Crude to chemicals: Part 1 – The basic
concept of crudes
Reactor platforms with novel heat integration designed around advanced separation
techniques and catalyst systems achieve 75% yields from selected crudes
Kandasamy M Sundaram, Ujjal K Mukherjee, Pedro M Santos and Ronald M Venner
Lummus Technology
S
team crackers traditionally use ethane, LPG, and naph-
tha as feedstock. Occasionally, heavier hydrocarbons
such as gasoils and unconverted oil from hydroc-
racking units have been utilised. Lummus Technology, CLG
(Chevron Lummus Global), and Saudi Aramco Technologies
Company have conducted intense joint research over sev-
eral years to understand the implications of steam cracking
crudes heavier than very light crudes and condensates. The
research involved understanding the distribution of molec-
ular species within the crude, including the very complex
structures in asphaltenes.
Advanced separation techniques avoiding conventional
crude atmospheric/vacuum distillation systems, appropriate
catalysts, and integrated reactor platforms with novel heat
integration permit the consistent yield of high-value chem-
icals from crude to increase to higher than 75%. Strategic
hydrogen addition optimises the molecular species for opti-
mum cracker yields and maximises ethylene plant heater
run lengths.
One important result that contributed to the success-
ful commercialisation award in 2020 was the elimination
of low-value stream production, such as pyrolysis gasoils,
even while processing heavier hydrocarbon feeds. Heat
integration, operability and reliability were key parameters
in the development, as was the significant reduction of
overall Capex, Opex, plot space, and CO₂ footprint.
Olefins and on-demand fuels production
Annually more than 200 million metric tons of ethylene are
produced worldwide. Most of the ethylene comes from the
thermal cracking of hydrocarbons, such as ethane, LPG,
naphtha, and hydrocracked vacuum gasoil (VGO). Steam
crackers produce very high-purity products suitable for
downstream polymer and chemicals production (for exam-
ple, 99.95% pure ethylene). Stringent feed specifications
are imposed when the feed is destined for steam cracking.
Thermal cracking, denoted as steam cracking in the indus-
try, is one petrochemical process that uses very high energy
and emits significant quantities of CO₂.
A typical naphtha cracker emits from 1.2 to 1.8 kg CO₂/
kg C₂H₄. When the ethylene plant is integrated with a
refinery, the feeds, products, and energy (especially steam/
electricity) are exchanged between the units for improved
efficiency. LPG and naphtha feeds used in the cracker are
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usually obtained from crude by separation in a distillation
train, an energy-intensive process. Do we really need crude/
vacuum distillation to obtain feeds to produce olefins?
Novel methods employed to process crude for produc-
ing olefins while bypassing the refinery will be further
discussed. This reduces the energy, Opex, Capex, and CO₂
emissions. Although, in principle, any crude can be used as
feed, some are more economically attractive than others.
A primary optimisation parameter is to maximise ethylene,
propylene, and other valuable chemicals while minimising
fuels but maintaining the flexibility to produce on-demand
fuel products.
Ethylene production
Most ethylene is produced by thermally cracking hydrocar-
bons mixed with dilution steam in the vapour phase at low
pressures/high temperatures in tubular reactors without
catalyst. The product recovery section consists of com-
pression, many distillation columns, and cryogenic fluids
as coolants. Fired heaters are used to supply the energy to
the cracking reactions. Heat is recovered primarily as super
high pressure (SHP) steam (100+ bar) that is used to drive
the compressors in the recovery section. Modern cracking
furnaces achieve more than 94% overall thermal efficiency.
Direct crude cracking has been studied since the 1960s
but has never been commercialised due to poor economics.1
With continued research and development in various dis-
ciplines, features such as the proprietary Short Residence
Time (SRT)/low-pressure drop coils led to superior olefin
selectivity and reduced feed consumption. Ethylene capac-
ity has increased from 25 KTA per furnace in the 1960s to
300 KTA per furnace today, and single-train plant capacity
has increased from 300 KTA to more than 2,000 KTA. The
feeds have not changed, but the once-through yields have
improved substantially. The latest innovations in crude
cracking to improve refinery economics (TC2C and heavy
oil processing scheme, HOPS) are discussed at recent
conferences.2-4
Fundamentally, thermal cracking proceeds via free radi-
cal mechanism;5,6 hence, low hydrocarbon partial pressure
and short residence time favour higher olefin selectivity.
However, during this process, side reactions leading to the
formation of coke occur. Coke, a solid phase, deposits on
the walls of the reactor and increases coil pressure drop
PTQ Q4 2023 43

