Petroleum Refining Chapter 2: Composition of Petroleum and its Products

Chapter 2: The Composition of Petroleum and its products

Introduction

Petroleum is a mixture of compounds - HCs (C & H).

Range from CH4 to C85H60.

Elemental Composition in rude oil1.

Table 2.1: Elemental Composition in crude oil.
Element

% wt

C
H
S
N
O
V
Ni
Cu

84 87
11 14
03
0 0.6
Traces
Traces
Traces
Traces

Hydrocarbon

Non-hydrocarbon

Non-hydrocarbon elements (O, S, and N) are present as components of complex molecules

predominantly HC in character.

Non-hydrocarbon elements (V, Ni, and Cu) are present from filed production operations.

The boiling point of crude oil ranges from 90 to 1500 F.

Compounds in crude oil are classified as - Paraffins and isoparaffins

- Olefins
- Naphthenes
- Aromatics

Not to mention, water, salt, sand, sediments, etc.

1

Copyrights 2001-2015, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University

RSH

R-S-R'

R-S-S-R'

Thiols
(Mercaptans)

Sulfides

Disulfides

Cyclic Sulfides

Thiophene

Benzothiophene

Dibenzothiophene

Naphthobenzothiophene
Figure 2.1: Examples of simple organic sulfur compounds in crude oil and its products.
(source: Speight, 'the chemistry and technology of petroleum', 1999, p.229)

ROH

R-COOH

R-COO

Alkylalcohols

Carboxylic acids

R-O-R'

R-COO-R'

R-CO-R'

Carboxylic acid esters

Ketones

Ethers

Carboxylic acid anhydrides

O
Diphenylether

Tetrahydropyran

Furan

Benzofuran

Figure 2.2: Examples of simple organic oxygen compounds in crude oil and its products.
(source: Speight, 'the chemistry and technology of petroleum', 1999, p.233)

Petroleum Refining Chapter 2: Composition of Petroleum and its Products

Paraffins

General formula (CnH2n+2)

Carbon is capable of forming single, double multi-branched chains which give rise to
isomers that have significantly different properties.

The number for possible isomers increases in geometric progression as the number of atom
increases (Table 2.2).

Crude oil contains molecules with up to 70-85 carbon atoms, & the number of possible
paraffinic HCs is very high.

propane

n-butane

isobutane

n-pentane

isopentane

Figure 2.3: Examples of simple paraffins in crude oil and its products

Table 2.2: Number of possible paraffinic hydrocarbon isomers.

Molecule
Methane
Ethane
Propane
Butanes
Pentanes
Hexanes
Heptanes
Octanes
Nonanes
Decanes
Undecane
Dodecanes
Tridecanes
Tetradecane
Pentadecanes
Hexadecanes
Heptadecanes
Octadecanes

Symbol

# of paraffin isomers

C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18

1
1
1
2
3

17

355

60,533

neopentane

Copyrights 2001-2015, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University

Olefins

Do not naturally occur in crude oils - but are formed during processing in the
thermal/catalytic cracking units like the delayed coker and the FCC.

They are very similar in structure to paraffins, but at least two of the C atoms are joined by
double bonds.

The general formula is CnH2n.

In gasoline boiling range, olefins are desirable because they have a higher RON than
paraffins.

However, olefins are generally undesirable in finished products, because:

1. Double bonds are reactive and the compounds are more easily oxidized and
polymerize to form gums and varnishes.
2. Some diolefins, formed during processing, react very rapidly with olefins to form
high MW polymers and form filter plugging compounds.
3. C5 olefins have high reaction rates with compounds in the atmosphere that form
pollutants.

Naphthenes

Are cycloparaffins in which all the bonds are single.

The general formula is CnH2n.

Naphthenes can have paraffin side chains.

Many types of naphthenes exist in crude oil (Figure 2.4)

Except for the lower MW compounds, such as cyclopentane and cyclohexane, Naphthenes
are generally not handled as individual compounds. They are classified according to boiling
range, and their properties are determined with the help of correlation factors such as Kw
factor, or CI.

