Oil Refining PDF
Oil Refining PDF
Oil Refining PDF
Contents
1 Oil refinery 1
1.1 Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Major products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3 Common process units found in a refinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3.1 Flow diagram of typical refinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3.2 The crude oil distillation unit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.4 Specialty end products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.5 Siting/locating of petroleum refineries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.6 Safety and environmental concerns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.7 Corrosion problems and prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.8 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.8.1 Oil refining in the United States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.9 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.10 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.11 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2 Continuous distillation 9
2.1 Industrial application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.2 Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3 Design and operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.1 Column feed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.2 Improving separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.3 Overhead system arrangements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.4 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.4.1 Continuous distillation of crude oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.5 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.7 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3 Vacuum distillation 15
3.1 Laboratory-scale applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.1.1 Rotary evaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.1.2 Distillation of high-boiling and/or air sensitive materials . . . . . . . . . . . . . . . . . . . 16
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ii CONTENTS
4 Hydrodesulfurization 19
4.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.2 Process chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.3 Process description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.4 Sulfur compounds in refinery HDS feedstocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.4.1 Thiophenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.5 Catalysts and mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.5.1 Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.5.2 Supports . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.6 Other uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.6.1 Hydrodenitrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.6.2 Saturation of olefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.6.3 Hydrogenation in the food industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.7 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.9 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
5 Catalytic reforming 23
5.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
5.2 Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
5.2.1 Typical naphtha feedstocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
5.2.2 The reaction chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
5.3 Process description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
5.4 Catalysts and mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
5.5 Economics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
5.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
5.7 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
6.2.1 Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
6.3 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
6.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
6.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
6.6 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
7 Cracking (chemistry) 35
7.1 History and patents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
7.2 Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.2.1 Initiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.2.2 Hydrogen abstraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.2.3 Radical decomposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.2.4 Radical addition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.2.5 Termination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.2.6 Example: cracking butane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.3 Cracking methodologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.3.1 Thermal methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.3.2 Catalytic methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
7.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
7.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
7.6 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
8 Visbreaker 40
8.1 Process objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
8.2 Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
8.2.1 Coil visbreaking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
8.2.2 Soaker visbreaking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
8.2.3 Process options . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.2.4 Soaker visbreaking versus coil visbreaking . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.3 Quality and yields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.3.1 Feed quality and product quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.3.2 Yields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.3.3 Fuel oil stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.4 Economics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.4.1 Viscosity blending . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.4.2 Example economics for a two-component blend . . . . . . . . . . . . . . . . . . . . . . . 42
8.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
8.6 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
9 Merox 43
9.1 Types of Merox process units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
9.2 Conventional Merox for extracting mercaptans from LPG . . . . . . . . . . . . . . . . . . . . . . 44
iv CONTENTS
10 Coker unit 47
10.1 Types of coker units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
10.2 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
10.3 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
10.4 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
11 Alkylation 48
11.1 Alkylating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
11.1.1 Nucleophilic alkylating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
11.1.2 Electrophilic alkylating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
11.1.3 Carbene alkylating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
11.2 In biology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
11.3 Oil refining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
11.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
11.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
11.6 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
12 Dimer (chemistry) 51
12.1 Noncovalent dimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
12.2 Covalent dimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
12.3 Polymer chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
12.4 Biochemical dimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
12.5 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
12.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
13 Isomerization 53
13.1 Instances of isomerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
13.2 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
13.3 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
15 Claus process 58
15.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
15.2 Process description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
15.2.1 Thermal step . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
15.2.2 Catalytic step . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
15.2.3 Sub dew point Claus process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
15.3 Process performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
15.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
15.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
16 Hydrogen sulfide 61
16.1 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
16.2 Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
16.3 Occurrence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
16.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
16.4.1 Production of thioorganic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
16.4.2 Alkali metal sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
16.4.3 Analytical chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
16.4.4 Precursor to metal sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
16.4.5 Miscellaneous applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
16.5 Removal from fuel gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
16.6 Removal from water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
16.7 Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
16.7.1 Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
16.7.2 Incidents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
16.7.3 Suicides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
16.8 Function in the body . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
16.9 Involvement in diseases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
16.9.1 Hydrogen sulfide deficiency after heart attack . . . . . . . . . . . . . . . . . . . . . . . . . 65
16.9.2 Other diseases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
16.10Induced hypothermia and suspended animation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
16.11Participant in the sulfur cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
16.12Mass extinctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
16.13See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
16.14References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
16.15Additional resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
16.16External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
17 Cooling tower 71
17.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
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18 Steam 84
18.1 Types of steam and conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
18.2 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
18.2.1 Agricultural . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
18.2.2 Domestic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
18.2.3 Electricity generation (and cogeneration) . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
18.2.4 Energy storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.2.5 Lifting gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.2.6 Mechanical effort . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.2.7 Sterilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.2.8 Steam in piping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.2.9 Wood treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.2.10 Concrete treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.2.11 Cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.3 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
CONTENTS vii
18.4 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
18.5 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
19 Boiler 87
19.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
19.2 Fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
19.3 Configurations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
19.4 Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
19.5 Superheated steam boilers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
19.5.1 Supercritical steam generator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
19.6 Hydronic boilers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
19.7 Accessories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
19.7.1 Boiler fittings and accessories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
19.7.2 Steam accessories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
19.7.3 Combustion accessories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
19.7.4 Other essential items . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
19.8 Draught . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
19.9 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
19.10References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
19.11Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Oil refinery
1
2 CHAPTER 1. OIL REFINERY
Storage tanks and towers at Shell Puget Sound Refinery (Shell Oil
1.2 Major products Company), Anacortes, Washington
Petroleum products are usually grouped into three cat- • Desalter unit washes out salt from the crude oil be-
egories: light distillates (LPG, gasoline, naphtha), mid- fore it enters the atmospheric distillation unit.
