ChE 404 ORGANIC TECHNOLOGY

Petroleum
2014-20155

1. Definition of Petroleum
2. Formation of Crude oil

3. Composition of Crude oil

4. Characterization Parameters of Crude Oil
5. Petroleum Refining (Seperation)
(desalting, atmospheric distillation, vacuum distillation)

6. Conversion Processes
(cracking, coking, visbreaking, polymerization, alkylation, isomerization, reforming)
7.

Characterization of Petroleum Fractions

(aniline point, octane number, cetane number, diesel index)

8. Blending (Upgrading)

What is the definition of petroleum?

Petra + oleum
Naturally occurred
C5 to C18
NG or NGL
Non-metallic compounds (S, O, N)
V, Ni, Cu, Fe and etc.
Black or dark brown

What is the importance of petroleum?

Demand is ever increasing, especially due to growth of

population & economy

84% of crude oil is refined

into energy-rich fuels.

CDs and DVDs

Food additives

Plastics

Fertilizers and
Pesticides

The remaining 16% of crude oil is used for a range of

purposes shown above as well as synthetic fibres, dyes and
detergents

 Organization of the Petroleum Exporting Countries (OPEC) is

a group of 13 countries that produce 36% of the worlds oil, or
33 million barrels of oil per day.
The biggest producer is Saudi Arabia, but Iran, United Arab
Emirates, Kuwait and Venezuela are also major suppliers.

 Organization for Economic Co-operation and Development

(OECD) produces 24% of all oil, or 22 million barrels per day.
The USA is the biggest single producer in OECD but Mexico,
Canada and the UK are also major suppliers

Outside OECD, the states of the former Soviet Union are also
major producers supplying a further 15% of global output

World Daily Petroleum Consumption

89.8 x106 barrels/day (14.27 x109 L/day)

What do you think about the

formation of crude oil?
8

Formation of Crude oil

Animal plankton

10,000 of these bugs

would fit on a pinhead!

Plant plankton

en.wikipedia.org/wiki/Image:Copepod.

Most oil and gas starts life as microscopic plants and animals
that live in the ocean.

formation theories
Inorganic theory
Berthelot 1866 and Mendeleyev 1879
Chemists could produce methane, acetylene and benzene
in the laboratory conditions.
And they could explain the formation of H2
However, Inorganic theory can explain just simple h.c. but
crude oil is complex liquid mixture

Organic theory
Almost all of oil contain N2 which is the main ingredient of
amino acids
Cholesterol is an ingredient only present in plants and
animals.
The most prevailing theory proposed by Engler in 1913.

Engler Theory
Step 1 Biologycal Formation

Step 3 Migration

Step 2 Catalytic Formation

Step 4 Formation of Petroleum

12

Reserves of Crude Oil

20.6

65.4

63.7

44.0

675.7
74.9

89.5

13

World Proven Reserves of Crude Oil (thousand billion barrels)

CRUDE OIL

Non-Hydrocarbons

Hydrocarbons
Paraffins;
15-60
Aromatics;
wt.%,
3-30 wt.%
ave. 30% ave. 15%

Sulfurs Comp;
0.05-6 wt.%

Naphthenes;
30-60 wt.%
ave. 49%

Oxygen
Comp; Nitrogen
< 2 wt.% Comp;
0.1-2 wt.%,

Metallic
Comp;
< 1000 ppm
14

Hydrocarbons
Paraffins, 30% ave
Satd.
CnH2n+2,
Lineers n-paraffin
Branched iso-paraffin
CH4, or C1 is the most
stable
Isoparaffins ON in
gasoline

Aromatics, 15% ave

Unsatd.
Cyclic compounds
Monoaromatics,
H can be substituted
by alkyl group,
Polynuclear aromatics,
Benzene is the most
stable

Napthenes, 49% ave

Satd.
CnH2n,
At least one ring of C
atom,
These rings usually
have alkyl
substituents,
Higher ON than same
C atom paraffins
15