Petroleum Refining Chapter 2: Composition of Petroleum and its Products

Cyclopentane

Methylcyclopentane

Dimethylcyclopentane

Cyclohexane

Methylcyclohexane

1,2-dimethylcyclohexane

.
Decalin
(Decahydronaphthalene)

n-decylcyclopentane

Figure 2.4: Examples of simple naphthenes in crude oil and its products

Aromatics

These are hydrocarbons that contain one or more benzene ring.

Aromatics can have paraffin side chains and can form a mixed structure with naphthenes.

These mixed types have many of the chemical & physical characteristics of both of the
parent compounds (the aromatic and the paraffin), but generally are classified according to
the parent cyclic compound.

Copyrights 2001-2015, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University

Benzene

Toluene

o-xylene

m-xylene

p-xylene

cumene

Naphthalene

Diphenylmethane

o-terphenyl

Pyrene

Indan

Tertahydronaphthalene

Anthracene

Phenanthrene

m-terphenyl

Chrysene

Diphenyl

p-terphenyl

Flourene

Figure 2.5: Examples of simple aromatic hydrocarbons in crude oil and its products

Petroleum Refining Chapter 2: Composition of Petroleum and its Products

Composition of Petroleum Distillates

Figure 2.6: Principal petroleum products, their boiling range temperatures and their number of
carbon atoms.

Copyrights 2001-2015, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University

Boiling point and carbon number range for petroleum products

No.
Petroleum product
Boling Point (C)
1
LPG
2
Gasoline
3
Naphtha
4
WS
5
Jet Fuel
6
Lamp Oils
7
Diesel Fuel & Home Heating oil
8
Paraffins
9
Base Stocks
380 610
10
Heavy Fuels
11
Waxes
12
Asphalts

Carbon Number
C3 C4
C4 C13
C5 C11
C8 C12
C9 C13
C10 C17
C11 C23
C22 C33
C23 C
C23 C
C36 C
C45 C

Petroleum Refining Chapter 2: Composition of Petroleum and its Products

Table 2.3: Compounds Completely Identifiable in Naphtha by a Detailed Hydrocarbon GC analyzer1.

No

Model Compound

No

Model Compound

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50

Propane
Isobutane
n-Butane
2,2-Dimethylpropane (Neopentane)
Isopentane
n-Pentane
2,2-Dimethylbutane (Neohexane)
Cyclopentane
2,3-Dimethylbutane
2-Methylpentane
3-Methylpentane
n-Hexane
2,2-Dimethylpentane
Methylcyclopentane
2,4-Dimethylpentane
2,2,3-Trimethylbutane
Benzene
3,3-Dimethylpentane
Cyclohexane
2-Methylhexane
2,3-Dimethylpentane
1,1Dimethylcyclohexane
3-Methylhexane
1-trans-3-Dimethylcyclopentane
1-cis-3-Dimethylcyclopentane
3-Ethylpentane
1-trans-2-Dimethylcyclopentane
2,2,4-Trimethylpentane (Isooctane)
n-Heptane
Methylcyclohexane
2,2-Dimethylhexane
Ethylcyclopentane
2,5-Dimethylhexane
2,4-Dimethylhexane
1-trans-2-cis-4-Trimethylcyclopentane
2,3,4-Trimethylpentane
1-trans-2-cis-3-Trimethylcyclopentane
2,3,3-Trimethylpentane
Toluene
2,3-Dimethylhexane
2-methyl-3-Ethylpentane
2-Methylheptane
4-Methylheptane
3,4-Dimethylhexane
1-cis-2-cis-4-trans-Trimethylcyclopentane
3-Methylheptane
1-methyl-2-Ethylcyclopentane
1-trans-4-Dimethylcyclohexane
1,1-Dimethylcyclohexane
1-cis-3-Dimethylcyclohexane

