PEMA 2021 RP2 Petrochemicals Tbpresented

From Oil and Gas to Polymers and Plastics
Refining and Petrochemicals

in the world of energy
N°2 to be presented
Robert PELLETIER PEM Akamigas
© R.Pelletier 2021
pelandco@yahoo.fr
Oct-Nov, 2021
Total Prof. Refining Petrochemicals 1
Introduction
Overall program of the module (to be confirmed)
▪ Day 1. October 4, 2021. Introduction to the module. “Safety first”.
▪ Day 2. October 5. Global view of Refining and Petrochemicals in world of energy
▪ Day 3 and 4. October 6 and 11. Polymers and Plastics. Definitions. Why such a high
growth rate? Diversity, adaptability. (Start-up of a “mini project”, by teams of ~5
students : to be confirmed).
▪ Day 5. November 3. Main problems in polymerization plants. “From arrival of raw
materials to delivery at customer gate” (1/2). Assessment of progress in mini project (to be
confirmed).
▪ Day 6. November 9 (date to be confirmed). Main problems in polymerization plants.
“From arrival of raw materials to delivery at customer gate” (2/2)
▪ Day 7. November 22. Presentation by the two best teams of each group of their work
in the “mini project” (to be confirmed). Small (open book) exam
© R.Pelletier 2021
▪ Day 8. November 21. Polymers and environment. Conclusion of the module.
Total Prof. Refining and Petrochemicals 2
Introduction
Detailed program of the module (1/3)
▪ D1 Introduction to the module. Review of content. Small poll among students about
different materials. “Safety first”: the absolute priority of all works by all employees and
partners.
▪ D2 Global view of the petrochemical chain in world of energy, leading mostly to

polymers and plastics. Energy. Exergy. Orders of magnitude of its economic importance.
Mass balance of world petrochemical industry. What future for the polymer markets?
▪ D3 and 4 Polymers and plastics. Definitions: (monomers, polymers, molecular weight,

molecular weight distribution, …). Various polymerization mechanisms: Polyaddition,
polycondensation. Initiators and catalysts. Copolymers (random, alternate, block, grafted,
reactivity ratios). Modifiers and additives: their critical influence on polymer properties (glass
transition temperature, haze, ...). Polymer characterization: melt index, MWD, shear-thinning
properties, impact strength, optical properties.
Start-up of mini project (to be confirmed)
© R.Pelletier 2021
Introduction
▪D5 and 6. Main problems in polymerization plants: “From arrival of raw materials to
delivery at customer gate”.
Monomers: stability, inhibition, purity and consistency. Explicit and implicit quality
requirements. Dramatic influence of tiny (ppb level) concentrations of impurities.
Polymerization engineering: heat of polymerization, heat removal in highly viscous or solid
media. Various types of polymerization reactors (in mass or in diluent; solution, slurry, gas phase,
suspension, emulsion). Residence time distribution: batch, semi-batch, plug-flow, CSTR reactors.
Use of cascade of reactors (catalyst efficiency, control of molecular weight distribution, influence
on particle size distribution and homogeneity).
Catalyst injection and reactor extraction: safety issues in those complex operations. Reaction
run-away: means to prevent such potentially catastrophic events.
Polymer finishing: recovery and degassing: influence on polymer quality. Storage in silos.
© R.Pelletier 2021
Introduction
▪ D7 “Mini project”. Presentation by the selected teams. Presentation should be on a
powerpoint format with only five significant slides. (To be confirmed)
Small open book exam. Rather easy exam for those who listened carefully. Students
will have to answer to questions from lecturer, then immediately send those answers
by email to the lecturer. (Delayed answers won’t be accepted).
▪D8 Polymers and environment. Can the high growth rate of polymer markets be sustainable?
Plastics now the “villains” among materials. A necessary tool “Life cycle analysis”. Surprising
examples, very in packaging, transport industry, buildings and construction.
End of life. Polymer recycling, energy recovery. Why are polymers different from glass or steel?
Biopolymers. Biodegradation: a poor solution to a real problem. Bio sourced polymers: waiting
for 2nd generation, not in competition with food market.
General conclusion of the program. Methodology of polymer development. Importance
© R.Pelletier 2021
of perfect unity between research, product and process development.

Refining & Petrochemicals
belong to world of energy
But, what is “energy” ? Your definition, please?
© R.Pelletier 2021
Refining & Petrochemicals belong to world of energy
Small recap: What is energy?