1.3. COMMON PROCESS UNITS FOUND IN A REFINERY 3
• Atmospheric distillation unit distills crude oil into • Steam reforming unit produces hydrogen for the hy-
fractions. See continuous distillation. drotreaters or hydrocracker.
• Vacuum distillation unit further distills residual bot- • Liquified gas storage vessels store propane and sim-
toms after atmospheric distillation. ilar gaseous fuels at pressure sufficient to maintain
them in liquid form. These are usually spherical ves-
• Naphtha hydrotreater unit uses hydrogen to desul- sels or “bullets” (i.e., horizontal vessels with rounded
furize naphtha from atmospheric distillation. Must ends).
hydrotreat the naphtha before sending to a catalytic
reformer unit. • Storage tanks store crude oil and finished products,
usually cylindrical, with some sort of vapor emis-
• Catalytic reformer unit is used to convert the sion control and surrounded by an earthen berm to
naphtha-boiling range molecules into higher octane contain spills.
reformate (reformer product). The reformate has
higher content of aromatics and cyclic hydrocar- • Amine gas treater, Claus unit, and tail gas treatment
bons). An important byproduct of a reformer is hy- convert hydrogen sulfide from hydrodesulfurization
drogen released during the catalyst reaction. The into elemental sulfur.
hydrogen is used either in the hydrotreaters or the • Utility units such as cooling towers circulate cooling
hydrocracker. water, boiler plants generates steam, and instrument
air systems include pneumatically operated control
• Distillate hydrotreater desulfurizes distillates (such
valves and an electrical substation.
as diesel) after atmospheric distillation.
• Wastewater collection and treating systems consist
• Fluid Catalytic Cracker (FCC) unit upgrades heavier of API separators, dissolved air flotation (DAF)
fractions into lighter, more valuable products. units and further treatment units such as an activated
• Hydrocracker unit uses hydrogen to upgrade heavier sludge biotreater to make water suitable for reuse or
fractions into lighter, more valuable products. for disposal.[3]
• Solvent refining units use solvent such as cresol or
• Visbreaking unit upgrades heavy residual oils by
furfural to remove unwanted, mainly aromatics from
thermally cracking them into lighter, more valuable
lubricating oil stock or diesel stock.
reduced viscosity products.
• Solvent dewaxing units remove the heavy waxy con-
• Merox unit treats LPG, kerosene or jet fuel by oxi-
stituents petrolatum from vacuum distillation prod-
dizing mercaptans to organic disulfides.
ucts.
• Alternative processes for removing mercaptans are
known, e.g. doctor sweetening process and caustic
washing.
1.3.1 Flow diagram of typical refinery
• Coking units (delayed coking, fluid coker, and flexi- The image below is a schematic flow diagram of a typi-
coker) process very heavy residual oils into gasoline cal oil refinery[4] that depicts the various unit processes
and diesel fuel, leaving petroleum coke as a residual and the flow of intermediate product streams that oc-
product. curs between the inlet crude oil feedstock and the final
end products. The diagram depicts only one of the lit-
• Alkylation unit uses sulfuric acid or hydrofluoric erally hundreds of different oil refinery configurations.
acid to produce high-octane components for gaso- The diagram also does not include any of the usual re-
line blending. finery facilities providing utilities such as steam, cool-
ing water, and electric power as well as storage tanks for
• Dimerization unit converts olefins into higher-
crude oil feedstock and for intermediate products and end
octane gasoline blending components. For example,
products.[1][5][6][7]
butenes can be dimerized into isooctene which may
subsequently be hydrogenated to form isooctane. There are many process configurations other than that de-
There are also other uses for dimerization. Gasoline picted above. For example, the vacuum distillation unit
produced through dimerization is highly unsaturated may also produce fractions that can be refined into end-
and very reactive. It tends spontaneously to form products such as: spindle oil used in the textile industry,
gums. For this reason the effluent from the dimer- light machinery oil, motor oil, and various waxes.
ization need to be blended into the finished gasoline
pool immediately or hydrogenated.