51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100

1-methyl-cis-2-Ethylcyclopentane
1-methyl-trans-3-Ethylcyclopentane
1-methyl-cis-3-Ethylcyclohexane
1-ethyl-1-Methylcyclopentane
1-trans-2-Dimethylcyclohexane
n-Octane
Isopropylcyclopentane
C9 Paraffin
C9 Paraffin
2,2,5-Trimethylhexane
2,2,4-Trimethylhexane
2,4,4-Trimethylhexane
2,3,5-Trimethylhexane
3,4-Dimethyheptane
2,4-Dimethylheptane
1-cis-2-Dimethylcyclohexane
n-Propylcyclopentane
Ethylcyclopentane
1-cis-2-Dimenthylcyclohexane
1,1,3-Trimethylcyclohexane
2,5-Dimethylheptane
3,3-Dimethylheptane
3,5-Dimethylheptane
2,4-Dimethylheptane
2,3,3-Trimethylhexane
Ethylbenzene
1-cis-3-cis-5-Trimethylpentane
1,1,4-Trimethylcyclohexane
2,3,4-Trimethylhexane
3,3,4-Trimethylhexane
m-Xylene
p-Xylene
2,3-Dimethylheptane
1-cis-2-trans-4-Trimethylcyclohexane
1-cis-2-trans-4-cis-Trimethylcyclohexane
3,4-Dimethylheptane
3-methyl-Ethylhexane
4-Ethylheptane
4-Methyloctane
2-Methyloctane
C9 Paraffin
3-Methyloctane
C9 Paraffin
o-Xylene
C9 Paraffin
1-methyl-2-Propylcyclopentane
1-methyl-trans-4-Ethylcyclohexane
1-methyl-cis-4-Ethylcyclohexane
C9 Paraffin
3,3-Diethylpentane

Source; Detailed Hydrocarbon Gas Chromatography Analyzer.

9

Copyrights 2001-2015, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University

Table 2.3: continued.

No

Model Compound

No

Model Compound

101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141

2,2,6-Trimethylheptane
1,1,2-Trimethylcyclohexane
n-Nonane
1-methyl-1-Ethylcyclohexane
C10 Paraffin
C10 Paraffin
Isopropylbenzene (Cumene)
tert-Butylcyclopentane
tert-Butylbenzene
Isobutylcyclopentane
C10 Paraffin
C10 Paraffin
1-methyl-4-Isopropylcyclohexane
Sec-Butylcyclopentane
1-cis-2-cis-3-cis-Trimethylcyclohexane
n-Butylcyclopentane
1-methyl-2-Ethylcyclohexane
3-Methylnonane
C10 Paraffin
n-Propylbenzene
n-Propylcyclohexane
C9-Aromatic
C9Aromatic
m-Ethyltoluene
p-Ethyltoluene
1,3,5-Trimethylbenzene
C10 Paraffin
C10 Paraffin
2-Methylnonane
0-Ethyltoluene
2,2-Dimethyloctane
3,6-Dimethyloctane
C10 Paraffin
C10 Paraffin
1,2,4-Trimethylbenzene (Psuedocumene)
1-cis-methyl-3-Ethylcyclohexane
1-trans-methyl-2-Ethylcyclohexane
1-trans-2-methyl-Propylcyclohexane
C10 Paraffin
C10 Paraffin
1-methyl-Ethylbenzene

142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182

1-ethyl-2,3-Dimethylcyclohexane
Isobutylbenzene
n-Decane
C11 Paraffin
C11 Paraffin
1,2,3-Trimethylbenzene (Hemimellitene)
C11 Paraffin
C11 Paraffin
C11 Paraffin
C11 Paraffin
4-Methyldecane
1-methyl-2-Isopropylbenzene (o-Cymene)
C10 Naphthene
sec-Butylbenzene
C11 Paraffin
n-Butylbenzene
C10 Aromatic
1-methyl-4-Propylbenzene
1-methyl-3-Propylbenzene
C10 Aromatic
Isobutylcyclohexane
C11 Paraffin
5-Methyldecane
1,4-Diethylbenzene
C10 Aromatic
C10 Aromatic
1-methyl-2-Propylbenzene
C11 Paraffin
C11 Paraffin
trans-1-methyl-2-(4-methylpentyl)-Cyclopentane
C11 Paraffin
C11 Paraffin
2-ethyl-1,4-Dimethylbenzene
C10 Aromatic
1,4-dimethyl-2-Ethylbenzene
n- Undecane
C11 Paraffin
1,2,4,5-Tetramethylbenzene
1,2-dimethyl-4-Ethylbenzene
C11 Paraffin
C11 Aromatic

10

Petroleum Refining Chapter 2: Composition of Petroleum and its Products

Table 2.4: Compounds Completely Identifiable in Naphtha by a Detailed Hydrocarbon GC analyzer 1.