▪ The ability of a system to do work or produce a change.
No activity is possible without energy
▪ Energy, in itself, is immaterial, even though it needs physical

supports to be stored or transported
▪ The various forms of energy:

• Mechanical
• Electrical
• Chemical = intra-molecular energy
• Nuclear = intra-atomic energy released by fission or fusion reactions,
(with a conversion from mass into energy, according to E = mc2)
• Radiant, typically energy as received from the sun (not usable for storage, no
material support)
© R.Pelletier 2021
• Thermal = kinetic energy of molecules (the less valuable form of energy,
into which all other forms tend to be downgraded)

What is energy consumption in the world? In Indonesia?
▪ About 14.109 and 200.106 TOE respectively. But, what does it mean?
▪ Common language can be misleading

▪ We do NOT consume energy. We convert it from one form to the
other forms of energy (no generation, no destruction of energy). First law
of thermodynamic tells us that total energy is kept unchanged
▪ “Consuming energy” actually means “downgrading energy”, by

converting usable energy into more diffuse energy (generally heat)
Example: gasoline used in motor to move a car
chemical energy → mechanical energy → ultimately heat
▪ “Producing energy” actually means “converting non-usable energy
© R.Pelletier 2021
into usable one”, according to various needs.
TOE= Ton of oil equivalent
Small recap: What is energy?
Energy of wind or water can be

converted into mechanical or
electrical energy
Thermal power plants (gas, fuel, coal,

nuclear) convert only 30 to 55% of
the primary energy into electricity
→ release a large amount of heat in
© R.Pelletier 2021
the atmosphere

▪ Refining and Petrochemicals are sister industries belonging to the world

of energy
▪ Refining processes crude oil and refines it into

more useful products such as naphtha, gasoline,
diesel fuel, asphalt base, heating oil, kerosene,
liquefied petroleum gas
▪ Base petrochemicals designate those intermediate reactive

molecules between refining and monomers of second generation,
polymers, solvents, detergents, …
Ethylene, propylene, C4 cut, aromatics are the main products
© R.Pelletier 2021
▪ Unless you are an expert, very difficult to differentiate a refinery from

a petrochemical complex just by looking at it!
▪ But they are very different

• In size (What percentage of crude oil is treated in refineries? How much of this crude oil will be
used for petrochemicals?)
• In economic structure and business approach
▪ 100% of crude oil go to refineries (no direct use of this dirty, corrosive and toxic
mixture), while petrochemical industry consumes about 10% of all
© R.Pelletier 2021
crude oils
No single definition of Petrochemical industry → some apparent discrepancies in statistics.
In this lecture, “Petrochemicals” encompass Base Chemicals and Polymers. Fertilizers not included.
▪ Global worldwide capacities for crude oil production and for refining
can only be similar
• If under-capacity of refineries, crude oil production must slow down
• If over-capacity of refineries, “refining margin” collapses and “laggard” (= most
inefficient) refineries lose money and are forced to shut-down
▪ Global primary energy growing at ~2%/y rate (+2,9% in 2018), crude oil
production nearly flat but petrochemicals growth rate close to 5%/y
▪ Synergies between refining and petrochemicals are increasing with

the price of crude oil. All modern refineries are now associated with a
petrochemical complex.
© R.Pelletier 2021
World primary energy 2019: world primary
energy grew by 1,3%
(+2,6% in 2018)
In %, highest growth
for Renewables, coal
diminished slightly
Please, remember this order of magnitude: (-0,6 %)**
~14 billions T.O.E. / year
In absolute value,
fossil fuels still
Petrochemicals usage: ~550 MT/y TOE
grew slightly more
→ ~430 MT/y polymers 2019 Sources: BP Statistical
review of world energy 2020 than renewables.
R. Pelletier
© R.Pelletier 2021
** Coal less competitive with development of shale oil/shale gas and drop of prices
World Primary Energy. Trend over the last 50 years

Paradoxical situation! As world Coal represented
realized danger of climate change, nearly 50% of the
incremental energy
fastest growing source of primary energy consumption
from 2000 to 2015 was Coal, with highest
CO2 content, while nuclear energy, virtually
CO2 free, declined (Germany, Japan, now at
~4%). Coal kept growing (+1.4%) in 2018!
Hydroelectricity (at ~7%) still the main

renewable source of primary energy. All
other forms of renewables now close to 4%
© R.Pelletier 2021
But share of fossil energies probably still
around 75% in 2035.
Total Prof. Refining and Petrochemicals
Primary energy consumption per capita

World demand for
primary energy likely
to continue growing,
because of extreme
needs of developing
countries.
Ecology and energy
issues should be
considered at the
world level, not only at
our petty national borders.
© R.Pelletier 2021
Indonesia: 33 GJ/cap
Energy
Others
Gasoline Petrochemical chain (~7% of oil and gas)

CRUDE
Naphtha Ethylene Polyethylene Film Packaging End of life
Jet fuel
Diesel
Eventually, all crude will end up as CO2 and H20. But the petrochemical chain is
much longer than the energy chain, bringing a very high added value to the
© R.Pelletier 2021
hydrocarbon molecules
No single definition of Petrochemicals. In this lecture, encompass Base Chemicals and polymers. Fertilizers not included.