1.3.2 The crude oil distillation unit
• Isomerization unit converts linear molecules to
higher-octane branched molecules for blending into The crude oil distillation unit (CDU) is the first processing
gasoline or feed to alkylation units. unit in virtually all petroleum refineries. The CDU distills
4 CHAPTER 1. OIL REFINERY
1.5 Siting/locating of petroleum re- accompanies the presence of a refinery. Aside from air
pollution impacts there are also wastewater concerns,[3]
fineries risks of industrial accidents such as fire and explosion,
and noise health effects due to industrial noise.
A party searching for a site to construct a refinery or a
chemical plant needs to consider the following issues: Many governments worldwide have mandated restric-
tions on contaminants that refineries release, and most
refineries have installed the equipment needed to com-
• The site has to be reasonably far from residential ar- ply with the requirements of the pertinent environmental
eas. protection regulatory agencies. In the United States, there
is strong pressure to prevent the development of new re-
• Infrastructure should be available for supply of raw fineries, and no major refinery has been built in the coun-
materials and shipment of products to markets. try since Marathon’s Garyville, Louisiana facility in 1976.
However, many existing refineries have been expanded
• Energy to operate the plant should be available. during that time. Environmental restrictions and pressure
to prevent construction of new refineries may have also
contributed to rising fuel prices in the United States.[9]
• Facilities should be available for waste disposal.
Additionally, many refineries (more than 100 since the
1980s) have closed due to obsolescence and/or merger
Refineries which use a large amount of steam and cool- activity within the industry itself.
ing water need to have an abundant source of water. Oil
refineries therefore are often located nearby navigable Environmental and safety concerns mean that oil refiner-
rivers or on a sea shore, nearby a port. Such location also ies are sometimes located some distance away from ma-
gives access to transportation by river or by sea. The ad- jor urban areas. Nevertheless, there are many instances
vantages of transporting crude oil by pipeline are evident, where refinery operations are close to populated areas and
and oil companies often transport a large volume of fuel pose health risks In California's Contra Costa County and
to distribution terminals by pipeline. Pipeline may not Solano County, a shoreline necklace of refineries, built
be practical for products with small output, and rail cars, in the early 20th century before this area was populated,
road tankers, and barges are used. and associated chemical plants are adjacent to urban ar-
eas in Richmond, Martinez, Pacheco, Concord, Pittsburg,
Petrochemical plants and solvent manufacturing (fine Vallejo and Benicia, with occasional accidental events
fractionating) plants need spaces for further processing that require "shelter in place" orders to the adjacent pop-
of a large volume of refinery products for further pro- ulations.
cessing, or to mix chemical additives with a product at
source rather than at blending terminals.
of the refinery, during which part or all of the refinery tory material such as standard Portland cement or other
must be shut down. The corrosion-related direct costs in special acid-resistant cements that are shot onto the inner
the U.S. petroleum industry as of 1996 was estimated as surface of the vessel. Also available are thin overlays of
US$3.7 billion per year.[10][11] more expensive metals that protect cheaper metal against
[15]
Corrosion occurs in various forms in the refining pro- corrosion without requiring lots of material.
cess, such as pitting corrosion from water droplets, em-
brittlement from hydrogen, and stress corrosion cracking
from sulfide attack.[12] From a materials standpoint, car- 1.8 History
bon steel is used for upwards of 80 per cent of refin-
ery components, which is beneficial due to its low cost.
The world’s first refinery opened at Ploiești, Romania, in
Carbon steel is resistant to the most common forms of
1856-1857,[16] with United States investment. After be-
corrosion, particularly from hydrocarbon impurities at
ing taken over by Nazi Germany, the Ploiești refineries
temperatures below 205 °C, but other corrosive chemi-
were bombed in Operation Tidal Wave by the Allies dur-
cals and environments prevent its use everywhere. Com-
ing the Oil Campaign of World War II.
