fpReid vapor pressure (RVP), determined by the ASTM test method D323,[1] is

widely used in the petroleum industry to measure the volatility of petroleum

crude oil, gasoline and other petroleum products. It is a quick and simple method
of determining the vapor pressure at 37.8 C (100 F) of crude oil and petroleum
products having an initial boiling point above 0 C (32 F).

Vapor pressure is an important physical property of volatile liquids. It is of critical

importance for automotive and aviation gasolines since it affect the starting and
warm-up of spark-ignited internal combustion engines as well as the tendency to
cause "vapor lock" in the fuel pumps with high operational temperatures and/or
high altitudes.

Air pollution regulatory authorities mandate maximum gasoline vapor pressures

in many areas so as to limit the evaporative emissions of smog-forming
hydrocarbons from gasoline.

Vapor pressure is also important as an indirect measure of the evaporation

tendency of volatile petroleum solvents.

The difference between RVP and TVP

True vapor pressure is referred to in the petroleum industry as TVP. Both the Reid
vapor pressure (RVP) and the true vapor pressure (TVP) are absolute pressures
as distinguished from gauge pressures (see Pressure).

Because of the presence air (and its of water vapor content) in the vapor space
within the test method's sample container, as well as some small amount of
sample vaporization during the warming of the sample to 37.8 C (100 F), the
RVP differs by a small amount from the TVP of the sample.

Weathering : LPG sample is chilled by means of a cooling coil and collected 100
mL of liquid is taken in a weathering tube. Allowed to evaporate at atmospheric
pressure under specied conditions . Correct the observed temperature, when 5
mL of liquid test portion remains, for barometric pressure and report as the 95 %
evaporation temperature. Signicance of the test is intended to nd out the
presence of heavier hydrocarbons in LPG like pentanes and hexanes etc , which
may not readily evaporate.
RVP : Vapour pressure is an important physical property of volatile liquids. It is
the pressure that a vapour exerts on its surroundings. For volatile petroleum

products, vapour pressure is used as an indirect measure of evaporation rate.

High vapour pressures and a low distillation temperature for 10% evaporated
both help cold starting. Under hot-operating conditions, high vapour pressure
also contributes to vapour lock and increases vapour formation in fuel tanks. The
most commonly used method for petroleum products has been the Reid vapour
pressure , as determined by ASTM D323 (American Society for Testing of
Materials) method (Reid Method). This test method determines vapour pressure
at 37.8 'C (100 'F) of petroleum products with initial boiling point above 0 'C (32
'F). It is measured by saturating a known volume of oil in an air chamber of
known volume and measuring the equilibrium pressure, which is then corrected
to one atmosphere (101.3 kPa).

Reid Vapor Pressure (RVP) is a test that measures the vapor pressure of the test
material under simulated storage conditions . It is NOT the 'true vapor pressure',
but is the apparent vapor pressure measured at 100F and saturated with water
and a 4:1 test liquid: water saturated air ratio inside a closed cylinder.
"Weathering" is a description of what happens when a liquid containing volatile
components is continuously exposed to atmospheric pressure through an open
vent or open top tank, allowing the more volatile components to evaporate into
the atmosphere or vapor space in the tank, with continuous vapor removal.
The matter of vapour pressure is important relating to the function and operation
of gasoline-powered, especially carburetted, vehicles. High levels of vaporization
are desirable for winter starting and operation and lower levels are desirable in
avoiding vapour lock during summer heat. Fuel cannot be pumped when there is
vapour in the fuel line (summer) and winter starting will be more difficult when
liquid gasoline in the combustion chambers has not vaporized. Thus, oil reneries
manipulate the Reid Vapour Pressure seasonally specically to maintain gasoline
engine reliability.

The Reid vapor pressure (RVP) differs slightly from the true vapor pressure (TVP)
of a liquid due to small sample vaporization and the presence of water vapor and
air in the conned space of the test equipment. That is, the RVP is the absolute
vapor pressure and the TVP is the partial vapor pressure.[1]