Paraffins in Crude Oil

16

Aromatics in Crude Oil

17

Naphthenes in Crude Oil

18

Non-Hydrocarbons
Sulfurs Comp;
0.05-6 wt.%
Sweet, if <1%
Sour, if >1%

CH3SH
Methyl mercaptan
SH

Phenyl mercaptan

Oxygen Comp;
< 2 wt.%
In variety form;
alcohols, ethers,
carboxylic acids,
phenolic comp,
ketones, esters and
anhydrides
Acidic Corrosion
Methyl Alcohol,

Nitrogen Comp;
< 1 wt.%
More
stable
than S, hard to
remove
Catalyst
poisoning in
cracking rxns

Pyridine

CH3CH2-O-CH3
Ethyl methyl ether

19

Characterization Parameters of Crude Oil

Specific Gravity
API Gravity
Boiling Point Curves (TBP & ASTM D86)
Watson characterization factor

Viscosity
Aniline Point
20

 Specific Gravity
Density of crude oil
at 1 atm and 15.6C
SG =
Density of water

Type of Crude
Light Crudes
Medium Crudes

Heavy Crudes

SG
SG < 0.825
0.825 < SG <0.875

SG > 0.875
21

 API Gravity
141.5
API =
131.5
SG

Type of Crude

Light Crudes
Medium Crudes
Heavy Crudes

API

API > 38
38 > API > 29
29 > API > 8.5

22

 Boiling Point Curves

TBP (True Boiling Point)
in columns 15 plates and reflux ratio of 5
ASTM D 86 Distillation
simple flask and condenser
TBP = a (ASTM D86)b [R]
a and b are constants varying with percent of liquid
sample distilled, temperature is in Rankin

23

EXAMPLE - I
A petroleum cut has the following ASTM D86 distillation
data;
Volume %
distilled
0
10
30
50
70
90
95

T (C)

36.50
54.00
77.00
101.50
131.00
171.00
186.50

0.9167
0.5277
0.7429
0.8920
0.9045
0.9490
0.8008

1.0019
1.0900
1.0425
1.0176
1.0226
1.0100
1.0355

Draw a ASTM D86 curve vs. distilled vol.%

Obtain the TBP curve.
Find the volume fraction of kerosene between 150-175C
boiling range by using TBP curve.

24

ASTM D86, C

ASTM D86
200
180
160
140
120
100
80
60
40
20
0

10

20

30

40 50 60 70
Vol. % Distilled

80

90

100
25

ASTM D86, C

ASTM D86

TBP

200
180
160
140
120
100
80
60
40
20
0

10

20

30

40 50 60 70
Vol. % Distilled

80

90

100
26

ASTM D86, C

ASTM D86
200
180
160
140
120
100
80
60
40
20
0

TBP

77 %

10

20

30

40 50 60 70
Vol. % Distilled

87 %

80

90

100

87 % - 77 % = 10 % of kerosene was distilled <> 150-175 C

27

Watson characterization factor

The Watson characterization factor ranges from less than 10 for
highly aromatic materials to almost 15 for highly paraffinic
compounds.

(Tb )1/3
K Watson =
SG
Tb : mean average boiling point (MeABP) [R]

28

EXAMPLE - II
A petroleum fraction has gravity of 18.8API & Watson Kfactor of 9.0.
What is the mean average boiling point this fraction?
Find the group of this fraction with respect to Tb by using
Table given below.
Fractions

Fuel Gas, LPG, Refinery Gas

Boiling points, C

<25

Naphtha

30-70

Gasoline - Petrol

70-180

Kerosene

180-260
29

Viscosity
The resistance to flow or pumpability of the crude oil is
indicated by the viscosity.
The viscosity of many petroleum fuels is important for the
estimation of optimum storage, handling, and operational
conditions.
Viscosity is measured at 37.8C (100F) by ASTM D 445 and D
446 at 99C (210F).

Aniline Point (C6H5NH2 )

Shows the degree of aromaticity
Aniline and crude is mixed with equal volume.

31

Petroleum Refining
Petroleum can be separated into different fractions and
converted to valuable products in refining processes.
The petroleum refining industry converts crude oil into more
than 2500 refined products, including liquefied petroleum gas,
gasoline, kerosene, aviation fuel, diesel fuel, fuel oil, lubricating
oil and petrochemical industry feedstock.

