Petroleum Refining

Crude Evaluation and product

characterization
Contents
 About Crude oil
 Common Refinery Units
 Crude Distillation
 Secondary Refinery Processes
 Residue processing
 Opportunity crudes and its compatibility
 Crude Evaluation and characterization
About Crude oil
 Composition by weight Element Percent range
 Carbon 83-87%
 Hydrogen10 - 14%
 Nitrogen0.1 - 2%
 Oxygen0.05 - 1.5%
 Sulfur0.05 - 6.0%
 Metals < 0.1%
 Four different types of hydrocarbon molecules appear in crude
oil. The relative percentage of each varies from oil to oil,
determining the properties of each oil
 Composition by weight Hydrocarbon
 Paraffins 30%; Naphthenes49%: Aromatics15% Asphaltene 6%
Common process units found in a
refinery

 Atmospheric distillation unit distills crude oil into fractions.

 Vacuum distillation unit further distills residual bottoms after atmospheric
distillation.
 Naphtha hydrotreater unit uses hydrogen to desulfurize naphtha from
atmospheric distillation. Must hydro treat the naphtha before sending to a
Catalytic Reformer unit.
 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
byproduct of a reformer is hydrogen released during the catalyst reaction.
The hydrogen is used either in the hydrotreaters or the hydrocracker.
 Distillate hydrotreater unit desulfurizes distillates (such as diesel) after
atmospheric distillation.
 Fluid catalytic cracker (FCC) unit upgrades heavier fractions into lighter,
more valuable products.
 Hydrocracker unit uses hydrogen to upgrade heavier fractions into lighter,
more valuable products
Common process units found in a
refinery
 Visbreaking unit upgrades heavy residual oils by thermally cracking them
into lighter, more valuable reduced viscosity products.
 Merox unit treats LPG, kerosene or jet fuel by oxidizing mercaptans to
organic disulfides.
 Alternative processes for removing mercaptans are known, e.g. doctor
sweetening process and caustic washing.
 Coking units (delayed coking, fluid coker, and flexicoker) process very
heavy residual oils into gasoline and diesel fuel, leaving petroleum coke as
a residual product.
 Alkylation unit produces high-octane component for gasoline blending.
 Dimerization unit converts olefins into higher-octane gasoline blending
components. For example, butenes can be dimerized into isooctene which
may subsequently be hydrogenated to form isooctane. There are also other
uses for dimerization.
 Isomerization unit converts linear molecules to higher-octane branched
molecules for blending into gasoline or feed to alkylation units.
 Steam reforming unit produces hydrogen for the hydrotreaters or
hydrocracker.
Common process units found in a
refinery

 Liquified gas storage vessels store propane and similar gaseous fuels at
pressure sufficient to maintain them in liquid form. These are usually
spherical vessels or "bullets" (i.e., horizontal vessels with rounded ends).
 Amine gas treater, Claus unit, and tail gas treatment convert hydrogen
sulfide from hydrodesulfurization into elemental sulfur.
 Utility units such as cooling towers circulate cooling water, boiler plants
generates steam, and instrument air systems include pneumatically
operated control valves and an electrical substation.
 Wastewater collection and treating systems consist of API separators,
dissolved air flotation (DAF) units and further treatment units such as an
activated sludge biotreater to make water suitable for reuse or for disposal.
 Solvent refining units use solvent such as cresol or furfural to remove
unwanted, mainly aromatics from lubricating oil stock or diesel stock.
 Solvent dewaxing units remove the heavy waxy constituents petrolatum
from vacuum distillation products
Addressing the concerns to
process Opportune crudes
 Blending of Lighter Crudes, Condensate etc
for transportation
 Modifying existing configuration and pipeline
of refinery for receipt and processing
Opportune crudes

Opportune Crudes could be of High TAN, high pour, Heavy crude of high density
Opportune Crudes and Compatibility
Structure of Crude Oil
A = Asphaltenes (Solute)
R = Resins (Dispersant)
A = Aromatics (Solvent)
S = Saturates(Nonsolvent)

Cause of Instability-Asphaltenes

Polyaromatic in nature with alkyl

substitution usually contain heteroatoms
such as oxygen, nitrogen, sulfur and metal
atoms

Dispersed in the oil with the resins and

this asphaltene-resin dispersion is
dissolved into petroleum oils with
aromatics (solvent) but opposed by
saturates (non-solvents).
Opportune Crudes and Compatibility
Methods For Determination
Conventional Process
P- test
Spot test- Insolubility & Solubility Approach
Colloidal Instability Index (CII)
Stability Number (Turbiscan)
Microscope Tests, etc .