Refining Margins Definition
Gross margin – Margin over variable cost
10 L
Px = Product X price
Cx = Cost of X 35 G
100 CRUDE Refinery 15 J
25 GO
5F
OTHER VARIABLES 10 F
GM = [(0.10*PL)+(0.35*PG)+(0.15*PJ)+(0.25*PGO)+(0.05*PF)] – (1*PCrude)
MVC = [(0.10*PL)+(0.35*PG)+(0.15*PJ)+(0.25*PGO)+(0.05*PF)] – [(1*PCrude)+COtherVariables]
When refining gross margin (GM) reaches ~50 $/t,
© R.Pelletier 2021
the refining activity is highly profitable!
Chain Value
End of life
(recycling, energy recovery)
€/TON PACKAGING ▪ Although relatively small in

volume (~6% wt of oil and
gas), the length of the
2000 POLYETHYLENE FILM petrochemical chain induces a
very high added value
▪ Gross margin is of the order of
1100 POLYETHYLENE RESIN a few 1000 $/t
▪ Its economic importance is
700 ETHYLENE
often overlooked : no direct
450 NAPHTHA
sales to public, very scattered
© R.Pelletier 2021
300 CRUDE OIL
industry…
What future for refining and
petrochemicals?
Where will they develop?
© R.Pelletier 2021
What future for refining and petrochemicals?
◼ If peak oil is going to occur within 20 years from now, what will
happen to the oil products? Why should I choose to work in
refining or petrochemicals?
◼ Oil will preferably be

reserved with mobile
usage of energy, as
substitutes likely to cost
much more.
◼ More efficient use of each single drop of oil will require more and
more sophisticated technologies
© R.Pelletier 2021
(Like in the mutton or the pig, "everything is eaten, nothing is wasted" !)

What future for refining and petrochemicals?
▪ Refineries will incorporate more and more complex chemical units,

for deep conversion and quality improvements
▪ Polymers will continue to grow, as their usage contribute to energy
savings and to environment protection
▪ Feedstock cost advantage will be a key factor for competitiveness
▪ Growth will occur in developing countries, where cheap labor will
promote the development of manufacturing activities
▪ New feedstock will emerge (biofuels from cellulosic biomass, gas
to methanol to olefins, …) requiring also new research, new
developments and new investments
© R.Pelletier 2021
→ Plenty of challenging jobs all over the world
What future for petrochemicals?
Example of a TV set sold in Europe (frame in Polystyrene)
Styrene in Saudi Arabia → PS pellets in China → TV frame in China → TV assembly in Vietnam
© R.Pelletier 2021
Can you find out the logic behind such a long trip for the styrene molecule which ends up into
your home as part of your new TV set? How would it be different for an ethylene molecule for PE?

What future for petrochemicals?
Example of a TV set sold in Europe (frame in Polystyrene)
Styrene in Saudi Arabia → PS pellets in China → TV frame in China → TV assembly in Vietnam
TV Market Proximity Styrene

of PS easy to
markets move
Technology
and low
labor costs
Feedstock
advantage
Low labor
costs
© R.Pelletier 2021
Can you find out the logic behind such a long trip for the styrene molecule which ends up into your
home as part of your new TV set? How would it be different for an ethylene molecule for PE?
A very short recap on Refining
© R.Pelletier 2021
The art of refining
The subtle art of Refining:

▪ From a mixture of widely different and dirty crude oils,
▪ Produce well defined products, by safe and clean operation,
▪ Of the right quality, in the right quantity,
▪ Daily optimizing the refining margin.
© R.Pelletier 2021
The art of refining
Crude Oil Main petroleum
products
Middle East
S. Arabia - Iraq - Iran Liquefied • Propane
Kuwait - UAE Petroleum gases • Butane
• LPG automotive fuel
Africa
Nigeria - Gabon - Congo • Regular gasoline
Angola - Algeria - Libya Gasoline • Premium gasoline
• Unleaded premium gasoline
North Sea
Jet fuels
Other countries
Diesel fuel
CIS (ex USSR)
Home heating fuel
Venezuela
Mexico
• Normal
Heavy fuel oils • Low sulphur content
• Very low sulphur content
Bitumen
• Naphtha
• Special gasoline (white spirit, aviation gasoline)
• Kerosene
© R.Pelletier 2021
Other
products • Light marine diesel
• Special fuel-oils
• Lube base stocks
• Paraffin-Waxes
The art of refining
Petroleum
Crude oils
(C, H, O, N, S, REFINING
Products
Metals : Ni, V) • LPG
• Gasoline
• Jet fuel
• Diesel/ home
heating fuel
Separations
• Heavy fuel oil
Catalytic Thermal • Bitumen
Processes Processes • Lubricants
• reformer
• ...
• isomerization Blending • visbreaking
•catalytic cracking • coker
• steam-cracking (petrochemicals)
© R.Pelletier 2021
•hydrocracking
•hydrotreatments

