into first-rate burning oils (which would eventually be called ker-
osene and paraffin) and that an additional 40% of what was left could be distilled
for other purposes, such as lubrication and gaslight. On the basis of this single
report, a company was launched to finance the drilling of the Drake Well at Oil
Creek, Pennsylvania, and in 1857 it became the first well to produce crude oil. It
would be another 50 years before the reference by Silliman to other fractions avail-
able from the oil through extra distillation would provide gasoline for the combus-
tion engine of the first automobile. The report by Silliman changed the world
because it made possible an entirely new form of transportation and helped turn the
UnitedStatesintoanindustrialsuperpower.
After completion of the first well (by Edwin Drake), the surrounding areas
were immediately leased and extensive drilling took place. Crude oil output in
the United States increased from approximately 2000 barrels (1barrel, bbl542
US gallons535 imperial gallons55.61ft35158.8L) in 1859 to nearly
3,000,000bbl in 1863 and approximately 10,000,000bbl in 1874. In 1861 the
first cargo of oil, contained in wooden barrels, was sent across the Atlantic to
London, and by the 1870s, refineries, tank cars, and pipelines had become char-
acteristic features of the industry, mostly through the leadership of Standard Oil
that was founded by John D. Rockefeller. Throughout the remainder of the 19th
century, the United States and Russia were the two areas in which the most strik-
ing developments took place.
Feedstocktypesandproperties 3
At the outbreak of World War I in 1914, the two major producers were the
United States and Russia, but supplies of oil were also being obtained from
Indonesia, Rumania, and Mexico. During the 1920s and 1930s, attention was also
focused on other areas for oil production, such as the United States, the Middle
East, and Indonesia. At this time, European and African countries were not consid-
ered major oil-producing areas. In the post-1945 era, Middle Eastern countries con-
tinued to rise in importance because of new discoveries of vast reserves. The
United States, although continuing to be the biggest producer, was also the major
consumer and thus was not a major exporter of oil. At this time, oil companies
began to roam much farther in the search for oil, and significant discoveries in
Europe,Africa,andCanadathusresulted.
Crude oil refining has grown increasingly complex in the last 20 years. Lower
quality crude oil (such as heavy crude oil, extra heavy oil, and tar sand bitumen),
crude oil price volatility, and environmental regulations that require cleaner
manufacturing processes and higher performance products present new challenges
to the refining industry. Improving processes and increasing the efficiency of
energy use withtechnologyresearch anddevelopment are keys to meeting the chal-
lenges and maintaining the viability of the refining industry in the United States
and the production of the hydrocarbon fuels upon which the modern world is
dependent.
It is the purpose of this chapter to present a general description of the types of
feedstocks that are currently accepted by refineries and to illustrate the evolution of
the acceptance of these feedstocks from the original conventional crude oil for
whichtherefinerieswereconstructed.
In the simplest definition, a refinery feedstock is the crude oil produced from a
reservoir (a geological formation) by means of one or more wells drilled into the
formation that is destined for processing in a refinery. By this means the crude oil
is transformed into one or more components and/or finished products (Parkash,
2003;Garyetal.,2007;Speight,2014,2017;HsuandRobinson,2017).
1.2 Terminology
Even though crude oil and its derivatives have been used for millennia, it is only in
the last decade or so that some attempts have been made to standardize the nomen-
clature and terminology. But confusion may still exist. Therefore it is the purpose
of this section to provide some semblance of order into the disordered state that
existsinthesegmentofcrudeoiltechnologythatisknownasterminology.
1.2.1 Conventional crude oil
The term “crude oil” and the equivalent term “petroleum” cover a wide assortment
ofmaterialsconsistingofmixturesofhydrocarbonderivativesandothercompounds
containing variable amounts of sulfur, nitrogen, and oxygen, which may vary