mon replacement materials are low alloy steels contain-
ing chromium and molybdenum, with stainless steels con- At one point, the refinery in Ras Tanura, Saudi Arabia
taining more chromium dealing with more corrosive en- owned by Saudi Aramco was claimed to be the largest
vironments. More expensive materials commonly used oil refinery in the world. For most of the 20th cen-
are nickel, titanium, and copper alloys. These are pri- tury, the largest refinery was the Abadan Refinery in
marily saved for the most problematic areas where ex- Iran. This refinery suffered extensive damage during
tremely high temperatures and/or very corrosive chemi- the Iran-Iraq war. The world’s largest refinery complex
cals are present.[13] is the Jamnagar Refinery Complex, consisting of two
refineries side by side operated by Reliance Industries
Corrosion is fought by a complex system of monitoring,
Limited in Jamnagar, India with a combined production
preventative repairs and careful use of materials. Mon-
capacity of 1,240,000 barrels per day (197,000 m3 /d).
itoring methods include both off-line checks taken dur-
PDVSA's Paraguaná Refinery Complex in Paraguaná
ing maintenance and on-line monitoring. Off-line checks
Peninsula, Venezuela with a capacity of 956,000 bbl/d
measure corrosion after it has occurred, telling the en-
(152,000 m3 /d) and SK Energy's Ulsan in South Korea
gineer when equipment must be replaced based on the
with 840,000 bbl/d (134,000 m3 /d) are the second and
historical information he has collected. This is referred
third largest, respectively.
to as preventative management.
On-line systems are a more modern development, and
are revolutionizing the way corrosion is approached. 1.8.1 Oil refining in the United States
There are several types of on-line corrosion monitor-
ing technologies such as linear polarization resistance, In the 19th century, refineries in the U.S. processed crude
electrochemical noise and electrical resistance. On-Line oil primarily to recover the kerosene. There was no
monitoring has generally had slow reporting rates in the market for the more volatile fraction, including gasoline,
past (minutes or hours) and been limited by process con- which was considered waste and was often dumped di-
ditions and sources of error but newer technologies can rectly into the nearest river. The invention of the automo-
report rates up to twice per minute with much higher ac- bile shifted the demand to gasoline and diesel, which re-
curacy (referred to as real-time monitoring). This allows main the primary refined products today. Today, national
process engineers to treat corrosion as another process and state legislation requires refineries to meet stringent
variable that can be optimized in the system. Immediate air and water cleanliness standards. In fact, oil companies
responses to process changes allow the control of corro- in the U.S. perceive obtaining a permit to build a modern
sion mechanisms, so they can be minimized while also refinery to be so difficult and costly that no new refiner-
maximizing production output.[14] In an ideal situation ies were built (though many have been expanded) in the
having on-line corrosion information that is accurate and U.S. from 1976 until 2014, when the small Dakota Prairie
real-time will allow conditions that cause high corrosion Refinery in North Dakota is set to begin operation.[17]
rates to be identified and reduced. This is known as pre- More than half the refineries that existed in 1981 are
dictive management. now closed due to low utilization rates and accelerating
Materials methods include selecting the proper material mergers.[18] As a result of these closures total US refin-
for the application. In areas of minimal corrosion, cheap ery capacity fell between 1981 to 1995, though the oper-
materials are preferable, but when bad corrosion can oc- ating capacity stayed fairly constant in that time period at
cur, more expensive but longer lasting materials should around 15,000,000 barrels per day (2,400,000 m3 /d).[19]
be used. Other materials methods come in the form of Increases in facility size and improvements in efficiencies
protective barriers between corrosive substances and the have offset much of the lost physical capacity of the in-
equipment metals. These can be either a lining of refrac- dustry. In 1982 (the earliest data provided), the United
States operated 301 refineries with a combined capacity
1.11. EXTERNAL LINKS 7
of 17.9 million barrels (2,850,000 m3 ) of crude oil each [4] Crude Oil Solids Removal
calendar day. In 2010, there were 149 operable U.S. re-
[5] Guide to Refining from Chevron Oil's website
fineries with a combined capacity of 17.6 million barrels
(2,800,000 m3 ) per calendar day.[20] [6] Refinery flowchart from Universal Oil Products' website
In 2009 through 2010, as revenue streams in the oil busi-
[7] An example flowchart of fractions from crude oil at a re-
ness dried up and profitability of oil refineries fell due finery
to lower demand for product and high reserves of supply
preceding the economic recession, oil companies began [8] Kister, Henry Z. (1992). Distillation Design (1st Edition
to close or sell refineries. ed.). McGraw-Hill. ISBN 978-0-07-034909-4.
• K factor crude oil refining [17] “North Dakota Builds A Refinery, First In The U.S. Since
'76”. Investors Business Daily. April 11, 2013. Retrieved
• List of oil refineries August 24, 2014.
• Natural-gas processing [18] White Paper on Refining Capacity, Federal Trade Com-
mission, April, 2007.
• Nelson complexity index
[19] “U. S. Operating Crude Oil Distillation Capacity (Thou-
• Sour gas sand Barrels per Day)". Eia.doe.gov. 2011-07-28. Re-
trieved 2011-11-05.