World Oil Refining Capacities
▪ Oil companies usually rate their refinery capacities by the amount

of oil they can treat (typically characterized by the Atmospheric Crude Oil
Distillation Capacity)
▪ The standard unit they use is: barrel of oil per day
or bl/d
▪ Since there are roughly 7 barrels in a metric ton and about 350
days in a year, conversion factor from bl/d to T/y is
350/7 or ~50
▪ Thus, a 200 000 bl/d refinery is able to treat about
10 MT/year
© R.Pelletier 2021
Conversion
Market requires lighter and lighter products, while more heavy oil
fields are put into service (such as extra heavy oil from Orinico region
in Venezuela or oil sands from Alberta in Canada)
This growing discrepancy between
%
100
Weight
market demand and yield structure of
18,6 24,4
Light the available crudes induces the need
31,3 40,0 products
GPL, naphta,
gasoline,
for more and more conversion units
35,5
37,8
50
Other Many of these conversion units also
43,4 intermediate
45,0 products
produce olefinic and aromatic
JET-A1
45,9
Diesel Oil
Heating oil, ... molecules, useful for petrochemicals
37,8
25,3 Heavy
15,0
0
Products Synergies between Refining and
1970 1980 1990 2010 Heavy fuels
Bitumen, ...
Petrochemicals are now a must
© R.Pelletier 2021
The art of refining
Synergies between Refining and Petrochemicals are now a must
▪ Indonesia still very dependent on the import of petrochemical

products. Around 80 % of petrochemical supply comes from other
countries. (Source ttps://convex.ipa.or.id/indonesia-needs-oil-and-gas-to-develop-the-petrochemical-industry/)
▪ Nicke Widyawati, President Director of PT Pertamina:
“Target of the Indonesian Government on Petrochemicals in 2024 is
a chance for its oil and gas business future”
▪ “We will integrate our refineries with petrochemical facilities so it

will have the flexibility to switch from producing gasoline to
petrochemical products. This is our long-term mitigation strategy
when gasoline demand is going downwards.”
© R.Pelletier 2021
30
A zoom on Base Chemicals
© R.Pelletier 2021
Base Chemicals
▪Molecules in extracted petroleum (oil and gas) are saturated

molecules (no double bonds): they are not chemically reactive
▪ Oxidation (i.e. combustion) is basically the only important

chemical reaction performed with them
▪Creating double bonds

–C=C–
within the molecules will make them reactive and useful for
further chemical transformation by :
• Polymerization
• Addition
• Oxidation
• Hydration …
© R.Pelletier 2021
Base Chemicals
▪Base chemicals designate those intermediates reactive

molecules, between refining and polymers
▪Main products are

• Ethylene, propylene, C4 cut (olefins)
• Benzene, paraxylene (aromatics)
▪Crackers (for olefins) and Catalytic Reformers (for aromatics)

are the main industrial tools of today
▪Syngas (synthetic gas) will receive renewed development to

make use of new feedstock (such as coal or biomass)
© R.Pelletier 2021
Petrochemical industry →Add Value To Crude
© R.Pelletier 2021
- Source UOP

Main stages and products of petrochemical industry
Uses
ENERGY
CO + H2
SYNTHETIC FUELS
NATURAL GAS HYDROGEN NITROGENOUS FERTILIZERS
PRODUCTION OF GLUES AND THERMOSETTINGS
GAS OF AMMONIA
SYNTHESIS GLUE
METHANOL THERMOSETTINGS
METHANE MTBE
ETHANE
PLASTICS
PROPANE ANTIFREEZE, FIBRES
DETERGENTS
BUTANE ETHYLENE
THERMOPLASTICS
STEAM- PROPYLENE ELASTOMERS
CRACKING BUTADIENE ELASTOMERS
NAPHTHA
GAS-OIL
VGO THERMOPLASTICS
BENZENE (ST) SYNTHETIC FIBRES
(CY) ELASTOMERS
CATALYTIC TOLUENE NYLONS (Nylons 6, Nylon 6.6)
REFORMING ANIONIC DETERGENTS
RESIDUE
© R.Pelletier 2021
POLYESTER FIBRES
PARAXYLENE
THERMOPLASTICS RESINS
CRUDE OIL
ORTHOXYLENE PLASTICISERS
(ST) Styrene
(CY) Cyclohexane
Ethylene
Olefins Propylene
Butadiene
…
© R.Pelletier 2021
Olefins definition
▪ Olefins, also called alkenes, are unsaturated hydrocarbons with

one or more pairs of carbon atoms linked by a double bond
▪ The simplest (and most important commercially)
of all olefins is ethylene (C2H4)
▪Substitution of one hydrogen atom by
one methyl group yields propylene (C3H6)
▪Substitution by other reactive groups
yields a whole set of vinyl monomers:
Chlorine → VCM, Benzene ring → Styrene,
Nitrile group→ Acrylonitrile, etc …
▪Butadiene is the most important
© R.Pelletier 2021
di-olefin molecule (C4H6)
Steam cracker scheme
Hydrogen +
methane
Ethylene Refinery
Gas oil
Hot section Cold section Propylene
Naphtha
Butane Cracking Separation C4 cut
Propane Pyrolysis Aromatics
Gasoline extraction
Ethane
Pyrolysis
© R.Pelletier 2021
Fuel