32

CRUDE

Petroleum delivered from well field

DESALTING

Removing impurities

SEPERATION

Distillation to separate by boiling point ranges

CRACKING

REFORMING

BLENDING

Heavy fractions are cracked into smaller

molecules
Conversion
structures

reactions

to

alter

molecular

Mixing to obtain maximum commercial

characteristics

33

Desalting

Crude oil often contains water, inorganic salts, suspended solids,

and water-soluble trace metals.
In the refining process, the aim is to remove these contaminants
so as to reduce corrosion, plugging, and fouling of equipment and
to prevent poisoning catalysts in processing units.
The two most typical methods of crude-oil desalting are chemical
and electrostatic separation, and both use hot water as the
extraction agent.
34

Desalting
First, the crude oil feedstock is heated to 65-180C to
reduce viscosity and surface tension for easier mixing and
separation of the water.
In chemical desalting, water and chemical surfactant
(demulsifiers) are added to the crude, which is heated
before so that salts and other impurities dissolve or attach
to the water, then held in a tank to settle out.

Electrical desalting is the application of high-voltage

electrostatic charges to concentrate suspended water
globules in the bottom of the settling tank.
In both methods other chemicals may be added. Ammonia
is often used to reduce corrosion. Caustic or acid may be
added to adjust the pH of the water wash.

35

36

Desalting

37

Distillation

Distillation is defined as a process in which a liquid or vapor

mixture of two or more substances is separated into its
component fractions of desired purity, by the application and
removal of heat.

38

Atmospheric Distillation

The first step in the refining process is the separation of crude

oil into various fractions or straight-run cuts by distillation in
atmospheric and vacuum towers.
The main fractions or "cuts" obtained have specific boilingpoint ranges and can be classified in order of decreasing
volatility into gases, light distillates, middle distillates, gas oils,
and residium.

39

40

Vacuum Distillation

To extract more distillates from the atmospheric residue,

the bottom from the atmospheric distillation unit is sent to
the vacuum distillation unit.
Vacuum distillation is required or applied to the fractions
which have boiling points greater than 350C.
Operated at 25-40 mmHg
Cracking may occur at higher temperatures

41

Vacuum Distillation

42

 Vacuum distillation evolved because of the need to

separate the less volatile products, such as lubricating oils,
from the petroleum without subjecting these high-boiling
products to cracking conditions.
The boiling point of the heaviest cut obtainable at
atmospheric pressure is limited by the temperature
(350C) at which the residue starts to decompose (crack).
When the feedstock is required for the manufacture of
lubricating oils, this can be achieved by distillation under
vacuum conditions.
43

Fractions of Petroleum

Fraction
Petroleum
Gas

Boiling
Range (C)

<40

# of C/mole

Uses

1-4

Fuel for
cooking

Fractions
ofof
Petroleum
Fractions
Petroleum

Fraction
Petrol
(Gasoline)

Boiling
Range C
40 - 75

# of C/mole

Uses

5 -10

Fuel for car

engines

Fractions
of Petroleum
Fractions
of Petroleum

Fraction

Boiling Range
(C)

No of carbon
atoms per
molecule

Uses

Naphtha

75 - 150

7 - 14

Chemical
feedstock

Fractions
of Petroleum
Fractions
of Petroleum

Fraction

Kerosene

Boiling
Range (C)

160 - 250

#of C/mole

Uses

11 - 16

Fuel for jet

engines,
cooking and
heating

Fractions of Petroleum
Fractions of Petroleum

Fraction

Boiling
Range (C)

#of C/mole

Uses

Diesel

250 - 300

16 - 20

Fuel for diesel

engines

Fractions of Petroleum

Fraction

Lubricants

Boiling
Range C

300 - 350

#of C/mole

Uses

20 - 35

Making waxes
and
lubricating
oils

Fractions
of Petroleum
Fractions
of Petroleum

Fraction

Boiling
Range, C

#of C/mole

Uses

Bitumen

Above 350

More than 70

Paving roads

Example III: Crude Distillation Material Balance

Consider the Kuwait export crude with the following TBP-vol%
data.
Volume %

TBP (C)

40

10

85

30

215

50

340

70

495

51

a) Plot TBP vs vol% for crude.