800
700 Arab Superlight
Bonny Light
Arab Medium
600
LAPA-Hvy
Alg. Cond.
500
TBP, ˚C
400
300
200
100
0
0 20 40 60 80 100
Volume distilled, %
Figure 1 Different types of crudes and Condensate: 1-Arab
Superlight (API=49.6, MCR=0.48 wt%), 2-Bonny Light
(49.6, 1.24), 3-Arab Medium (30.9, 5.4), LAPA Brazil (22.7,
7.0); Dashed line-Algerian Condensate (70.1, 0.0009)
and tube metal temperature, which limits ethylene produc-
tion. Periodically, the heater must be steam/air decoked.
When the frequency of cleaning is increased, it may not be
economical to crack that feed.
Typically, Lummus SRT heaters run between 30 and 60
days before a cleaning is required. When contaminants are
present in the feed, the run length between decoking can be
reduced significantly. Cracking is a homogeneous reaction
and hence is independent of coil surface-to-volume ratio,
but coking reactions are surface dependent. Though chem-
ical reaction engineering principles can be used to improve
the run length to some extent, feeds or reactor designs that
result in short heater run lengths are not preferred.
The difference between traditional feeds such as naphtha
or gasoil and crude is the run length of the heater. Typically,
when crudes are used as feeds, the run length can be a matter
of hours. Therefore, crudes were not considered good feeds
for olefin production in traditional coil technology. In addition,
each type of feed requires optimum processing conditions;
hence, even with good-quality crude, the ethylene yield will
not be high if optimum conditions are not chosen. How do
we achieve maximum performance with crude cracking?
Crudes
Unlike ethane or propane, crude is not a single species but
a mixture of species boiling from very low temperatures
(~10°C) to very high temperatures (>700°C) with compo-
sitions that vary widely. Typical distillation curves for some
light and heavy crudes are shown in Figure 1. Material boil-
ing above 525°C is typically called residue. They cannot be
cracked in pyrolysis heaters since the residue feeds cannot
be vapourised completely, and the residue deposits as coke.
These crudes are currently sent to a refinery crude dis-
tillation unit (CDU) after going through a desalter and then
separated into different cuts, such as naphtha, kerosene,
diesel, VGO, and residue. These cuts are made to specifi-
cations (such as specific gravity, distillation range, and sul-
phur) so that these cuts can be used as fuel or processed
in downstream units. When the fractions from the crude
44 PTQ Q4 2023
distillation tower do not meet the required specifications
of transportation fuels such as gasoline, the fractions must
be processed in other units, such as fluid catalytic cracking
(FCC), hydrocracking, and many other units.
When not used as fuels, these cuts are sent to olefin
plants as feeds. Olefin plant feeds must meet certain con-
taminant levels and boiling ranges. Ethylene plants can
tolerate a wide range of feed properties when properly
designed. Therefore, some of the refinery operations can
be bypassed when used for olefin production. Field con-
densates are often used as cracker feeds. These are much
lighter than crudes but contain some characteristics similar
to crude.7 For example, the distillation curve of an Algerian
condensate feed is also shown in Figure 1. When these
condensates are cracked without proper heater design, the
heater run lengths are very short.
The Algerian condensate shown in Figure 1 is success-
fully cracked in many plants only when it is successfully
vapourised in the convection section coils without coking.
It also has some unwanted contaminants (Hg & As) at high
levels, which cause problems in the recovery section. If not
properly handled, they will damage the recovery section.
Therefore, for every crude, the effect of the contaminants
with respect to olefin plant operation is important.
Without a detailed compositional analysis, it cannot
be predicted which crude is suitable for steam cracking.
Typically, light crudes have low levels of contaminants.
Super light crudes are almost like field condensates. Super
light crudes and condensates have a high fraction (>60%) of
naphtha boiling range material (<200ºC) in the whole crude
and a small fraction of residue (<5%) that boils above 525ºC.
Inspection of many crudes shows that many light and super
light crudes are potential candidates as olefin plant feeds.
When sulphur is present at high levels, a larger acid gas
(H₂S) removal system must be used in the ethylene plant.
In addition, other sulphur species such as mercaptans and
thiophenes act as catalyst poisons for the hydrogenation
reactors within the ethylene plant, making the ethylene
plant more expensive. Often high sulphur crudes contain
other contaminants such as high micro carbon residue
(MCR) and high levels of basic nitrogen species. Though
high sulphur can be removed in the ethylene plant, it may
not be worthwhile spending extra Capex in the ethylene
plant for a large acid gas removal system. It is better to
condition the feed in the refinery and reduce the sulphur
content. When there is no refinery near the petrochemical
complex, it is preferable to consider crudes with less than
0.5 wt% sulphur for ethylene production due to economic
reasons. The basic crude-to-chemicals scheme outlined in
this discussion can be used for any type of crude.
Crude to chemicals scheme
Many light crudes with low sulphur can be economically
processed to produce ethylene. High residue-contain-
ing crudes cause short heater run length. What are good
feeds to produce olefins? As shown in Figure 2, normal
paraffins are the best feeds to produce olefins, especially
ethylene. Normal paraffins produce very high ethylene
and propylene yields. Isoparaffins produce lower ethylene
www.digitalrefining.com
 multi-ring aromatics, the principal components of fuel oil,
90 are produced in place of solid carbon. Fuel oil components
80 N. paraffins are so-called coke precursors that will produce solid coke
Ultimate ethylene yield, wt%