Consider the distillation column of gure 1. It is called stabilizer and has the
task of

removing LPG from naphtha. Every renery has at least three of them, and often
ve or
more, one each in every crude unit, reformer, FCC, hydrocracker, coker,
isomerization,
and possibly other units. Being simple in structure, and with a well dened
objective you
would think controlling a stabilizer is a cinch. Why then we encounter so many of
them
being run with the main DCS controllers in manual?
The name stabilizer reflects a historical task of removing enough LPG to reduce
the RVP
(Reid Vapor Pressure) of naphtha, permitting its storage in floating roof tanks.
Economics have changed however, and today the objective is to remove
essentially all
LPG from the naphtha, subject to a constraint on LPG purity of about 1% C5
contamination. The reasons why operating targets have changed vary from unit
to unit,
and usually have to do with RVP and alkylation economics. On FCC gas plants it
is of
value to remove butane from naphtha because olenic FCC butane is one of the
alkylation ingredients. On saturated gas plants we try to maximize isobutane
recovery
because it is the other alkylation ingredient. That calls for removal of all butane
and
processing it in a deisobutanizer tower. Furthermore, stabilized virgin naphtha is
split
into light and heavy naphtha, and light naphtha is processed in an isomerization
unit.
LPG is problematic in the isomerization unit and should be removed from the
feed. Even
where these considerations do not apply, RVP specications have tightened, and
gasoline blending is easier when the components have low RVP

Crude Assay, ASTM, TBP distillations, Evaluation of

crude oil properties.
Crude Oil Distillation

Crude oil distillation is an open art technology.

The crude oil is distilled at atmospheric pressure and

separated into various fractions as desired in Crude
oil distillation unit .

The reduced crude oil is further fractionated under

vacuum to produce vacuum gas oil (VGO) as a feed
to Hydrocracker or FCCU in a Fuel type Vacuum
Unit,or distilled to produce Lube oil feed stock in a
Lube type Vacuum Unit.
Crude Oil Distillation Scheme

[1,2]

Fig:2.5 Crude Oil Distillation Scheme

Crude Oil Properties

Sulfur, nitrogen, and metals content.

Sulfur.

Sour vs sweet ~0.5 wt% cutoff restrictions on

sulfur in final products.

Nitrogen

Usually tolerate up to 0.25 wt%.

Nickel, vanadium, copper

Can poison catalysts.

Tend to be in the largest molecules/highest boiling

fractions.

Properties appropriate for certain boiling point

ranges
[1,2]

Octane number

Cetane number

Viscosities

Carbon residue

Crude Assay
The complete and definite analysis of a crude oil is called
crude assay.A complete crude assay will contain some or
all of the following:
1. Whole crude gravity, Viscosity, S content, pour point
etc.
2. TBP curve, Mid Volume plot of gravity, Viscosity etc.
3. Light end analysis up to C8 and C9.
4. Properties of fractions. (naphtha, middle distillates,
gas oil residue).Yield vs Vol.%, gravity, S, viscosity,
octane no., diesel index, Flash point , Fire point,
Smoke point, Pore point, Vapor Pressure etc.
5. Properties of lube distillates ( only if the crude is

suitable for the manufacture of lube base stocks).

6. Properties of asphalt (only if residue have suitable
characteristics for preparation of asphalt.
7. EFV curve run at atm. Pressure. Not useful for design
work but is of great importance to the refinery or to
a crude oil purchaser.
Crude Oil Characterization

[1,2]

Trading: Density,API Gravity

Transportation: RVP,Pour Point,KV,Wax content

Contamination: Salt content,BS&W

Processability: Sulfur,Nitrogen,TAN,Asphaltene,MCR

Cracking Point: ASTM Distillation

LPG Potential: Light hydrocarbons(GC)

Classification: Characterization factor

API & S, N & Asphaltene

Fig:2.6 API & S, N & Asphaltene

Crude Oil Assay

Indicates distribution quantity and quality of crude oil

feedstock based upon boiling point temperature
range.

Represents expected
vacuum distillation.

Quality measures

products

from

[1,2]

Specific gravity and API gravity.

Sulfur content.

Octane number and Cetane number.

Viscosity.

Carbon residue.

TBP Curves

Fig:2.7 TBP Curves

crude

and

Watson characterization factor.

12 13 (Paraffinic) to 10 (Aromatic)

Laboratory Distillation

[1-6]

Helps to characterize a product and also helpful in

data designing.

Forms a basis of design of distillation.

Three different types:

A:True boiling point distillation (TBP) for crude used to
obtain true boiling point distillation curve good
fractionation.

Number of
specified.

plates

and

amount

of

reflux

must

True Boiling Point(TBP)(ASTM D2892)

10 to 20 theroretical stages near infinite

reflux.

1 atm; no hotter than 650oF minimize

cracking.

TBP DATA

Large no. of stages and a high reflux to distillate

ratio so as the temperature at any point on
temperature Vs volumetric yields curve represents
the actual boiling (true boiling) points of the
hydrocarbon material present at the Vol. % point.