Limitations in the study of Blend Compatibility of

Asphaltenic/waxy Crude

Crude oil is a blend containing both saturates and

Asphaltene
Compatibility of saturate and asphaltenic crudes
depends on their content and type
Structure property correlation not explored much
and is of complex nature
 High TAN Crudes

Corrosion due to Naphthenic acids

• Less than 2000C not a problem since NAs are heavier compounds
• Greater than 4200C not a problem because NAs breaks down lighter
acids.
• Problem for streams in the range 2000C – 4200C (Kero, HSD, and VGO
etc)
 Difficulties while processing HAC
 Desalting (high calcium crude oils)
Naphthenic acids can form stable emulsions, foaming problems,
formation of calcium naphthenates are particularly bad factors
 Rapid corrosion with higher fluid Velocity & dual phase flow
 Rapid corrosion due to more physical contact between fluid & metal,
Transfer line
 Crude Distillation Unit
Furnace, Overhead, Column, Side-cut piping etc
Points of vaporization or condensation
Vacuum towers and tower internals
 Problem in Product Streams Diesel and ATF cuts (Higher TAN)
 RCO, LVGO, HVGO and VR circuits,
 Furnace tubes and transfer lines,
 Secondary Processing Units (FCC feed… etc)
 Accumulation of NAs are more in boiling ranges 2000C to 4200C
 Methods of Processing HAC Crudes
S.N APPROACH REMARKS
Blending/dilution with low TAN Diminishing the value of low
1.
crude oils TAN crude oils
2. Caustic treatment Effluent and emulsion problem
Changing the hardware/plant Higher capital cost
3.
metallurgies
Processing High TAN crudes Small size Refineries like in
4. without any hardware change China, Dismantle the plants
after making profits
Processing high TAN crudes
with the use of corrosion Not commercialized at larger
5.
inhibitors & continuous scale
monitoring
Crude TAN Removal
6. New Approach
Processing Opportune Crude Oils
What Determines Average Crude Prices and Hence Differentials
Specific gravity – API – a positive factor :Distillate yields
Sulfur (% by weight) – a negative factor :Cost of Refining
Acidity (TAN) – a negative factor :Corrosion & Fouling
High Pour :Transportation/pumping

Advantages of Processing Opportune Crudes

Ability to process low cost crudes - Crude constitutes more than 80% of
input costs of a refinery e.g., For a 15 MMT capacity refinery, processes 1/3
of opportune crudes costing 1$ less would make over 100 crores additional
profit which is substantial.
Enlarging crude basket – reduced dependency of specific crudes i.e.,
ability to process wide variety of crudes

Each ° API per $ of Brent is worth +$0.00969.

Each % of sulfur is worth -$1.979
Each unit of TAN is worth -$1.435
Crude oil evaluation and product
characterization
Detailed Crude Evaluations

Crude Characterizations
• Density/SG/API
• SUL
• KV
• PP
• CCR
• Nitrogen
• Asphaltene
• Salt
• Metals
• BS&W etc.