Continuous distillation
9
10 CHAPTER 2. CONTINUOUS DISTILLATION
increasing the efficacy of the distillation tower. The more Distillation towers (such as in images 3 and 4) use var-
reflux that is provided, the better is the tower’s separation ious vapor and liquid contacting methods to provide the
of the lower boiling from the higher boiling components required number of equilibrium stages. Such devices are
of the feed. A balance of heating with a reboiler at the commonly known as “plates” or “trays”.[8] Each of these
bottom of a column and cooling by condensed reflux at plates or trays is at a different temperature and pressure.
the top of the column maintains a temperature gradient The stage at the tower bottom has the highest pressure
(or gradual temperature difference) along the height of and temperature. Progressing upwards in the tower, the
the column to provide good conditions for fractionating pressure and temperature decreases for each succeeding
the feed mixture. Reflux flows at the middle of the tower stage. The vapor–liquid equilibrium for each feed com-
are called pumparounds. ponent in the tower reacts in its unique way to the dif-
ferent pressure and temperature conditions at each of the
Changing the reflux (in combination with changes in feed
and product withdrawal) can also be used to improve the stages. That means that each component establishes a dif-
ferent concentration in the vapor and liquid phases at each
separation properties of a continuous distillation column
while in operation (in contrast to adding plates or trays, of the stages, and this results in the separation of the com-
ponents. Some example trays are depicted in image 5. A
or changing the packing, which would, at a minimum,
require quite significant downtime). more detailed, expanded image of two trays can be seen
in the theoretical plate article. The reboiler often acts as
an additional equilibrium stage.
Plates or trays If each physical tray or plate were 100% efficient, then
the number of physical trays needed for a given sepa-
ration would equal the number of equilibrium stages or
theoretical plates. However, that is very seldom the case.
Hence, a distillation column needs more plates than the
required number of theoretical vapor–liquid equilibrium
stages.
Packing
tured packing is liquid and vapor distribution entering the a higher octane rating value.
packed bed. The number of theoretical stages required to The naphtha cut, as that fraction is called, contains many
make a given separation is calculated using a specific va- different hydrocarbon compounds. Therefore it has an
por to liquid ratio. If the liquid and vapor are not evenly initial boiling point of about 35 °C and a final boiling
distributed across the superficial tower area as it enters point of about 200 °C. Each cut produced in the frac-
the packed bed, the liquid to vapor ratio will not be cor- tionating columns has a different boiling range. At some
rect in the packed bed and the required separation will distance below the overhead, the next cut is withdrawn
not be achieved. The packing will appear to not be work- from the side of the column and it is usually the jet fuel
ing properly. The height equivalent to a theoretical plate
cut, also known as a kerosene cut. The boiling range of
(HETP) will be greater than expected. The problem is that cut is from an initial boiling point of about 150 °C
not the packing itself but the mal-distribution of the flu-
to a final boiling point of about 270 °C, and it also con-
ids entering the packed bed. Liquid mal-distribution is tains many different hydrocarbons. The next cut further
more frequently the problem than vapor. The design of
down the tower is the diesel oil cut with a boiling range
the liquid distributors used to introduce the feed and re- from about 180 °C to about 315 °C. The boiling ranges
flux to a packed bed is critical to making the packing
between any cut and the next cut overlap because the dis-
perform at maximum efficiency. Methods of evaluating tillation separations are not perfectly sharp. After these
the effectiveness of a liquid distributor can be found in come the heavy fuel oil cuts and finally the bottoms prod-
references.[9][10] uct, with very wide boiling ranges. All these cuts are pro-
cessed further in subsequent refining processes.
2.3.3 Overhead system arrangements
Vacuum distillation
15
16 CHAPTER 3. VACUUM DISTILLATION
tool to reduce the number of stages needed is to utilize The constraint imposed by limiting the column inlet
vacuum distillation.[9] Vacuum distillation columns (as crude oil to a temperature of less than 370 to 380 °C
depicted in Figures 2 and 3) typically used in oil refineries yields a residual oil from the bottom of the atmospheric
have diameters ranging up to about 14 metres (46 feet), distillation column consisting entirely of hydrocarbons
heights ranging up to about 50 metres (164 feet), and feed that boil above 370 to 380 °C.
rates ranging up to about 25,400 cubic metres per day To further distill the residual oil from the atmospheric
(160,000 barrels per day). distillation column, the distillation must be performed at
Vacuum distillation increases the relative volatility of the absolute pressures as low as 10 to 40 mmHg (also referred
key components in many applications. The higher the rel- to as Torr) so as to limit the operating temperature to less
ative volatility, the more separable are the two compo- than 370 to 380 °C.
nents; this connotes fewer stages in a distillation column Figure 2 is a simplified process diagram of a petroleum
in order to effect the same separation between the over- refinery vacuum distillation column that depicts the inter-
head and bottoms products. Lower pressures increase rel- nals of the column and Figure 3 is a photograph of a large
ative volatilities in most systems. vacuum distillation column in a petroleum refinery.