Hempel
Distillation:Semi
fractionating
type
distillation, but can be used TBP data, where TBP
data are insufficient.

ASTM Distillation or Engler Distillation

Simple distillation carried out with standard ASTM

flask of 100, 200, 500 ml capacity.

No reflux is provided.

Rapid batch distillation employing no trays or reflux

between the still pot and condensation.

Separation is poorer: more volatile and high volatile

components are present in initial condition. So IBP is
higher than TBP.
[1,7]

Distillation Analyses

ASTM D86

Low resolution - no packing reflux from heat

loses.

1 atm; no
cracking.

Correlation to correct to TBP basis.

hotter

than

650 oF

minimize

ASTM Distillation Analyses

ASTM D1160

Used on Resids (650 oF).

Relatively low resolution.

Vaccum conditions- 10 to 40mmHg,no hotter

than 1000oF AEBP.

Correlations to correct to atmospheric pressure

& TBP basis.

ASTM Distillation

At the end in TBP only pure component less volatile

component is present. Whereas in ASTM more
volatile components and less volatile both are
present so FBP is lower in ASTM.

Separation is poorer compared to TBP.

IBP for ASTM is higher than that for the TBP.

FBP for ASTM is lower than that for the TBP.

e.g. Kerosene TBP Range 135-300oC.
ASTM range 160-275oC.

Equilibrium Flash Vaporization

[1,2,7]

By
conducting
operation
at
a
series
of
temperature,curve,% vaporized Vs temperature may
be plotted.

Mixture is heated without allowing the vapor to

separate from the remaining liquids, the vapor assist
in causing the high boiling point of the mixture to
vaporize.

Similar to ASTM but vapor and liquid are kept in

contact till the desired degree of vaporization is
reached. Poorer separation. (Higher IBP LOWER FBP
than ASTM).

CRUDE OIL PRETREATMENT (DESALTING)

Crude oil contains water, inorganic salts, suspended

solids, and water-soluble trace metals.

First step in the refining process is to remove salt

and solids to reduce corrosion, plugging, and fouling
of equipment and to prevent poisoning of the

catalysts in processing units.

contaminants must
(dehydration).

If the salt content of the crude is greater than 10

lb/1000 bbl (expressed as NaCl), the crude requires
desalting to minimize fouling and corrosion caused
by salt deposition on heat transfer surfaces and acids
formed by decomposition of chloride salts.(<1000
lb/bbl).

be

removed

by

desalting

Typical Configuration Atmospheric Column w/o

Preflash
[1,2]

Fig:2.1 Typical Configuration Atmospheric Column

w/o Preflash
[3]

Fig:2.2 Atmospheric Distillation Unit Overview

[3]

Most typical methods of crude-oil desalting:

Chemical and Electrostatic separation:Washing

of the salt from crude oil with water oil and water
phases are separated in a settling tank by adding
chemicals to assist in breaking up emulsion or by the
application of electrostatic field to colapse the
droplets of saltwater more rapidly.

Chemical desalting:Water and chemical surfactant

(demulsifiers) are added to the crude, heated so that

salts and other impurities dissolve into the water or

attach to the water, and then held in a tank where
they settle out.

Electric desalting:Under charge condition polar

molecules get oriented and get separated. More than
90% of salt can be removed in just less than half an
hour.
Desalting of Crude

Fig:2.3 Desalting of Crude

Electric Dehydration and desalting

[1-3]

Electrical desalting is the application of high-voltage

electrostatic charges to concentrate suspended water
globules in the bottom of the settling tank.Either AC
or DC fields may be used and potentials from 12,000
to 35,000 volts are used to promote coalescence.

Surfactants are added if the crude has a large

amount of suspended solids.

The feedstock crude oil is heated to between 150 and

350oF to reduce viscosity and surface tension for
easier mixing and separation of the water.

The temperature is limited by the vapor pressure of

the crude-oil feedstock.

Electric desalting

[1]

The dual field electrostatic process provides efficient

water separation at temperatures lower than the
other processes and as a result,higher energy
efficiencies are obtained.

The salts are dissolved in the wash water and the oil
and water phases separated in a settling vessel
either by adding chemicals to assist in breaking the
emulsion or by developing a high-potential electrical
field across the settling vessel to coalesce the
droplets of salty water more rapidly.

Desired pH <6,at higher pH emulsion forms.

Ammonia is used to reduce corrosion. Caustic or acid

may be added to adjust the pH of the water wash.