Product Characterizations
• LPG
• NAPHTHA (IBP-140)
60-70;70-90;110-140 etc.
• KERO (140-240 &140-290)
• HSD (240-360 & 290-360)
• VGO (360-565)
• LR (360+)
• SR (530+ & 565+)

TBP Distillation following ASTM D2892 and D5236

Objectives of Detailed Crude
Evaluation
 Given the crudes, identifying the suitable crudes for blends through
scientific
 studies.
 Characterize the individual crudes in terms of :
 Assay
 Corrosivity
 Fouling and emulsifying species
 Assess the compatibility of blends
 Simulate the deslater performance
 Impact of Corrosion in atmospheric and vacuum units
 Assess fouling tendencies of the identified crude blends
 Suitability of products to meet Euro (III)/(IV) norms.
 Evaluate economic impact of processing opportune crude blends
THE CHEMISTRY OF CRUDE
OIL
 Crude oils are organic in nature and are made up of carbon and
hydrogen (hydrocarbons) with lesser amounts of sulphur,
nitrogen, oxygen and traces of different metals such as cobalt,
nickel, potassium, calcium, sodium, silicon, copper vanadium etc
 Elemental composition of crude oil can be summarized thus:
Element/Component Percentage Weight Carbon 85.0 Hydrogen
12.0 Sulphur 0.8 Nitrogen 0.6 Oxygen 0.6 Trace metals (e.g. Fe,
Al, Ni, Ca etc) 0.2 Sediments 0.8
 The hydrocarbon contents of crude oils are complex but are
principally:
1. Paraffins (Alkanes) 2. Napthenes (Cycloparaffins) 3. Aromatics
The predominance of one group gives the petroleum certain
properties valuable in formulating a general idea of the
usefulness of the crude in producing various refinery products.
Crude Characteristics
 Density , API, Specific Gravity
 Flow properties – Viscosity, Pour Point
 Sulfur
 Residue – CCR, Ramsbottom
 Total Acid Number
 Mercaptans
 Basic Nitrogen
 Asphaltene content
 Distillation Profile – SIMDIST, D86, D1160
Properties of Fuels and their
significance
 Density

 Essential for quantity calculations, setting purifier, indicates

specific energy and ignition quality.
 Density is the absolute relationship between mass and volume at
a stated temperature and the SI unit is kg/m3. The standard
reference temperature used in international trade for density
calculation of petroleum and its products is 15°C.
 Knowledge of density is required for quantity calculations. Its
value also needs to be known in order to select the optimum size
of gravity disc for the centrifuge. In addition the density gives an
indication of other fuel characteristics, including specific energy
and ignition quality.
 Specific gravity of a substance is the ratio of the mass of a given
volume to the mass of an equal volume of water at the same
temperature. As it is a ratio there are no units.
 API gravity (degrees) = (141.5 / Relative density @ 60 / 60 °F) -
131.5
Viscosity
 Dynamic viscosity is a property of the internal resistance of a fluid that
opposes the motion of adjacent layers. The unit of measure of this
resistance in SI units is a Pascal.s. Frequently the unit of a Poise is
used, where 1 Pascal.s = 10 Poise. It should be noted that dynamic
viscosity is also referred to as absolute viscosity.
 Fuel viscosity is usually expressed as kinematic viscosity, which is
measured in Stokes. Kinematic viscosity is the quotient of the dynamic
or absolute viscosity divided by the density, with both expressed at the
same temperature.
 The storage and handling temperature is determined by the viscosity if
the pour point of the fuel is low. Typical maximum fuel viscosity for
transfer is 800 - 1000 cSt . The temperature for atomisation of the fuel
also depends on viscosity.
 For distillate fuels the reference temperature used is 40°C. However for
residual fuels 50°C is still commonly used, even though the
international marine fuel specification has a reference temperature of
100°C.
Flash point
 The flash point of a fuel is the temperature at
which vapour given off will ignite when an
external flame is applied under standardised
conditions. A flash point is defined to
minimise fire risk during normal storage and
handling.
 Important for volatility of fuels
 Used to evaluate potential hazards on
storage and transportation
Pour Point
 The pour point is the lowest temperature at which a
marine fuel can be handled without excessive
amounts of wax crystals forming out of solution
 If a fuel is below the pour point wax will begin to
separate out, which will block filters. Also the wax
will build up on tank bottoms and on heating coils.
 When heat is reapplied difficulties may be
experienced in getting the wax to re-dissolve
because of its insulating nature
Residue &Ash Content
 Residue content of a fuel signifies the tendency to
form deposits in the exhaust and the quantum of tail
pipe emissions of CO2, SO2, NOx and unburnt HC
 The ash value is related to the inorganic material in
the fuel. The actual value depends upon three
factors, firstly the inorganic material naturally
present in the crude oil, secondly the refinery
processes employed, and thirdly, upon possible
subsequent contamination due to sand, dirt and rust
scale.
 The ash level signifies the deposit formation
tendency of the fuel.
Sulphur
 Sulphur is a naturally occurring element in crude oil that is
concentrated in the residual component of the crude oil
distillation process. Hence the amount of sulphur in the fuel oil
depends mainly on the source of the crude oil and to a lesser
extent on the refining process
 In a diesel engine the sulphur in the fuel having first burnt to
SO2, then combines with excess oxygen to form SO3. In the
presence of water vapour the SO3 is converted to sulphuric acid,
which forms on the cylinder walls if the temperature is below the
dew point for condensation of the acid. This dew point is a
function of the sulphur content of the fuel and the pressure in the
cylinder.
 World wide refineries have implemented various technologies to
reduce fuel sulphur Euro 2 to Euro 5
Total Acid Number
 Acidity inherent in crude oils
 Due to Naphthenic acids and some inorganic
acidity
 Naphthenic acids pose corrosive hazards
while processing
 Quantification of NA – still to be explored
 Literature reports that NA effect is minimized
when crude oil sulfur is high
SARA analysis
 Saturate-Aromatics-Resins-Asphaltene
 Components which decide the distillate yield
of crude oil
 Characterization of residue for SARA can aid
its application as bitumen, fuel oil, coker feed
Oxidation Stability
 Indicates fuel stability on storage
 Significant for automotive fuels viz., MS, HSD
 Severely processed fuels show poor
oxidation stability due to presence of olefins
Typical Detailed evaluation
format
 Cut Range