70
60
50
40
30
20
10
0
0 5
Carbon number
Figure 2 Ethylene yield potential as a function of carbon
number
yields and comparable propylene yields to normal paraffins.
Naphthenes produce less ethylene and propylene yields
than isoparaffins. Aromatics produce very low ethylene and
propylene yields. Multi-ring aromatics produce almost no
olefins and high amounts of fuel oil that forms coke.
The hydrogen content of olefins (C₂H₄, C₃H₆) is 14.3
wt%. The hydrogen content of aromatics is exceptionally
low, and multi-ring aromatics have even lower hydrogen
content (often <8 wt% H). Therefore, a feed with higher
hydrogen content than mono-olefins (14.3%) can eas-
ily dehydrogenate (lose hydrogen) and produce an olefin.
A feed with lower hydrogen content than an olefin must
reject carbon to produce an olefin for carbon-hydrogen bal-
ance. Carbon is a solid and hence hydrogen-deficient feeds
will shorten the heater run length.
This is a simple rule applicable to all types of pyrolysis
technologies. Rarely in practice is elemental carbon found
in pyrolysis coils. Hydrogen-deficient products such as
nP
35 Multi-ring naphthenes
Naphenoaromatics
Porphyrin
30 Polar polyfunctional
compounds
i. paraffins eventually. Thermodynamically, the ultimate products of
Napthenes
Aromatics thermal cracking are carbon and hydrogen.
By manipulating reactor operating conditions, we max-
imise intermediate products. One of the intermediate prod-
ucts is ethylene. Thus, reactor design and operations play
a vital role in maximising ethylene for any feed. Hence, for
high ethylene production, it is preferable to crack feeds
with reasonable or high hydrogen content in feed. In that
PNA respect, light crudes with high paraffin content also have a
10 15 20 25 higher ethylene potential than heavy crudes; the selection
of crude is important for good economic return.
The type of compounds present in a crude can be used to
illustrate the salient features of crude cracking technology.
Altgelt and Boduszynski⁸ studied the type of compounds
present in a typical crude as a function of atmospheric
equivalent boiling point. A crude characterisation is shown
in Figure 3. In every crude and condensate feed, all these
classes of species are present, although the quantity (or
concentration) of each species varies in each crude.
Every crude contains normal and isoparaffins, mono and
multi-ring naphthenes, mono and multi-ring aromatics,
hydrocarbons with sulphur, nitrogen, oxygen, and metals
(heteroatoms) containing straight chain and/or ring com-
pounds. The species that contain heteroatoms are generally
called polar species. For any given carbon number, normal
paraffin has the lowest boiling point, and polynuclear polar
and non-polar compounds have the highest boiling points.
For example, Figure 4 shows different C₂₀ species.
As shown in Figure 4, nC₂₀H₄₂ (eicosane) boils at 343ºC
while C₂₀H1₂ (perylene) boils at 468ºC. C₂₀H12 is a highly
condensed molecule with four rings surrounding a benzene
ring and has the lowest hydrogen content (4.8 wt%). A
four-ring aromatic compound with some side chains, C₂₀H1₈
(butyl pyrene) boils slightly lower than C₂₀H₁₂ (BP=407ºC).
C₂₀H₁₂ is a highly hydrogen-deficient molecule compared
to nC₂₀H₄₂.
Hence C₂₀H₁₂ and C₂₀H1₈ will produce mainly coke rather
than ethylene. It is the aim of this technology to remove
these species selectively and keep the hydrogen-rich spe-
cies in the cracker feed slate.