Steam cracker scheme
Olefins usage: nearly exclusively for polymers
Demand 2017
(millions tons) Usages
• Polypropylene 65 %
102 MT • Acrylonitrile (acrylic fibers) 9%
Propylene • Propylene oxyde 8%
• Oxo alcools 7%
• Cumene/phenol (phenolic resins) 4%
• Acrylic acid 4%
• Others 3%
Steam • Polyethylenes, LDPE, LLDPE, HDPE 59 %

cracker Ethylene 152 MT • Polyvinyl chloride 12 %
• Polystyrene 7%
• Ethylene oxide and derivatives (polyesters) 14 %
• Alpha-olefins 3%
• Vinyl acetate 1%
• Other derivatives (ethanol, acetic acid …) 10 %
Butadiene • Styrene-butadiene 48 %
13 MT • Polybutadiene 27 %
(~45% of C4 cut)
© R.Pelletier 2021
• Other elastomers 9%
• ABS (styene-acrylonitrile-butadene) 10 %
Sources: IHS Markit June 4, 2018 Prismane Consulting Sept, 2019 • Adiponitrile – adipic acid 6%
39
Crackers: heavy investments
Crackers require very heavy investments. Above 1500 €/T/y. A modern

1MT/y ethylene cracker will cost ~ 2 billons Euros
Ethylene and Propylene very hard to store and transport. Any major
olefins investment project needs to be associated with the investment
of downstream units, such as Ethylene Glycol, VCM, Styrene, PE, PP, ...
This can more than double the overall investment cost
Demand for petrochemicals growing much faster than for fuels.

Synergies between Refining and Petrochemicals now a must. Huge joint
projects now being built.
© R.Pelletier 2021
40
Crackers: heavy investments
All new major projects ~1 MT/y ethylene or more

Some examples
▪ CNOOC-SHELL in Huizhou (CSPC: ~800 kT/y ethylene + SM-PO +

PP), or SINOPEC-BPC in Shanghai (SECCO : ~900 kT/y ethylene + PE
+PP +PS + AN)
▪ SONATRACH in Algeria has selected TOTAL Petrochemicals to

participate in a new cracker (1.1 MT/y ethylene) based on ethane
and in three downstream units (MEG 410 kT/y, HDPE 350 kT/y,
LLDPE 450 kT/y)
© R.Pelletier 2021
41
An extreme case of refining/petrochemical complex
Example : Petrochemical Complex of Petrobras (Project COMPERJ)

▪ Project COMPERJ (Rio de Janeiro). Initial plan: US$ 8.5 billion. Start-up 2012,
completion 2013. But postponed after 2008/09 crisis and Petrobras scandal
• Refinery processing 150,000 bpd of Brazilian heavy oil,
• "Petrochemical FCC" and Cracker for basic petrochemical products
• Second-generation monomers units, (Styrene, Ethylene Glycol, Terephtalic Acid),
• Polymerization units for Polyethylene, Polypropylene, PET, PS,...,
• Incentives for Polymer Processing Industries to settle nearby
• Altogether, over 50,000 jobs after the complex comes on stream.
(http://www2.petrobras.com.br/AtuacaoInternacional/PetrobrasMagazine/pm51/eng/retorno.html 2008)
▪ Project cancelled. But started a new trend: in lieu of producing transportation

fuels, Crude Oil to Chemicals (COTC, or COC) refineries aim at converting
maximum of crude oil directly to chemical feedstocks.
▪ Still in infancy, but potential for doubling the value refiners can get from a
barrel ~8.5 to 17 $/bl according to IHS Markit estimate (05/2019). Already many COTC projects, in
the range 40 to 60% conversion to petrochemicals (esp. in China).
© R.Pelletier 2021
Example: Hengli Petrochemicals, 20 MT/y refinery, 42% petrochemicals, Start Up: Dec/2018

New olefins technology
Influence of feed on stream cracker yields (wt %)
© R.Pelletier 2021
Virtually no propylene out of ethane crackers
Typical yields above are obtained at very high severity, after recycling of ethane and/or propane, unconverted or produced in pyrolysis.
44
Products split associated to feedstock nature
Thousand tons for 1000t of C2H4
- Source : CMAI
For same 1 MT/y ethylene outlet, a liquid feed cracker yields 3 to 4 MT/y
© R.Pelletier 2021
products, which are processed into valuables petrochemicals.
Long term supply chain needs to be strategically secured.
45
▪ Ethane contained in natural gas has a very low net back price,
when sold along with natural gas
▪ Gas producers searched for a higher added value
→ ethane cracking
▪ Since ethylene difficult to move, simultaneous development
of downstream units (PE, VCM, …)
▪ Very fast development of highly competitive ethane crackers
for the ethylene chain lead to
•Fewer liquid crackers being built

•Too much ethylene and not enough propylene
© R.Pelletier 2021
Competitive feedstock advantage of field ethane based ethylene

Naphtha cracker in Europe or in China
/ unit delivered polyethylene
/ PE delivered locally
Ethane cracker in ME
/ PE delivered to Europe or China
Cash cost
35
Ethylene capacity inMioT (end of year)....

