OM - 04 - Fuels-2 - Refining & Liquid Fuels PDF

Department of Maritime Studies
Dr.-Ing.
Wolfgang Busse
E-Mail: wolfgang.busse@hs-wismar.de
www.sf.hs-wismar.de
Operating Media and Dangerous Materials

Chapter 2: Fuels
Lesson 4 :
- Crude Oil Processing
- Liquid Fuels
Operating Media & Dangerous Materials
Chapter 2: Fuels
Lesson 4: Refining & Liquid Fuels
18-Oct-13
2
Dr.-Ing. Wolfgang Busse 2013
Refining & Liquid Fuels
Content
Crude Oil Processing
o Pre-treatment, Fractional distillation, Conversion,
Removing impurities, Blending
Properties of Liquid Fuels, Fuel oil performance & Test
methods
o Physical properties
(density, viscosity, )
o Ignition & combustion properties
(cetane number, calorific value, )
o Chemical properties
(sulphur content, ash content, )

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3
Each crude-oil field has a different composition.
The composition be determined by a combination of gas-chromatography,
fluorescence-spectroscopy and infrared-spectroscopy techniques.
That may be used, for instance, in forensic analysis of oil spills at sea; Even
after refining, crude-oil derivatives may be associated to their source field.

Crude Oil Composition & Properties
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Crude Oil Components:
Alkanes = Paraffins
Alkene = Olefins
Cycloalkane = Naphtenes
Aromatics

Crude Oil Classification:
Paraffin based crudes (a waxy residue)
Asphalt based crudes (an asphalt type residue)
Mixed type-based crudes (a combination residue)

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Properties of Crude Oil:
Crude Oil is a mixture, the properties therefor vary in a wider range:
Density: from 700 kg/m
3
to 1000 kg/m
3
at 20 C
Freezing and boiling points: solid-liquid equilibrium may exist in the range
210 K to 280 K, and liquid-vapour above 280 K (at 100kPa); vapours start to
decompose at about 900 K
Pour point: 5..15 C
Viscosity: 5 20 10-6 m
2
/s at 20 C
Vapour pressure: 5..20 kPa at 20 C / 40..80 kPa at 38 C; vapours are
heavier than air (2 to 3 times).

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Crude Oil = Petroleum that has been separated from natural gas;
Complex mixture of alkanes, and small amounts of alkenes,
alkynes, cycloalkanes, aromatic and inorganic compounds

Types:
Light crude oil:
low sulphur and metal content, brightly colored, low
viscosity
Heavy crude oil:
high sulphur and metal content, dark, high viscosity

The different boiling points of the various components enables
their separation by fractional distillation.

Crude Oil Processing
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Dehydration & Desalting Plant
Removing natural gas, water, salt and sludge are removed from the wet oil

Crude Oil Pre-Treatment
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Refinery Process Steps

1. Fractional Distillation
Crude Oil is physically separated into product groups (fractions) with
different boiling range (different molecule range). The hydrocarbons
within a fraction have similar properties.

2. Conversion
chemically converting the separated hydrocarbons into more desirable
reaction products by changing the size and/or the structure of the
molecules

3. Removing Impurities / Treatment
Removing unwanted ingredients such as sulphur

4. Blending
Improving the product qualities by mixing compositions

Crude Oil Refining
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Car fuel
Jet fuel
Road tar
Step 1: Fractional Distillation
Hydrocarbons are separated in a
distillation plant, which produces
different fractions of oil and gas.

Fractions are groups within a
certain range of boiling points.
Marine
Fuel
Oil (MFO)
LPG
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Crude oil can be separated by physical methods, in this case by fractional distillation,
because the many hydrocarbons have different boiling and condensation points.
The crude oil is vaporised by heating and the vapour passed into the fractionating
column - a large construction of many levels and pipes.
This is a continuous process (not a batch process). The fractionating column works
continuously with heated-vaporised crude oil piped in at the bottom and the various
fractions condensed and constantly tapped off from various levels, each with a different
condensation temperature range.
The most volatile fraction, i.e. the molecules with the lowest boiling points, go higher up
the column and condense at the higher levels in the column at the lowest temperatures.
The rest separate out according to their boiling/condensation point so that the highest
boiling fraction, i.e. the less volatile molecules with higher boiling points, tend to
condense more easily lower down the column, albeit at the higher temperatures.
The bigger the molecule, the greater the intermolecular attractive forces between the
molecules, so the higher the boiling or condensation point (see lesson hydrocarbons).
Note: Covalent chemical bonds like C-C or C-H are not broken in the process, only the
intermolecular force of attraction is weakened to allow the initial evaporation or boiling
and this.

