Petroleum Refining

Dr. Phan Thi To Nga

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 Recommended books
1. Lê Văn Hiếu (2005). Công nghệ chế biến dầu. NXB Khoa học kỹ thuật

2. James H. Gary and Glenn E. Handwerk (2001). Petroleum Refining

Technology & economics. Fourth edition. New York.

3. M. A. Fahim, T. A. Al-Sahhaf, and A. S. Elkilani (2009). Fundamentals

of Petroleum refining. Elsevier.

4. Robert A. Meyers (2003). Handbook of Petroleum Refining Processes

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Outline

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Oil history

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Petroleum pathway

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 Components of the upstream
➢Find Oil & Gas Reservoir
- Which regions and basins?
- Which blocks?
- Where on the block?
➢How to get it out
- Where, in detail, are the reserves?
- What to build (facilities)?
- Will it be profitable?

➢ From the ground, to the Refinery

- How to manage the field?
- How to deliver the ‘crude’?

How can we determine where to drill and predict

what we will find before we start drilling?

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Overview of refinery processes

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Flow scheme of a modern refinery

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 What crude oil makes
Crude oil, in its raw natural form, must undergo refinement to make it useful for
consumers. An oil refinery, separates, converts, and purifies the components of crude
oil into valuable petrochemicals. Many products, from propane to petrol to bitumen, can
come from just one barrel of crude oil through refining.

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What is crude oil?

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 Crude oil is a complex mixture
Crude oil range is in consistency from water to tar-like solids, and in colour from clear
to black.

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Classification of crude oil

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 Types of hydrocarbons
The first crude oil classification is by the types of hydrocarbons (paraffins, napthenes,
and aromatics), depending on the relative ratio of the hydrocarbon classes that
predominates in the mixture. This rating is important to the refinery since the value of
crude oil decreases from classification 1 to 6.

Classification of
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crude oil
 oAPI of different crude oils
➢ Light crude oil is defined as having an API
gravity higher than 31.1 oAPI (density is less
than 870 kg/m3)
➢ Medium crude oil is defined as having an API
gravity between 22.3 oAPI and 31.1 oAPI (870
to 920 kg/m3)
➢ Heavy crude oil is defined as having an API
gravity below 22.3 oAPI (920 to 1000 kg/m3)
➢ Extra heavy crude oil is defined as having an
API gravity below 10 oAPI (greater than 1000
kg/m3)
As heavy oil requires more refining than light oil to yield
useful products, light oil is valued higher than heavy oil.
Classification of
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crude oil
 Sulfur content in crude oil
Depending on the amount of sulfur, the crude oil is referred to as sweet or sour.

➢ Low sulfur (<0.5% weight) is called sweet

➢ High sulfur (>1% weight) is called sour

Classification of Oil that is sweet is more valuable than oil that is sour
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crude oil
 Crude oil quality by types

Two of the most important

attributes when comparing the
quality of different crude oils
are sulfur content and density

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Hydrocarbons in crude oil

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 Alkanes (Paraffins)
 Paraffins: CnH2n+2 (n = 1 to 4: gas; n = 5 to 17: liquid; > 17: from viscous liquids to
solid waxes).
+ The simplest alkane, methane (CH4), is the principal constituent of natural gas.
+ Methane, ethane, propane, and butane: gaseous hydrocarbons (at ambient T and
P), found associated with crude oils in a dissolved state (petroleum gases).

+ Depending on demand and the cost of recovery, these gases are either flared off,
sold as liquified petroleum gas under pressure, or used to power the refinery's own
burners

+ During the winter, butane (C 4H 10), is blended into the petrol pool at high rates,
because its high vapor pressure assists with cold starts.
 Boiling point and density increase with increasing the number of C atoms.
Paraffins from C 1 to C40 usually appear in crude oil and represent up to 20% of
crude by volume.
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 Two types of paraffin molecules: straight chains and branched chains.
Branching in the carbon chain causes significant changes in physical
properties (boiling point, density) and chemical behavior (octane number)
of parrafins with the same carbon number.

 n-paraffins, with simple linear structures and no side chains, turn waxy at
low temperatures and make poor lubricants for products that need to
operate in a wide range of temperatures.
 Isoparaffins, with side-branching carbon atoms to keep the molecules
from crystallizing, remain fluid at low temperatures and are preferred
base stock components. In addition, the isoparaffins have excellent VI,
oxidation stability, and low toxicity.
Alkanes (Paraffins) 27
 Naphthenes (Cyclo alkanes)
➢ Naphthenes or cycloalkanes are ring or cyclic saturated hydrocarbons: CnH2n. They are
higher in density than equivalent paraffins and are more viscous.
➢ Cyclopentane (C5H10), cyclohexane (C6H12),
and their derivatives such as n-alkylcyclopentanes
are normally found in crude oils (up to 60%).
➢ Naphthene rings with five and six carbon atoms
are the most stable.
➢ Desirable lube molecules: single-ring
naphthenics (good VI); quality drops: the
naphthenic content: too high +/ a high concentration
of multi-ring naphthenic material (VI becomes
too low for use in engine oils even though
pour point and solubility are excellent).
➢ Good feed for BTX production

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 Aromatics
➢ Cyclic but unsaturated hydrocarbons with alternating double bonds
➢ All aromatics have poor VI properties,
exhibiting significant changes in viscosity
with changes in temperature.
➢ Single-ring substituted monoaromatics
are considered fair performers in conjunction
with isoparaffins (improve solubility and pour
point)
➢ Aromatics such as benzene, toluene o/m/p-xylene (BTX) are also available in the crude oil.
These contribute towards higher octane number products and the target is to maximize
their quantity in a refinery process.
➢ Benzene: cancer-inducing compound → the amount of benzene allowed in petroleum
products such as gasoline or fuel oil is limited by government regulations in many countries.
➢ Under standard conditions, BTX are in liquid form whereas higher aromatics such as
naphthalene occur as solids in isolation, but dissolve to form a liquid solution with simple

aromatics. BTX: Important petrochemical feedstocks

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 Polyaromatic and hydroaromatic compounds
 More complex aromatic compounds consist of a number of ‘‘fused’’ benzene rings.
(polynuclear aromatic compounds).