30
25
Ethylene in M.E.
20
15
Oil price / bbl 10
18-20 $/bbl
5
0
Very difficult to maintain a competitive 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012
Ethylene/Polyethylene chain in Europe or Japan.
© R.Pelletier 2021
Development of shale gas enabled a similar boom in USA.
But Middle East producers still main exporters to Asia
New Routes To Light Olefins: Search for C3= optimization
Methane Methanol MTP (MTO and MTP in

development stage)
Methane Methanol MTO Ethylene
+OCP
Ethane
Field Dehydro
Natural Gas
Propane
Propylene Metathesis
Butane Crackers
+OCP
Naphtha
Crude Oil FCC
Butenes
Gas Oil +OCP
© R.Pelletier 2021
GTO: Gas To Olefins
MTO: Methanol To Olefins (ethylene + propylene) OCP: TP/UOP Olefin Cracking Process® (C4 + to propylene)
Metathesis: ethylene + butene → propylene 48
MTP: Methanol to Propylene
48
Syngas
Syngas*: an old but promising technology
▪ Generic name given to gas mixtures that contain varying amounts of

carbon monoxide (CO) and hydrogen (H2) …
• together with CO2, residual CH4, and steam…
• produced from any hydrocarbon feedstock (typically methane or naphtha), coal, biomass, wastes &
refuses, …
• through a conversion by steam, oxygen or air, …
• preferably with a minimum level of inert.
▪ Used for the production of

• H2 → hydro-treatments in refineries, …
• H+N2 → ammonia and urea
• methanol → formaldehyde, MTBE, MMA, …
• oxo-alcohols → plasticizers, higher acrylates, …
• Fischer-Tropsch conversion → liquid hydrocarbons
© R.Pelletier 2021
*Syngas= Synthesis gas = « Gaz de synthèse » in French language
49
Syngas
Syngas: an old but promising technology

Main Reactions for Steam Reforming
CH4 + H2O <======> CO + 3 H2 (highly endothermic ~55 Kcal/mole)
CnH2n+2 + n H2O <===> n CO + (2n+1) H2
Shift Reaction (for H2 maximization)

CO + H2O <========> CO2 + H2 (exothermic ~ - 8 Kcal/mole)
Main Reactions for Partial Oxidation

CH4 + ½ O2 ======> CO + 2 H2
CnH2n+2 + n/2 O2 ===> n CO + (2n+2) H2
C2H5OH + ½O2 ===> 2 CO + 3 H2
Shift Reaction (for H2 maximization)
© R.Pelletier 2021
CO + H2O <========> CO2 + H2
50
Syngas
Syngas: an old but promising technology

Some of the main syngas derivatives
(orders of magnitude of worldwide production 2019)
• Hydrogen: 65 MT/Y
• Ammonia: 235 MT/Y →
• Urea: 220 MT/Y
• Methanol: 150 MT/Y
• Formaldehyde: 50 MT/Y
• Acetic acid: 18 MT/Y
• Vinyl Acetate: 8 MT/Y
• …
• 2-ethyl hexanol: 4,5.0 MT/Y
© R.Pelletier 2021
Source Statista, Technip, RP
51
New Syngas
▪ Two major technology developments enable a « new life » for Syngas:
« Gas to Liquid » and « Methanol to Olefins »
▪ Gas to Liquid (GTL) transforms methane into sulfur free diesel oil or
naphtha. Shell Pearl GTL (Qatar): world’s largest plant to turn natural
gas into cleaner-burning fuels and lubricants (140000 b/d)
▪ Methanol to olefins
(MTO) produces
ethylene from
methanol
→Very high growth
rate for methanol
© R.Pelletier 2021
▪ Largest MTO single train: 850 kT/y from
coal, in Jiangsu Sailboat Petrochemical Co.
52 52
AROMATICS
MONOMERS
Bz+Eth -> EB -> SM ->

PS, ABS, …
PX-> PTA (+EG)

-> PET
© R.Pelletier 2021
53
Aromatics
Aromatics: Definition
▪ Aromatics: chemical species containing an hexagonal cyclic
structure, « benzene ring », with 6 carbon atoms linked by 3
single bonds and 3 doubles bonds
▪ Actually, all 6 bonds are equivalent. Benzene
C6H6 is the simplest aromatic molecule
▪ Substitution of one hydrogen atom by a

methyl group yields Toluene (C7 aromatic)
▪ Xylenes (C8 aromatic, or

dimethylbenzenes) derive from
benzene by 2 methyl groups
replacing 2 hydrogen atoms.
© R.Pelletier 2021
Benzene and paraxylene are the two most valuable aromatics
Aromatics
Main commercial aromatics products
Among all aromatics, benzene and paraxylene have the largest market
Aromatics producers organize their production tool according to nature

of their main raw material :
•Reformate
•Pyrolysis gasoline
•Coke oven light oil
and to their commercial strategy:

•Maximum of benzene
•Maximum of paraxylene
•Balanced production of benzene and paraxylene
© R.Pelletier 2021
Catalytic Reformers in refineries are the
work horses of aromatics production
▪ Reformate ex Continuous catalyst

reformer (CCR)
▪ Pyrolysis Gasoline ex Steam Cracker
▪ Coke Oven Light Oil ex Coking Plants
The problem: low native

Benzene and PX 
© R.Pelletier 2021
Aromatics Complex – Technologies
 The solution: various separation and conversion units