Wastewater and contaminants are discharged from

the bottom of the settling tank to the wastewater
treatment facility.

The desalted crude is continuously drawn from the

top of the settling tanks and sent to the crude
distillation (fractionating) tower.

Wash water and T requirement in Desalter:

[1,2]

(3-4vol%, T 240-260oF (API >30), to 7-10 vol%,T

280-300o F for API<30)

For single-stage desalting units 90 to 95%

efficiencies are obtained and two-stage processes

achieve 99% or better efficiency.

Efficiencies of up to 99% water removal in a single

stage are claimed for the dual field process. About
90% of desalters use AC field separation only.

Heavy naphthenic crudes form more stable

emulsions than other crudes. Higher temperature is
required.
Crude Electrostatic desalting

Fig:2.4 Crude Electrostatic desalting

[1,2]

Evaluation of properties of crude oil and

its fractions.
General Procedure for evaluation of crude oil/
fractions
1. From the crude distillation data,plot TBP and gravitymidpercent curves.
2. Select TBP cut-points of products to be made from
atmospheric and vacuum pipe stills.
3. From TBP and gravity curves, determine percentages
and gravities of fractions.
4. Convert volumes percent to weight percents.
5. Determine weight of bottoms stream by difference.If
the volume of bottom stream is taken from the TBP
curve, then gravity is calculated from weight and
volume.
6. For crude oils containing significant amounts of sulfur
or nitrogen, it is also necessary to make sulfur
and/or nitrogen balances around each unit.
Example: Whole crude TBP Data (API Gravity 36.3)
Table:2.2 Plot TBP, M.W , API AND Wt% CURVES FOR
THE CRUDE oil
Volume
percent

5 10 20 30 40 50 60

TBP
6 14 25 34 43 53 62
Temperat
2 4 5 4 7 1
3
ure (oF)
Volume percent
TBP Temperature
(oF)

70

80

85

717 819 897

CALCULATIONS
SP.Gr.For whole crude = 141.5/ (131.5+ API)

Sp. Gr. = 0.84 (for the crude oil)

VABP for whole crude = (t20+t50 + t 80)/3
==>VABP =[ ( 255+ 531+819)/3 ]= 535 oF
TBP Slope =[ (t70- t10)/ 60 ]
= (717-144)/60
= [9.6 oF/%]

Correction Factor (from graph ) = - 70 oF

Mean Average Boiling Point ( MABP) = 535 - 70 =

465 oF

Characterisation Factor
constant) (From graph)

Divide whole crude into various cuts

Kw

11.5

(Assumed

Basis :100 Barrel of crude oil ( 1bbl= 42 US gallon,

1 US Gallon= 3.78 L)
Basis 100 Barrel of crude oil( Weight of the crude =
100x0.843x 349.7=29500 Lb)
(density of water = 349.7 lb/bbl)
Table:2.3

[1,2]

Boili
Cumulat VAB
ng
MABP( AP M.
ive vol. P( F
rang
F)
I W
%
)
e (F)

Mid
vol
%

IBP200

15

110

110

65 78

7.5

200300

25

251

251

15

11
2

20

300400

46.5

482

482

35

18
6

41.
0

Calculation for weight percent

Table:2.4

[1,2]

Wt.
Densi
% Cumula
Vol.
A Sp.
ty
weig
of tive wt.
%cuts PI Gr (lb/b ht
cut
%
bl)
s
65

0.7
377
251.7
2
0

12.
8

12.8

15-25 51

0.7
272
272.7
8
7

9.2

22.0

0.8
297
283.2
1
3

10.
1

32.8

15

2535.5

44

wt.%,calculated based on total mass of crude

(29500 lb)
[1,2]

Fig:2.18 wt.%,calculated based on total mass of

crude (29500 lb)
[1,2]

Exercise

Complete the Table for other fractions (cuts).

Plot API vs mid volume, Molecular weight vs MID

Volume and weight percent vs mid volume for these
cuts.

Calculate
50%
ASTM
and
50%EFV
Boiling
temperatures for each fraction and plot. Draw astm
and EFV curves for the crude.