25
Separation strategies
Carbon number

Figure 4 shows that boiling point is one measure of sep-

20
arating hydrogen-rich species from hydrogen-deficient
species. By limiting the boiling point, the concentration
15
of multi-ring compounds can be reduced in the cracker
feed. Thermodynamically, they cannot be easily removed,
10
but concentrations can be reduced to acceptable levels.
5
Therefore, cut points are critical parameters. A crude dis-
tillation column contains many theoretical stages, and the
Naphtha AGO VGO Residue
overlapping between various fractions is small. That prin-
0 90 200 320 430 540 650 ciple is followed in the technology developed by Lummus
Atmospheric equivalent boiling point, ˚C
Technology in HOPS, which has been in operation for con-
densate cracking for many years.
Figure 3 Carbon number vs atmospheric equivalent boiling This is further improved in Lummus’ patented crude
point for different classes of species cracking technology.⁹ The concept is explained in Figure

46 PTQ Q4 2023 www.digitalrefining.com

 CH3

Tetradecylcyclohexane CH2 Perylene

C20H40 CH2 C20H12
Butyl perylene
Eicosane CH2 H H
C20H18 H H
nC20H42 H H
H H
H H
H H
H H
H H
H H H H
H
BP = 343˚C BP = 358˚C BP = 407˚C BP = 468˚C
H = 15 wt% H = 14.3 wt% H = 7.0 wt% H = 4.8 wt%
H/C = 2.1 H/C = 2.0 H/C = 0.9 H/C = 0.6
D = 0.787 g/cc d = 0.8219 d = 1.13 d = 1.3

Best Olefin yields Worst Olefin yields

Very Low coking Very High coking

Figure 4 Characterisation of different C₂0 species

5 for crude cracking. Desalted crude is preheated to mod-
erate temperatures in the convection section and sent to
the HOPS unit. Here, the crude feed is mixed with super-
heated dilution steam. The HOPS unit contains trays and/
or packing. Dilution steam reduces the hydrocarbon partial
pressure and reduces the vapourisation temperature. The
overhead temperature is controlled, and only the vapour
(vapourised hydrocarbons + dilution steam) is sent to the
lower portion (hot flue gas region) of the convection sec-
tion for further superheating and then cracked in the radi-
ant section.
With the improved HOPS design, the cut-point overlap
is significantly reduced. First-generation HOPS units have
been successfully operating since the 1990s for conden-
sate cracking. Condensates are like light crudes with the tail
portion end boiling point well over 700ºC. The bottom frac-
tion of the HOPS unit (unvapourised crude) can be sent to
another heater for further preheating and then to another
HOPS tower and/or processed further by different technol-
ogies, such as hydrocracking, fluid catalytic cracking, and
delayed coking. When using a second HOPS, it is known
as two-stage HOPS. One can consider two or three stages

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www.digitalrefining.com PTQ Q4 2023 47

 ethylene yield. The residue contains a significant portion of
Cracking Heater asphaltene molecules.
convection section
Asphaltene is a class of high molecular weight com-
Crude pounds containing many heteroatoms (S, N, O, and met-
als). Considerable research has been done in recent years
FPH
to understand these compounds.¹0 These are multi-ring
compounds with very high molecular weight and are pres-
ent in peptised form in the crude. Depending upon ther-
modynamic conditions, they will separate out and cause
UMPH
coking. By removing these species from crude, processing
the remaining portion of crude is easier. These molecules
should not enter the cracking heater.
There is a direct relation between the asphaltene content
of crude and MCR. Therefore, potential crudes with high
MCR should be avoided. Conversion of asphaltenes rather
DSSH
Dilution steam Residue/liquid
than rejection through processes such as solvent deas-
phalting (SDA) forms the basis of special reactor platforms
(liquid circulation or slurry bubble) and catalyst systems,
LMPH
Lights through VGO cut which form part of the new crude-to-chemicals scheme.