b) Determine the volumetric yield of the products given in
table.
c) Perform a material balance for a feed rate of 1000
m3/day. Then calculate mass flowrate of each cut.
d) Plot the TBP for kerosene

52

TBP, C

600
500

TBP, C

400
300
200

100
0
0

20

40
60
Volume fraction %

80
53

b) Determine the volumetric yield of the products

given in table by using TBP curve.
Cut

Product

End point (C)

MW

SG

Off gas

40

55.6

0.635

LSR naphtha

70

71.2

0.680

Naphtha

180

112.4

0.754

Kerosene

240

159.8

0.803

Light diesel

290

200.1

0.831

Heavy diesel

340

243.6

0.854

Atm. gas oil

370

284.7

0.870

Vacuum gas oil

390

313.2

0.880

Vac. distillate

550

434.7

0.910

54

600
y = 6.8372x + 9.3708
R = 0.9983

500

TBP (C)

400
300
200
100
0
0

10

20

30

40
Vol.%

50

60

70

80
55

y = 6.83x+ 9.37
where y is temperature and x is vol. fraction
For 1st cut;
T= 40 C
then 40 = 6.83x+9.37
volume fraction or x = 4.48 %
For 2nd cut;
T= 70 C
then 70 = 6.83x+9.37
volume fraction or x = 8.88%
Apply this method for all cut. Then, we will obtain the
following table
56

Cut

Product

End point (C)

Vol%

Off gas

40

4.48

LSR naphtha

70

8.88

Naphtha

180

24.98

Kerosene

240

33.77

Light diesel

290

41.09

Heavy diesel

340

48.41

Atm. gas oil

370

52.80

Vacuum gas oil

390

55.73

Vac. distillate

550

79.16
57

c) Perform a material balance for a feed rate of 1000

m3/day. Then calculate mass flowrate of each cut.
Take Cut 1
F = 1000 m3/day and Vol%= 4.48
1000 m3/day x 0.0448 = 44.8 m3/day for Cut 1

SG = oil/ water then assume water is 1g/cm3

oil = 635 kg/m3
44.8 m3/day x 635 kg/m3 = 1185.3 kg/h
58

Take Cut 2:
Net volume fraction of Cut 2= Vol fraction of Cut2 - Vol
fraction of Cut1
Net vol fraction = 8.88 4.48 = 4.4 %

F = 1000 m3/day and Vol%= 4.40

1000 m3/day x 0.044 = 44.0 m3/day for Cut 2
SG = oil/ water then assume water is 1g/cm3
oil = 680 kg/m3
44.0 m3/day x 680kg/m3 = 1244.5 kg/h

59

SG

Vol
%

Q
(m3/day)

M (kg/h)

Off gas

0.635

4.48

44.8

1185

LSR naphtha

0.680

4.39

43.9

1244

Naphtha

0.754

16.10

161.1

5059

Kerosene

0.803

8.78

87.8

2939

Light diesel

0.831

7.32

73.2

2534

Heavy diesel

0.854

7.32

73.2

2604

Atm. gas oil

0.870

4.39

43.9

1592

Vacuum gas oil

0.880

2.93

29.8

1073

Vac. distillate

0.910

23.4

234.2

8882

Cut

Product

60

d) Plot the TBP for kerosene.

Cut

Product

End point (C)

Net Vol%

Off gas

10

4.48

LSR naphta

70

4.39

Naphta

180

16.1

Kerosene

240

8.78

The cumulative vol.% at initial boiling point (180C) =

(4.48+4.39+16.1)=24.98%
The cumulative vol.% at end boiling point (240 C) =
24.98+8.78=33.77%
33.77 24.98 = 8.78 vol.% between 180C and 240C.

61

Vol. %
kerosene

Vol. %

TBP(C)

24.9

180

20

24.9+0.2(8.78) = 26.7

192.0

40

24.9+0.4(8.78) = 28.4

203.9

60

24.9+0.6(8.78) = 30.2

215.8

80

24.9+0.8(8.78) = 32.0

100

33.77

227.8
240
62

250
240

TBP (C)

230

220
210
200
190
180

170
0

20

40
60
vol% of kerosene

80

100
63