A second advantage of vacuum distillation is the reduced The 10 to 40 mmHg absolute pressure in a vacuum distil-
temperature requirement at lower pressures. For many lation column increases the volume of vapor formed per
systems, the products degrade or polymerize at elevated volume of liquid distilled. The result is that such columns
temperatures. have very large diameters.[13]
Vacuum distillation can improve a separation by: Distillation columns such those in Images 1 and 2, may
have diameters of 15 meters or more, heights ranging up
• Prevention of product degradation or polymer for-
to about 50 meters, and feed rates ranging up to about
mation because of reduced pressure leading to lower
25,400 cubic meters per day (160,000 barrels per day).
tower bottoms temperatures,
The vacuum distillation column internals must provide
• Reduction of product degradation or polymer for- good vapor–liquid contacting while, at the same time,
mation because of reduced mean residence time es- maintaining a very low pressure increase from the top
pecially in columns using packing rather than trays. of the column top to the bottom. Therefore, the vac-
uum column uses distillation trays only where withdraw-
• Increasing capacity, yield, and purity. ing products from the side of the column (referred to as
side draws). Most of the column uses packing material
Another advantage of vacuum distillation is the reduced for the vapor–liquid contacting because such packing has
capital cost, at the expense of slightly more operating a lower pressure drop than distillation trays. This packing
cost. Utilizing vacuum distillation can reduce the height material can be either structured sheet metal or randomly
and diameter, and thus the capital cost of a distillation dumped packing such as Raschig rings.
column. The absolute pressure of 10 to 40 mmHg in the vacuum
column is most often achieved by using multiple stages of
steam jet ejectors.[14]
3.2.1 Vacuum distillation in petroleum re-
fining Many industries, other than the petroleum refining indus-
try, use vacuum distillation on a much a smaller scale.
Petroleum crude oil is a complex mixture of hundreds
of different hydrocarbon compounds generally having
from 3 to 60 carbon atoms per molecule, although there 3.3 Molecular distillation
may be small amounts of hydrocarbons outside that
range.[10][11][12] The refining of crude oil begins with dis- Molecular distillation is vacuum distillation below the
tilling the incoming crude oil in a so-called atmospheric pressure of 0.01 torr[15] (1.3 Pa). 0.01 torr is one or-
distillation column operating at pressures slightly above der of magnitude above high vacuum, where fluids are in
atmospheric pressure.[8][10][11] the free molecular flow regime, i.e. the mean free path
In distilling the crude oil, it is important not to subject the of molecules is comparable to the size of the equipment.
crude oil to temperatures above 370 to 380 °C because The gaseous phase no longer exerts significant pressure
the high molecular weight components in the crude oil on the substance to be evaporated, and consequently, rate
will undergo thermal cracking and form petroleum coke of evaporation no longer depends on pressure. That is,
at temperatures above that. Formation of coke would re- because the continuum assumptions of fluid dynamics no
sult in plugging the tubes in the furnace that heats the longer apply, mass transport is governed by molecular dy-
feed stream to the crude oil distillation column. Plug- namics rather than fluid dynamics. Thus, a short path be-
ging would also occur in the piping from the furnace to tween the hot surface and the cold surface is necessary,
the distillation column as well as in the column itself. typically by suspending a hot plate covered with a film of
18 CHAPTER 3. VACUUM DISTILLATION
feed next to a cold plate with a line of sight in between. [9] Karl Kolmetz, Andrew W. Sloley et al. (2004), Design-
Molecular distillation is used industrially for purification ing Distillation Columns for Vacuum Service, 11th India
of oils. Oil and Gas Symposium and International Exhibition,
September 2004, Mumbai, India (also published in Hy-
drocarbon Processing, May 2005)
3.4 Gallery [10] Gary, J.H. and Handwerk, G.E. (1984). Petroleum Refin-
ing Technology and Economics (2nd Edition ed.). Marcel
Dekker, Inc. ISBN 0-8247-7150-8.
• A simple short path vacuum distillation apparatus
[11] Leffler, W.L. (1985). Petroleum refining for the nontech-
• Kugelrohr - a short path vacuum distillation appara- nical person (2nd Edition ed.). PennWell Books. ISBN
tus 0-87814-280-0.