▪ Separation units:
– Aromatics / non-Aromatics
– C8 aromatic isomers (Paraxylene purification)
▪ Conversion units
– Toluene/heavy aromatics transalkylation
TOL + C9A(+) ➔ x C8A + y BZ
– Toluene (selective) disproportionation
2 TOL ➔ C8A + BZ
– C8 aromatics isomerization
(EB, MX, OX) ➔(EB, PX, MX, OX)
– Xylenes isomerization with EB dealkylation
(MX, OX) ➔ (PX, MX, OX) EB ➔ BZ+ C2
– C7+ aromatics hydrodealkylation for benzene production
© R.Pelletier 2021
TOL + H2 ➔ BZ + C1

Aromatics Complex - Technologies
Light Naphtha
Naphtha Raffinate
Benzene
Naphtha Extractive
Hydrotreater Distillation
C7-
Tol-A9-A10
NS Transalkylation
Reforming
(CCR) Paraxylene
Heavy Naphtha PX Xylenes
Separation Isom.
C8+
C9+C10
C9+
© R.Pelletier 2021
Source: Axens

Heavies 58
Will benzene be long or short?
© R.Pelletier 2021
Will Benzene be long or short ? …
▪ Aromatics are at the interface between Refining and

Petrochemicals.
▪ World Gasoline production: of the order of 1 billion

tons/y
▪ World Benzene consumption: ~45 million tons/year
▪ Although very different in size, strong links between the

two industries.
© R.Pelletier 2021
Naphtha --> Benzene/Ethylene --> Styrene --> PS 1999-2005
1.500
1.400
Long lasting high price can induce
1.300 PS GP
1.200 STYRENE
material substitution
1.100 ETHYLENE
1.000 BENZENE
In 2001, as more severe limits on
900 NAPHTHA aromatics and Bz in gasoline were being
EUR / T
800
700
enforced, what would have been your
600 guess: long or short Benzene?
500
400
If you were a cup manufacturer, would
300
200
you select PS or PP as raw material for
100 your new equipment?
0
99
9 99 00
0 00 00
1 01 00
2 02 00
3 03 00
4 04 00
5 05
.1 l.19 .2 l.20 .2 l.20 .2 l.20 .2 l.20 .2 l.20 .2 l.20
n Ju n Ju n Ju n Ju n Ju n Ju n Ju
Ja Ja Ja Ja Ja Ja Ja
© R.Pelletier 2021
NAPHTHA - Platt's - Cargo CIF NWEARA High
BENZENE - Icis - Contract Price - FOB NWE Low
ETHYLENE - Icis - Contract Price - FD NWE Low
STYRENE - Icis - Contract Price- FD Barge NWE Low
PS (GPPS) - Icis - GPPS Domestic Price - Germany Low
Example of inter-polymer competition
•Disposable cups
•Trays and boxes
1.300 •Dairy packaging 900
1.200 •Consumer goods

PS cups 800
1.100 700
1.000 600
PS
500
900
400
Price HIPS-GPPS 50/50 & PP
800
300
700 PP
200
600
100
Delta PP-PS
500
0
400
Substitution occurs -100
300 Substitution
Possible Substitution at ΔPrice (PS - PP)
-200
200
occurs
when Delta PS/PP > 150 €/T around
~ 150 €/T
-300
100 PP cups -400
0
Delta Price PS- -500
© R.Pelletier 2021
PP ~ 150 €/T
Delta PP / PS Net Price GPPS / HIPS 50/50 PP Indicator

Naphtha --> Benzene/Ethylene --> Styrene --> PS 1999-2005
1.500
1.400
1.300 PS GP
1.200 STYRENE
1.100 ETHYLENE
1.000 BENZENE
900 NAPHTHA
EUR / T
800
700
Unexpectedly, Benzene price skyrocketed.

600
Easier to give a-posteriori explanations!

500
400
High gasoline demand from China and USA drove

300
toluene out of TDA or TDP units, leading to a

200
100
relative
0
BZ shortage.
9 99 0 00 1 01 2 2 3 03 4 04 5 05
n
Processors
.199
Ju
l.19
n.2who
00
Ju
l.ordered
20
n.200 PS
Ju
l.20extruders
n.200
Ju
l.2to
00
n.200
Ju
l.20
n.200
Ju
l.20
n.200
Ju
l.20
© R.Pelletier 2021
Ja Ja Ja Ja Ja Ja Ja
manufacture cups in 2002 lost aNAPHTHA lot of -money!
Platt's - Cargo CIF NWEARA High
BENZENE - Icis - Contract Price - FOB NWE Low
ETHYLENE - Icis - Contract Price - FD NWE Low
STYRENE - Icis - Contract Price- FD Barge NWE Low
Total Prof. Refining and Petrochemicals PS (GPPS) - Icis - GPPS Domestic Price - Germany Low
Example of inter-polymer competition
•Disposable cups
•Trays and boxes
1.300 900
•Dairy packaging
1.200 800
•Consumer goods 700
1.100
1.000 600
PS
500
900
400
Price HIPS-GPPS 50/50 & PP
800
300
700 PP
200
600
100
500
0
400
-100
300 -200
Possible Substitution
200 when Delta PS/PP > 150 €/T -300
100 PP cups -400
0 -500
© R.Pelletier 2021
Delta PP / PS Net Price GPPS / HIPS 50/50 PP Indicator
The petrochemical “squeeze”
Energy
Suppliers
Petrochemical
manufacturer
who suffers! OEMs, WalMart
© R.Pelletier 2021
Resin Buyers
Source: CANY
H426 - May 2002 OEM = Original Equipment Manufacturer
Controlled by
demand/supply
equilibrium and
competition from
other materials
Margin
PRICE of Controlled by
polymers Costs
energy price
© R.Pelletier 2021
T
E
C
H
N
O
L
O
Petrochemical G
manufacturer Y
who wins!
• Total cost reduction
An industry in constant move
© R.Pelletier 2021
• Product differentiation
Source: CANY
H427 - May 2002