No Formula Model Compound

No Formula

Model Compound

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34

35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68

cis-1,3-ethylmethylcyclopentane
trans-1,2-ethylmethylcyclopentane
trans-1,3-ethylmethylcyclopentane
2,2,3-trimethylpentane
2,2-dimethylhexane
2,3-dimethylhexane
2,4-dimethylhexane
2,5-dimethylhexane
2-methyl-3-ethylpentane
2-methylheptane
3,3-dimethylhexane
3,4-dimethylhexane
3-ethylhexane
3-methyl-3-ethylpentane
3-methylheptane
4-methylheptane
N-octane
2,2,5-trimethylhexane
2,2-dimethylheptane
2,3,5-trimethylhexane
2,3-dimethylheptane
2,4-dimethylheptane
2,5-dimethylheptane
2,6-dimethylheptane
2-methyl-4-ethylhexane
2-methyloctane
3,3-dimethylheptane
3,4-dimethylheptane
3,5-dimethylheptane
3-ethylheptane
3-methyloctane
4-ethylheptane
4-methyloctane
n-nonane

C3H8
C4H10
C4H10
C5H10
C5H12
C5H12
C6H12
C6H12
C6H14
C6H14
C6H14
C6H14
C6H14
C6H6
C7H14
C7H14
C7H14
C7H14
C7H14
C7H16
C7H16
C7H16
C7H16
C7H16
C7H16
C7H16
C7H16
C7H16
C7H8
C8H10
C8H10
C8H10
C8H10
C8H16

Propane
isobutane
n-butane
Cyclopentane
2-methyl butane (isopentane)
n-pentane
Cyclohexane
methylcyclopentane
2,2-dimethyl butane (neohexane)
2,3-dimethyl butane
2-methyl pentane
3-methyl pentane
N-hexane
Benzene
1,1-dimethyl cyclopentane
1,2-dimethyl cyclopentane-trans
cis-1,3-dimethylcyclopentane
Ethylcyclopentane
trans-1,3-dimethylcyclopentane
2,2,3-trimethylbutane (Triptane)
2,2-dimethylpentane
2,3-dimethylpentane
2,4-dimethylpentane
2-methylhexane
3,3-dimethylpentane
3-ethylpentane
3-methylhexane
N-heptane
Toluene
Ethylbenzene
M-xylene
o-xylene
P-xylene
cis-1,2-ethylmethylcyclopentane

C8H16
C8H16
C8H16
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C9H20
C9H20
C9H20
C9H20
C9H20
C9H20
C9H20
C9H20
C9H20
C9H20
C9H20
C9H20
C9H20
C9H20
C9H20
C9H20
C9H20

Source; Detailed Hydrocarbon Gas Chromatography Analyzer.

11

Copyrights 2001-2015, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University

Table 2.5: Compounds Completely Identifiable in Naphtha by a PIONA GC analyzer2.

No Formula Model Compound

No Formula Model Compound

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18

19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36

C5H10
C5H12
C6H12
C6H14
C6H14
C7H14
C7H16
C7H16
C8H16
C8H18
C8H18
C9H20
C9H20
C9H20
C10H20
C10H22
C10H22
C11H24

Cyclopentane
n-pentane
Cyclohexane
2-methyl pentane
N-hexane
Methylcylohexane
2-methylhexane
N-heptane
Ethylcyclohexane
2-methylheptane
N-octane
isopropylcyclohexane
2-methyloctane
n-nonane
tert-butylcylohexane
2-methylnonane
n-decane
n-undecane