HVG
CR LPG Naphtha Kerosene Diesel LR SR
O

140 290
- -
Whole 60 - 70 - 110 - 140 - 290 240 - 360 450 - 360 565+
Crude LPG 70C 90C 140 240C C 360C C 565C +C C

Test Method
Fractional
D2892 X
Distillation

Volume Yield D5236 X

Density @15°C D4052 X X X X X X X X X X X

Specific Gravity
D4052 X X X X X X X X
@60/60°F

API Gravity D4052 X X X X X X X X

Aniline Point D611 X X X X

Aniline Gravity
Calc X X X X
Product

Appearance Visual X

Arsenic ICPMS X

Ash D482 X X X X

Asphaltenes IP143 X X X

Carbon Content D5291 X X X X X X X X X X

Hydrogen
D5291 X X X X X X X X
Content
Carbon Residue
D4530 X X X X
- Micro

Characterization
UOP 375 X X
Factor,calc
Cloud Point D2500-02 X X X X X X

Colour - Saybolt D156-00 X X X

DHA - Aromatics D6730-01 X X X

DHA - Naphthenes D6730-01 X X X

DHA - Olefins D6730-01 X X X

DHA - Paraffins D6730-01 X X X

DHA - Unknowns D6730-01 X X X

Distillation D86-01 X X X X X X X

Distillation - vacuum D1160 X X X

FIA - Aromatic D1319-99 X X X X

FIA - Olefins D1319-99 X X X X

FIA - Saturates D1319-99 X X X X

Hydrogen Sulphide UOP163 X

Kinematic Viscosity @40°C D445-01 X X X X X X

Kinematic Viscosity @50°C D445-01 X X X X X X

Kinematic Viscosity @100°C D445-01 X X X

Kinematic Viscosity @135°C D445-01 X X

LPG Composition (Extended) GPA2286 X

Mercury Content UOP938-00 X

Metal - Aluminium ICP X X X X X X

Metal - Calcium ICP X X X X X X

Metal - Chromium ICP X X X X X X

Metal - Copper ICP X X X X X X

Metal - Iron ICP X X X X X X

Metal - Lead ICP X X X X X X

Metal - Magnesium ICP X X X X X X