Fig:2.19
Crude Oil Assay Example-1
Table:2.5

Table:2.6

Table:2.7

50% Boiling Point on ASTM curve :can be calculated

from the slope of TBP curve of a crude and its 50%

B.P can be estimated

Fig:2.20

Fig:2.21 Different Slope and Interconversion

Table:2.8

Fig:2.22

Fig:2.23
Linearized Distillation Yield Curves

Fig:2.24 Linearized Distillation Yield Curves

PONA Analysis (GC)

PONA analysis is the analysis of hydrocarbon mixtures by separation and quantitation of fractions
according to the carbon number or type of hydrocarbon. Analysis can be performed on
hydrocarbon types including naphtha, a primary ingredient of petroleum products; gasoline

automobile fuel; reformed gasoline (reformate), which is a base ingredient of gasoline, and
catalytically cracked gasoline (FCC gasoline).
PONA is an acronym for Paraffins, Olefins, Naphthenes and Aromatics.

Analytical standards include the fluorescent indicator adsorption (FIA) method (JIS K-2536) for
determining aromatic (A), olefinic (O) and saturated (S) hydrocarbons by type, but this method
has the disadvantage of a long analysis time and vulnerability to human error. PONA analysis by
capillary gas chromatography utilizes a non-polar chemically bonded capillary column with a high
theoretical plate number to separate constituent hydrocarbons into as many peaks as possible. It
then identifies each peak and obtains quantitative values according to the number of carbons and
hydrocarbon type. PONA analysis features quantitation of olefins at sub-percentage levels,
quantitation of individual components in addition to type identification, and calculation of mean
density and mean molecular weight.

The analysis of an FIA standard sample is shown below.

Gas Chromatograph

A gas chromatograph (GC) measures the content of various components in a sample. The sample
solution injected into the instrument enters a gas stream, which transports the sample into a
separation tube known as the "column." Helium or nitrogen is used as this so-called carrier gas.
The components are separated inside the column, and a detector measures the quantity of the
components that exit the column. To measure a sample with an unknown concentration, a
standard sample with a known concentration is injected into the instrument. The standard sample
peak retention time (appearance time) and area are compared to the test sample to calculate the
concentration.

Sulfur is used in many EP oils and metal-working fluids as an EP additive. The basic way
this works is for the sulfur to react at elevated temperatures, such as those experienced
by meshing gears to form a sulfide layer. For example, for steel gears, an iron sulfide
layer forms on the gear tooth surface. This ductile layer improves sliding contact,
preventing scuffing or galling.
There are two types of sulfur compounds used active and inactive sulfur. The main
difference is that for active additives, the sulfur-containing additive reacts with the
surface at much lower temperatures, whereas inactive compounds react only at much
higher temperatures. While active additives have advantages of greater reactivity and
hence may offer better anti-scuff protection, especially at lower temperatures, they are
also mildly corrosive, particularly to yellow metals (brass, bronze, etc.), and should be
avoided where these alloys are present.
The amount of active sulfur additive can be measured by first determining the total
sulfur content using an appropriate ASTM test method, then reacting the active sulfur
with copper powder and removing the copper sulfate by filtration, and again measuring
the remaining total sulfur.

Cross head engines operating on residual fuel would typically use an alkaline
cylinder lubricating oil of SAE 50 viscosity grade, with a minimum kinematic
viscosity of about 18 20 cSt at 1000 C. The alkaline reserve of the oil is
indicated by its Base Number (BN, unit mgKOH/g), and must be chosen with

regard to the sulphur content of the fuel. The higher the sulphur content, the
higher the lubricating oils alkaline reserve (BN) must be

It means that, by using circulating reflux (pumparound) from lower points in the column, you are
drawing a stream that is at a higher temperature than the column overhead stream. Since it is at
a higher temperature, you have more driving force for heat transfer than if you were just to use
the overhead stream for the same purpose.
That is exactly the configuration of real crude distillation towers, where you can find up to 4
circulating reflux streams - Heavy Naphtha, Kero, Diesel, and AGO. All these streams are used
for preheating the Crude oil feed, and at the same time you are removing heat from the column at
several locations instead of using only top reflux. Using only the top reflux would not allow you to
preheat the Crude higher than the column overhead temperature is, and by using pumparounds
you can heat the crude up to 250 degC or even higher, depending on the column/unit
configuration.

Internal reflux (IR) provides the liquid traffic necessary for the VLE for the section below the total draw
off / accumulator / chimney trays. IR is returned to column without any cooling. This helps in returning
some of the excess material flashed up (asphaltenes / metals / heavier material from the product below)
towards end point correction. Circulating reflux and pump around are names used for the reflux that
gets a cooled a bit and enters the column in the area above the draw off tray and helps in controlling the
draw off temperatures and draw tray levels (prevents suction loss of the withdrawing pumps). Draw off
temperatures control bulk part of the product quality.