C12H26
C6H6
C8H10
C9H12
C10H14
C10H18
C8H10
C9H12
C11H16
C10H12
C5H10
C6H12
C6H10
C7H14
C8H16
C9H18
C10H20
C7H8

n-dodecane
Benzene
Ethylbenzene
isopropylbenzene
sec-butylbenzene
cis-decaline
o-xylene
1,2,3-trimethylbenzene
pentamethylbenzene
1,2,3,4-tetrahydronaphthalene
1-pentene
1-hexene
1-methylcyclopentene-1
1-heptene
1-octene
1-nonene
1-decene
Toluene

Source; PIONA Gas Chromatography Analyzer.

Table 2.6: Compounds Completely Identifiable in Naphtha by a PINA GC analyzer3.

No Formula Model Compound

No Formula Model Compound

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15

16
17
18
19
20
21
22
23
24
25
26
27
28
29
30

C5H10
C5H12
C6H14
C6H14
C7H14
C7H16
C7H16
C8H16
C8H18
C8H18
C9H20
C9H20
C9H20
C10H20
C10H22

Cyclopentane
n-pentane
2-methyl pentane
N-hexane
Methylcylohexane
2-methylhexane
N-heptane
Ethylcyclohexane
2-methylheptane
N-octane
isopropylcyclohexane
2-methyloctane
n-nonane
tert-butylcylohexane
2-methylnonane

C10H22
C11H24
C12H26
C6H6
C8H10
C9H12
C10H14
C10H18
C8H10
C9H12
C11H16
C10H12
C7H8
C6H12
C6H12

n-decane
n-undecane
n-dodecane
Benzene
Ethylbenzene
isopropylbenzene
sec-butylbenzene
cis-decaline
o-xylene
1,2,3-trimethylbenzene
pentamethylbenzene
1,2,3,4-tetrahydronaphthalene
Toluene
Cyclohexane
methylcyclopentane

Source; Detailed Hydrocarbon Gas Chromatography Analyzer.

12

Petroleum Refining Chapter 2: Composition of Petroleum and its Products

Composition of Vacuum Residue

Vacuum residue contains thousands of complex (high molecular weight, high boiling point)
hydrocarbons and organic compounds.

This is divided into three main fractions.

1. Oil fraction.
2. Resin fraction
3. Asphaltene fraction.

Oil + C3
Vacuum Residue

C3 EXTRACTION

Resin + C5/C6/C7
C5/C6/C7 EXTRACTION
Asphaltene
(insoluble in C3 - C7)

Figure 2.7: Separation of vacuum residue.

1. Oil fraction.
-

Highly paraffinic.
Usually contains no metals.
Has lower S and N content than the vacuum residue.

2. Resin fraction
-

Contains certain condensed-ring aromatics

Has substantial amount of paraffinic structure
Sulfur concentrations are approximately the same as the vacuum residue (from which they
are derived)
Contain 10-20 %wt of the metals in the crude.
Serves as a solvent for the asphaltenes
MW 600 5,000 (solution techniques)
MW 60 500 (mass spectrometer)

3. Asphaltene fraction.
-

Very low H/C ratio.

Contains 80-90% of the metals in crude (Ni, V).
Consists of highly condensed aromatic ring compounds
MW 5,000 10,000 (solution techniques)
MW 500 1000 (mass spectrometer)

13

Copyrights 2001-2015, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University

Naphthenic rings
S

S
Valence
bonds
Paraffinic side chain

hetro atom
(N, S, O, V, Ni)
Sheets of highly condensed ring structure (3-5)

Figure 2.8: Hypothetical asphaltene molecule structure

14

Petroleum Refining Chapter 2: Composition of Petroleum and its Products

References
1. David R. Lide, CRC Handbook of Chemistry and Physics, 82nd ed, CRC Press, 2001. (QD
65 C7 2001-2002)
2. James Speight, The Chemistry and Technology of Petroleum, CRC Press, 1999.
3. Klaus H. Altgelt and Boduszynski, Composition and analysis of heavy petroleum fractions,
CRC Press, 1993.

15