• Perkin triangle - for air-sensitive vacuum distillation [12] James G, Speight (2006). The Chemistry and Technology
of Petroleum (Fourth Edition ed.). CRC Press. 0-8493-
• Vacuum distillation apparatus 9067-2.
• Kugelrohr
3.7 External links
3.6 References • D1160 Vacuum Distillation
Hydrodesulfurization
Not to be confused with Flue-gas desulfurization. metal, laying the foundation of the modern catalytic hy-
drogenation process.
Hydrodesulfurization (HDS) is a catalytic chemical Soon after Sabatier’s work, a German chemist, Wilhelm
process widely used to remove sulfur (S) from natural gas Normann, found that catalytic hydrogenation could be
and from refined petroleum products such as gasoline or used to convert unsaturated fatty acids or glycerides in
petrol, jet fuel, kerosene, diesel fuel, and fuel oils.[1][2] the liquid phase into saturated ones. He was awarded a
The purpose of removing the sulfur is to reduce the sulfur patent in Germany in 1902[7] and in Britain in 1903,[8]
dioxide (SO which was the beginning of what is now a worldwide in-
2) emissions that result from using those fuels in auto- dustry.
motive vehicles, aircraft, railroad locomotives, ships, gas In the mid-1950s, the first noble metal catalytic reforming
or oil burning power plants, residential and industrial process (the Platformer process) was commercialized. At
furnaces, and other forms of fuel combustion. the same time, the catalytic hydrodesulfurization of the
Another important reason for removing sulfur from the naphtha feed to such reformers was also commercialized.
naphtha streams within a petroleum refinery is that sulfur, In the decades that followed, various proprietary catalytic
even in extremely low concentrations, poisons the noble hydrodesulfurization processes, such as the one depicted
metal catalysts (platinum and rhenium) in the catalytic re- in the flow diagram below, have been commercialized.
forming units that are subsequently used to upgrade the Currently, virtually all of the petroleum refineries world-
octane rating of the naphtha streams. wide have one or more HDS units.
The industrial hydrodesulfurization processes include fa- By 2006, miniature microfluidic HDS units had been im-
cilities for the capture and removal of the resulting plemented for treating JP-8 jet fuel to produce clean feed
hydrogen sulfide (H stock for a fuel cell hydrogen reformer.[9] By 2007, this
2S) gas. In petroleum refineries, the hydrogen sulfide gas had been integrated into an operating 5 kW fuel cell gen-
is then subsequently converted into byproduct elemental eration system.[10]
sulfur or sulfuric acid (H
2SO
4). In fact, the vast majority of the 64,000,000 metric
tons of sulfur produced worldwide in 2005 was byproduct 4.2 Process chemistry
sulfur from refineries and other hydrocarbon processing
plants.[3][4] Hydrogenation is a class of chemical reactions in
An HDS unit in the petroleum refining industry is also which the net result is the addition of hydrogen (H).
often referred to as a hydrotreater. Hydrogenolysis is a type of hydrogenation and results in
the cleavage of the C-X chemical bond, where C is a
carbon atom and X is a sulfur (S), nitrogen (N) or oxygen
4.1 History (O) atom. The net result of a hydrogenolysis reaction is
the formation of C-H and H-X chemical bonds. Thus,
hydrodesulfurization is a hydrogenolysis reaction. Using
Although some reactions involving catalytic hydrogena- ethanethiol (C
tion of organic substances were already known, the prop- 2H
erty of finely divided nickel to catalyze the fixation of hy- 5SH), a sulfur compound present in some petroleum
drogen on hydrocarbon (ethylene, benzene) double bonds products, as an example, the hydrodesulfurization reac-
was discovered by the French chemist Paul Sabatier in tion can be simply expressed as
1897.[5][6] Through this work, he found that unsaturated
hydrocarbons in the vapor phase could be converted into
saturated hydrocarbons by using hydrogen and a catalytic
19
20 CHAPTER 4. HYDRODESULFURIZATION
For the mechanistic aspects of, and the catalysts used in 2S that it contains. The H
this reaction see the section catalysts and mechanisms 2S-free hydrogen-rich gas is then recycled back for reuse
in the reactor section. Any excess gas from the gas sep-
arator vessel joins the sour gas from the stripping of the
4.3 Process description reaction product liquid.
The liquid from the gas separator vessel is routed through
In an industrial hydrodesulfurization unit, such as in a re- a reboiled stripper distillation tower. The bottoms prod-
finery, the hydrodesulfurization reaction takes place in a uct from the stripper is the final desulfurized liquid prod-
fixed-bed reactor at elevated temperatures ranging from uct from hydrodesulfurization unit.