(restructuration and R&D)

Product differentiation
One of the major keys to success in polymer business
▪ In the refining industry, all producers MUST deliver exactly the same
products, according to specifications fixed by authorities
▪ In the polymer industry, all producers strive to deliver maximum of
differentiated products, i.e. polymer grades especially developed by
R&D to fit specific applications for specific customers. A single large
polyolefin producer may offer hundreds of different grades of
polyethylene and polypropylene
▪ In the following lectures, we shall see the most important
polymerization parameters used by R&D to design those specific
© R.Pelletier 2021
polymers.
**************** 68

PEMA 2021 RP2 Petrochemicals Tbpresented

Uploaded by

Copyright:

Available Formats

You might also like

PEMA 2021 RP2 Petrochemicals Tbpresented

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

PEMA 2021 RP2 Petrochemicals Tbpresented

Uploaded by

Copyright:

Available Formats

From Oil and Gas to Polymers and Plastics

Refining and Petrochemicals

Robert PELLETIER PEM Akamigas

▪ D2 Global view of the petrochemical chain in world of energy, leading mostly to

▪ D3 and 4 Polymers and plastics. Definitions: (monomers, polymers, molecular weight,

General conclusion of the program. Methodology of polymer development. Importance

Total Prof. Refining and Petrochemicals 5

Small recap: What is energy?

▪ Energy, in itself, is immaterial, even though it needs physical

▪ The various forms of energy:

Total Prof. Refining and Petrochemicals 7

▪ Common language can be misleading

▪ “Consuming energy” actually means “downgrading energy”, by

Energy of wind or water can be

Thermal power plants (gas, fuel, coal,

Total Prof. Refining and Petrochemicals 9

▪ Refining and Petrochemicals are sister industries belonging to the world

▪ Refining processes crude oil and refines it into

▪ Base petrochemicals designate those intermediate reactive

▪ Unless you are an expert, very difficult to differentiate a refinery from

▪ But they are very different

▪ Synergies between refining and petrochemicals are increasing with

World Primary Energy. Trend over the last 50 years

Hydroelectricity (at ~7%) still the main

Primary energy consumption per capita

Gasoline Petrochemical chain (~7% of oil and gas)

Naphtha Ethylene Polyethylene Film Packaging End of life

Total Prof. Refining and Petrochemicals 16

100 CRUDE Refinery 15 J

MVC = [(0.10*PL)+(0.35*PG)+(0.15*PJ)+(0.25*PGO)+(0.05*PF)] – [(1*PCrude)+COtherVariables]

When refining gross margin (GM) reaches ~50 $/t,

€/TON PACKAGING ▪ Although relatively small in

◼ Oil will preferably be

Total Prof. Refining and Petrochemicals 20

▪ Refineries will incorporate more and more complex chemical units,

Total Prof. Refining and Petrochemicals 22

Styrene in Saudi Arabia → PS pellets in China → TV frame in China → TV assembly in Vietnam

TV Market Proximity Styrene

The subtle art of Refining:

▪ Produce well defined products, by safe and clean operation,

▪ Of the right quality, in the right quantity,

▪ Daily optimizing the refining margin.

Total Prof. Refining and Petrochemicals 27

▪ Oil companies usually rate their refinery capacities by the amount

Synergies between Refining and Petrochemicals are now a must

▪ Indonesia still very dependent on the import of petrochemical

▪ “We will integrate our refineries with petrochemical facilities so it

▪Molecules in extracted petroleum (oil and gas) are saturated

▪ Oxidation (i.e. combustion) is basically the only important

▪Creating double bonds

▪Base chemicals designate those intermediates reactive

▪Main products are

▪Crackers (for olefins) and Catalytic Reformers (for aromatics)

▪Syngas (synthetic gas) will receive renewed development to

Total Prof. Refining and Petrochemicals 34

▪ Olefins, also called alkenes, are unsaturated hydrocarbons with

Total Prof. Refining and Petrochemicals 38

Steam • Polyethylenes, LDPE, LLDPE, HDPE 59 %

Crackers require very heavy investments. Above 1500 €/T/y. A modern

MVC = [(0.10PL)+(0.35PG)+(0.15PJ)+(0.25PGO)+(0.05PF)] – [(1PCrude)+COtherVariables]