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Crude oil is heated in a boiler using high-
pressure steam up to ~600C. The crude
oil vapor is passed to the bottom of the
distillation tower.

In the distillation tower, the vapor moves
up along the trays, passing holes equipped
with bubble caps.

On its upward movement, the vapor cools
down. In every tray, a certain fraction of
the vapor falls below its boiling point and
condensates. The condensate falls and
gathers on the tray under the bubble cap
from where it is flowing out of the tower bubble cap trays
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..
Section of an industrial distillation tower showing detail of trays with bubble caps
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Schematic flow diagram of an atmospheric and vacuum distillation plant
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Properties of the various fractions
The physical properties of different fractions which vary with molecular size. The
longer the carbon chain, the bigger the molecule gets ...
1. the more viscous the molecule as the intermolecular attractive forces between
molecules increases the bigger the molecule in a series of molecules of similar
structure.
2. the molecule has a higher melting point as more vibrational kinetic energy is
needed to overcome the intermolecular attractive forces holding the molecules
together
3. the molecule has a higher boiling point as more particle kinetic energy is
needed to overcome the increasing intermolecular forces between the liquid
molecules.
4. the molecule is less flammable as they become less volatile, again due to
increasing intermolecular forces with increasing size of molecule so for example,
petrol (small molecules) is much more flammable than lubricating oil (much bigger
molecules).

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Step 2: Conversion
From the distillation tower the fractions are passed to various
conversion processes - to get qualities and quantities suited to the
market demands:

Cracking

Reforming

Alkylation

Coking

Breakdown of large molecules into small molecules,
e.g. cracking light oil fractions into gas, heavy oil fractions
into diesel oil etc.
Change of straight chains into branched chains / alicyclics /
aromatics, e.g. n-octane to isooctane for gasoline (=> higher
knocking resistance)
Merging of small molecules into big molecules, e.g. the
combination of propene and butene into compounds for
gasoline
Cracking of residue fractions into heavy oil and hydrocarbon
intermediates. In this process, coke is produced.
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Step 2: Conversion
Cracking (to crack = to break-down)

= splitting of hydrocarbon molecules (molecule decomposition) into smaller
hydrocarbon molecules (less C-atoms)

The molecules increasingly vibrate when heating. At temperatures higher then
360C the bonds between the C-atoms loosen, and shorter hydrocarbon
chains are formed.

The splitting also produces coke forming a deposit in the pipes of the cracking
furnace or on the catalyst. It must be removed (burned) periodically.

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Step 2: Conversion
Cracking - Processes

Thermal Cracking
From the residue of atmospheric or vacuum distillation a light heating oil (middle distillate)
is extracted. Visbreaking is only a mild cracking, Target is saving gas oil for the viscosity
adjustment of the heating oil, not the production of gasoline or diesel fuel.

Steam Cracking
Saturated hydrocarbons are broken down into smaller, often unsaturated, hydrocarbons.
A gaseous or liquid hydrocarbon feed like naphtha, LPG or ethane is diluted with steam
and briefly heated in a furnace without the presence of oxygen.

Catalytic Cracking
Only for high-boiling distillates, the high sulphur amounts in the residue would poison the
catalyst. The process is better controllable and as about 10% higher yield.

Hydrocracking
At pressure of 15 to 17 MPa and temperature of 480C with the help of an hydrogenating
catalyst a high cracking yield is achieved. The process requires high effort.

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Step 2: Conversion
Catalytic
Cracking

Reaction
Feedstock reacts with
catalyst and cracks into
different hydrocarbons

Regeneration
Catalyst is reactivated
by burning off coke

Fractionation
Cracked hydrocarbon
stream is separated
into various products.
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Step 2: Conversion
Reforming
Catalytic reforming = removing hydrogen from hydrocarbons producing
compounds with higher octane ratings such as aromatics.
Catalytic reformer unit is used to convert the naphtha-boiling range molecules
into higher octane reformate (reformer product). The reformate has higher
content of aromatics and cyclic hydrocarbons. An important by-product of a
reformer is hydrogen released during the catalyst reaction. The hydrogen is
used either in the hydrotreaters (uses hydrogen to desulfurize distillates after
atmospheric distillation) or in the hydrocracker.