Crude to olefins
Processing more than one cut of crude and cracking them
To Radiant section optimally in different heaters maximises olefins. For each
species, there is an optimum cracking condition that will
Figure 5 One stage HOPS unit for crude cracking give maximum ethylene yield or maximum ethylene + pro-
pylene or other combinations. Note that the cracking reac-
and select appropriate boiling (cut) points, depending on tion proceeds via a free radical mechanism, and hence the
the crude properties. One or two stages are adequate for initiation rate controls the overall rate. Up to certain tem-
most feeds. peratures, both ethylene and propylene yields increase with
The bottom stream of the final HOPS unit (residue) is sent increasing coil outlet temperature.
to fuel or for further processing as it is not processed in the The mechanism dictates that the largest olefin reaches
radiant coils for olefin production. The amount of residue the maximum first and then the smaller olefins. Ethylene is
removed depends upon the crude quality. Controlling this primarily formed from ethyl radical decomposition, which is
residue portion is critical since this material primarily pro- the main reaction in the thermal cracking of all hydrocarbon
duces coke during the vapourisation process in the convec- species. It can be shown one cut of crude from C5 to 525ºC
tion section, radiant section and transfer line exchangers. boiling range will not produce optimum olefin yields for a
The amount of dilution steam and the level of superheat light crude. Calculations show 2-3 HOPS stages are rea-
dictate the maximum possible cut point for the crude. sonable, and often two stages are sufficient.
Rejecting the residue from processing in the cracking heat- In the first stage, the cut end point is selected around 160-
ers leads to improved run length and better once-through 240ºC (pseudo-naphtha cut) and in the second stage, a
350-525ºC end point (pseudo-gas
oil cut) is selected depending upon
Different ideal cuts of Arab Light crude
the crude and the scope of the pro-
ject. When three cuts are produced
Cut# 1 2 3 4
(three-stage HOPS), naphtha, gas-
Name Naphtha & light AGO cut VGO cut Residue
oil and VGO cuts are produced.
Cut point, ºC <160 160-350 350-525 525C+
Yield of crude, wt% 18.83 32.77 24.80 23.61
The heaviest portion (residue) is
S.G. 0.7112 0.8322 0.9162 1.0133 rejected. Generally, residue is mixed
Sulphur, wt% 0.04 0.83 2.64 4.16 with fuel oil produced in the pyroly-
Nitrogen, wt% 0.00 0.00 0.06 0.25 sis unit and sold as a product. As an
Metals, ppm 0.00 0.00 1.68 63.50 example, the properties of different
MCR, ppm 0.00 0.00 0.33 16.55 cuts are shown in Table 1 for Arab
Paraffins, wt% 74.79
Light crude. Typically, naphtha feed
Naphthenes, wt% 16.78
Aromatics, wt% 8.43
will produce 30 wt% ethylene and 5
Polyaromatics, wt% 0.00 8.76 52.09 >60 wt% fuel oil. Gasoil will produce 26
C7 Asphaltenes, wt% 0.00 0.00 0.20 3.84 wt% ethylene and 16 wt% fuel oil,
H-Content, wt% 15.4 13.6 and VGO will produce more than 20
wt% fuel oil yield, and the residue is
Table 1 not cracked. Even when the crude is

48 PTQ Q4 2023 www.digitalrefining.com

fractionated with HOPS or using a CDU, the overall fuel oil reactors and other process reactor designs. He holds a Bachelor’s
production is excessively high on a crude basis. degree in chemical engineering from Madras University, a Master’s in
While Part 1 has discussed basic concepts of crudes to chemical engineering from the Indian Institute of Science, and a PhD
chemicals, Part 2 will expand on the use of hydroprocess- from the University of Ghent, Belgium.
Email: kandasamy.sundaram@Lummustech.com
ing technology to maximise the chemicals.
Ujjal Mukherjee is Chief Technology Officer, responsible for Lummus’
existing portfolio and the development of technologies at the forefront
References
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and a Master’s in business administration from Rutgers University, US.
2 Masen T, Santos P, TC2CTM – Thermal crude to chemicals – A
Email: ujjal.mukherjee@lummustech.com
unique technology maximizing crude to chemicals, ERTC, Madrid, Nov
Pedro Santos is Technology Director leading the commercial deployment
17-18, 2020.
and further technology development of Thermal Crude to Chemicals
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(TC2C™), a technology co-developed by Saudi Aramco Technologies
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Company, Lummus Technology, and Chevron Lummus Global. He
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crude to chemicals, presented at the AIChE spring meeting, Houston,
Institute of technology, and he has been granted five patents related to
March 13-16, 2023.
crude to chemicals. Email: pedro.santos@lummustech.com
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Ronald Venner is Chief Business Officer, Clean Fuels, leading the
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from pyrolysis of normal and branched paraffins, Ind.Eng.Chem.
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Fundam. 22, 132-139, 1983.
Chevron Lummus Global. He holds a Bachelor’s degree in chemistry
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and a Master’s in chemical engineering from Manhattan College.
application, presented at Refining, LNG and petrochem Asia 92, Dec
Email: ronald.venner@lummustech.com
1-4, Singapore.
8 Altgelt K H, Boduszynski M M, Composition and Analysis of Heavy
Petroleum Fractions, Marcel Deckker, NY, 1994. LINKS
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More articles from: Lummus Technology
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of sediment deposition in the LC-FINING Process, Energy & Fuels, 22, Crude to Chemicals
3226-3236, 2008. Crude and Vacuum Units
Emissions Reduction
Kandasamy M Sundaram is a Technologist responsible for pyrolysis

www.digitalrefining.com PTQ Q4 2023 49