 Found in the heavy petroleum cuts, undesirable:

because they cause catalyst deactivation and coke deposition

during processing, causing environmental

problems (highly toxic nature) when presenting

in diesel and fuel oil Normally, high-molecular-weight

➢ Polynuclear aromatics: poor lubricants polyaromatics contain several

heteroatoms such as sulfur,
with respect to VI, pour point, and oxidation
nitrogen, or oxygen, but these
stability
compounds are still called
 The heaviest portion of the crude oil
aromatic compounds because
contains asphaltenes (condensed polynuclear
their electronic configurations
aromatic compounds of complex structure (M = 150-500) maintain the aromatic character.
➢ A crude with high quantities of resins and asphaltenes (heavy crude) is usually targeted
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for coke production
Non-hydrocarbons in crude oil

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 Sulfur compounds
➢Sulfur in crude oils is mainly present in the form of organosulfur
compounds.
➢Hydrogen sulfide is the only important inorganic sulfur compound found in
crude oil. Sour crudes contain a high percentage of hydrogen sulfide. Its
presence, however, is harmful because of its corrosive nature.
➢Organosulfur compounds may generally be classified as acidic and non-
acidic.
+ Acidic sulfur compounds are the thiols (mercaptans).
+ Thiophene, sulfides, and disulfides are examples of non-acidic
sulfur compounds found in crude fractions.

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 ➢ Many organic sulfur compounds are
not thermally stable hydrogen
sulfide is often produced during
crude processing.
➢ High-sulfur crudes are less desirable
because treating the different
refinery streams for acidic hydrogen
sulfide increases production costs.
➢ Most sulfur compounds can be
removed from petroleum streams
through hydrotreatment processes,
where hydrogen sulfide is produced
and the corresponding hydrocarbon
released. Hydrogen sulfide is then
absorbed in a suitable absorbent

Organic sulfur compound and recovered as sulfur. 33

 Nitrogen compounds
➢ Organic nitrogen compounds occur in crude oils:
+ simple heterocyclic form as in pyridine (C5H5N),pyrrole (C4H5N)
+ complex structure as in porphyrin.
➢ The nitrogen content in most crudes is very low and does not exceed 0.1
wt%.
➢ In some heavy crudes, the nitrogen content may reach up to 0.9 wt %.

➢ Nitrogen compounds in crudes may generally be classified into basic

and non-basic categories:
+ Basic nitrogen compounds: having a pyridine ring,
+ Non-basic compounds: having a pyrrole structure.
Both pyridine and pyrrole are stable compounds (aromatic nature)

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 ➢ Nitrogen compounds are more
Basic Nitrogen Compounds
thermally stable than sulfur compounds
➢ Concentrated in heavier petroleum
fractions and residues.
➢ Light petroleum streams may contain
trace amounts of nitrogen compounds

Non-Basic Nitrogen Compounds

→ remove (poison many processing
catalysts)
➢ Nitrogen compounds are
hydrodenitrogenated to ammonia and the
corresponding hydrocarbon

Nitrogen compounds 35
 Oxygen compounds
➢ Oxygen compounds: more complex than the sulfur types
➢ The total acid content: low (<2 % by Weight) in the crude oil (may reach as
much as 3%, as in some California crudes)
➢ Presence: not poisonous to processing catalysts, however they can
cause corrosion
→ need to be effectively handled.
➢ Many of the oxygen compounds found in crude oils are weakly acidic:
carboxylic acids, cresylic acid, phenol, and naphthenic acid
+ Naphthenic acids in the naphtha fraction have a special commercial
importance and can be extracted by using dilute caustic solutions
➢ Non-acidic oxygen compounds: esters, ketones, and amides are less
abundant than acidic compounds. They are of no commercial value.
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 Acidic Oxygen Compounds Non-Acidic Oxygen Compounds

Esters Amides

Cyclohexane Ketone Furan

Carboxylic acid

Phenol Benzofuran

Oxygen compounds 37
 Metallic compounds
➢Many metals occur in crude oils.
➢More abundant: sodium (Na), calcium (Ca), magnesium (Mg), aluminium (Al),
iron (Fe), vanadium (V), and nickel (Ni)
➢Existence: inorganic salts (sodium and magnesium chlorides), organometallic
compounds (those of Ni and V (as in porphyrins))
➢In crudes: trace amounts but harmful → remove to avoid operational problems
and to prevent them from contaminating the products
+ Calcium and magnesium can form salts or soaps with carboxylic acids, act as
Emulsifiers → undesirable
+ sodium and magnesium chlorides produce hydrochloric acid (very corrosive)
→ desalting to reduce these salts

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 ➢Metals affect many upgrading processes:
+ poisoning to the catalysts used for hydroprocessing and cracking.
Ex: trace amounts of metals (iron, nickel and vanadium) in the feedstock to the
catalytic cracker affect the activity of the catalyst and result in increased gas
and coke formation and reduced gasoline yields.
+ For high-temperature power generators, the presence of vanadium in the fuel
may lead to ash deposits on turbine blades and cause severe corrosion, and
the deterioration of refractory furnace linings.
➢ Most of the vanadium and nickel compounds are concentrated in the heavy
residues
→ Solvent extraction processes are used to reduce the concentration of heavy
metals in petroleum residues.

Metallic compounds 39