Steam reforming unit produces hydrogen for the hydrotreaters or hydrocracker.
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Step 2: Conversion
Alkylation

= assembly of hydrocarbon molecules (the opposite of cracking)

Catalytic high-pressure hydrogenetion
Production of gasoline (petrol) from distillation residue (low hydrogen content)
by adding hydrogen under pressure and temperature. Analogous to the
process of producing gasoline from coal.

Hydrogeneting refining under pressure
Production of fuel from unsaturated hydrocarbons by attaching hydrogen, after
removing S, N, O, H
2
S, NH
3
und H
2
O at pressures of 1 to 10 MPa and
temperatures of 300 to 400C. These fuels have a good storage stability and
dont cause corrosion

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21
Step 2: Conversion
Coking

Coking is a severe method of thermal cracking used to upgrade heavy
residuals into lighter products or distillates such as gasoline and diesel fuel .
Coking produces straight-run gasoline (coker naphtha) and various middle-
distillate fractions used as catalytic cracking feedstock.
The process so completely reduces hydrogen that the residue is a form of
carbon called "coke" (petroleum coke).
The two most common processes are delayed coking and continuous
(contact or fluid) coking.

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Step 3: Removing Impurities
Fractions contain impurities such as S, N, O, water, metals, inorganic
salts. They are removed by:

Sulfuric acid tower

Absorption tower

Scrubber

Separates unsaturated hydrocarbons, nitrogen,
oxygen, and solid residues such as asphalt
Separates water using a drying agent
Separates sulphur & sulphur compounds
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Step 3: Removing Impurities
Desulphurization
Hydrofiner and Claus-Unit
Sulphur is natural component of crude oil. Depending on the deposit, the
sulphur content is between some tenth percent (North Sea, North-Africa)
and several percent (Arabia, Russia, South-America)
The quality standards for distillate products from crude oil such as liquefied
gas, gasoline/petrol, diesel fuel, and heating oil EL can only be met by
desulphurization.
This is done in the Hydrofiner (hydro-desulfurization): The sulphur
compounds in the distillate react at a catalyst with hydrogen, forming
gaseous hydrogen sulfide H
2
S.
The hydrogen sulfide gas is separated and then in the Claus-Unit processed
to sulphur. Overall main reaction equation: 2 H
2
S + O
2
S
2
+ 2 H
2
O (The
real process runs in several steps, with SO2 as intermediate product.)
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24
Step 4: Blending
Blending is done to obtain the specific characteristics of the end
products, for example:

Blending gasoline fraction with branched chains / alicyclics /
aromatics and various additives to obtain a certain gasoline grade
(octane number)

Blending lubricating oil fraction with various hydrocarbons and
additives

Blending of naphtha fraction to obtain various grades for
petrochemical industries

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Utilization of the Petroleum Fractions

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26

Fraction C-
atoms
Boiling
point [C]
Utilization
Gas 1 - 4 < 20 LPG liquefied petroleum gas, as fuel and as
raw material for synthesizing organic compounds
Gasoline 5 - 10 40 180 Fuel for vehicles
Naphtha 6 - 10 70 180 Synthesizing organic compounds for plastic,
synthetic rubber, detergent, medicine, paint,
Kerosene 11 - 14 180 250 Fuel for airplane, paraffin stove,
Diesel oil 15 - 17 250 300 Fuel for diesel engines, and for industries
Lubricating oil 18 - 20 300 350 Lubricant (high viscosity)
Wax > 20 > 350 Paraffin wax for candles, matches, shoe polish, ...
Heavy oil > 20 > 350 Fuel for ships, boiler plants, power plants
Bitumen > 40 > 350 Materials for asphalts, roofing, anticorrosion
coating, electric isolator,
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Deepen your knowledge:

Select some typical marine engineering applications of
petroleum products.
What are important quality requirements for these products?
Which petroleum fractions are used?
How are the petroleum fractions processed to achieve the
quality requirements on the products?

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Tks

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Questions ?

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Literature
1. OSHA_Petroleum Refining Process.docx

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Web links
1. http://www.en.wikipedia.org/wiki/Cracking_(chemistry)
2. http://www.world-petroleum.org/index.php?/Technology/petroleum-refining-
courtesy-of-aip.html
3. https://www.osha.gov/dts/osta/otm/otm_iv/otm_iv_2.html

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