300 to 400 °C and elevated pressures ranging from 30 The overhead sour gas from the stripper contains hydro-
to 130 atmospheres of absolute pressure, typically in the gen, methane, ethane, hydrogen sulfide, propane, and,
presence of a catalyst consisting of an alumina base im- perhaps, some butane and heavier components. That sour
pregnated with cobalt and molybdenum (usually called a gas is sent to the refinery’s central gas processing plant
CoMo catalyst). Occasionally, a combination of nickel for removal of the hydrogen sulfide in the refinery’s main
and molybdenum (called NiMo) is used, in addition to the amine gas treating unit and through a series of distilla-
CoMo catalyst, for specific difficult-to-treat feed stocks, tion towers for recovery of propane, butane and pentane
such as those containing a high level of chemically bound or heavier components. The residual hydrogen, methane,
nitrogen. ethane, and some propane is used as refinery fuel gas. The
The image below is a schematic depiction of the equip- hydrogen sulfide removed and recovered by the amine gas
ment and the process flow streams in a typical refinery treating unit is subsequently converted to elemental sulfur
HDS unit. in a Claus process unit or to sulfuric acid in a wet sulfuric
acid process or in the conventional Contact Process.
Note that the above description assumes that the HDS
unit feed contains no olefins. If the feed does contain
olefins (for example, the feed is a naphtha derived from a
refinery fluid catalytic cracker (FCC) unit), then the over-
head gas from the HDS stripper may also contain some
ethene, propene, butenes and pentenes, or heavier com-
ponents.
It should also be noted that the amine solution to and from
the recycle gas contactor comes from and is returned to
the refinery’s main amine gas treating unit.
was within the range of 300 to 500 ppm by weight of to- cobalt-modified MoS2 catalyst, nickel and tungsten are
tal sulfur. As of 2006, the total sulfur limit for highway also used, depending on the nature of the feed. For ex-
diesel is in the range of 15 to 30 ppm by weight.[11] ample, Ni-W catalysts are more effective for hydrodeni-
trogenation (HDN).
4.4.1 Thiophenes
4.5.2 Supports
A family of substrates that are particularly common
in petroleum are the aromatic sulfur-containing hete- Metal sulfides are “supported” on materials with high
rocycles called thiophenes. Many kinds of thiophenes surface areas. A typical support for HDS catalyst is γ-
occur in petroleum ranging from thiophene itself to alumina. The support allows the more expensive catalyst
more condensed derivatives called benzothiophenes and to be more widely distributed, giving rise to a larger frac-
dibenzothiophenes. Thiophene itself and its alkyl deriva- tion of the MoS
tives are easier to hydrogenolyse, whereas dibenzoth- 2 that is catalytically active. The interaction between the
iophene, especially its 4,6-disubstituted derivatives, are support and the catalyst is an area of intense interest, since
considered the most challenging substrates. Benzothio- the support is often not fully inert but participates in the
phenes are midway between the simple thiophenes and catalysis.
dibenzothiophenes in their susceptibility to HDS.
Most metals catalyse HDS, but it is those at the mid- The hydrogenolysis reaction may also be used to saturate
dle of the transition metal series that are most active. or convert olefins (alkenes) into paraffins (alkanes). The
Ruthenium disulfide appears to be the single most active process used is the same as for an HDS unit.
catalyst, but binary combinations of cobalt and molyb- As an example, the saturation of the olefin pentene can
denum are also highly active.[14] Aside from the basic be simply expressed as:
22 CHAPTER 4. HYDRODESULFURIZATION
Further information: Hydrogenation, Wilhelm Normann [15] Kinetics and Interactions of the Simultaneous Catalytic Hy-
and Trans fat drodenitrogenation of Pyridine and Hydrodesulfurization
of Thiophene (John Wilkins, PhD Thesis, MIT, 1977)
The food industry uses hydrogenation to completely or [16] Simultaneous Catalytic Hydrodenitrogenation of Pyridine
partially saturate the unsaturated fatty acids in liquid and Hydrodesulfurization of Thiophene (Satterfield,C.N.,
vegetable fats and oils to convert them into solid or semi- Modell, M. and Wilkens, J.A., Ind. Eng. Chem. Process
solid fats, such as those in margarine and shortening. Des. Dev., 1980 Vol. 19, pages 154-160)
[10] Fuel cells help make noisy, hot generators a thing of the
past (December 2007) Pacific Northwest National Labo-
ratory
Catalytic reforming
5.1 History
In the 1940s, Vladimir Haensel,[1] a research chemist
working for Universal Oil Products (UOP), developed
a catalytic reforming process using a catalyst containing
platinum. Haensel’s process was subsequently commer-
cialized by UOP in 1949 for producing a high octane
gasoline from low octane naphthas and the UOP process
become known as the Platforming process.[2] The first
Platforming unit was built in 1949 at the refinery of the
A catalytic reformer unit in a petroleum refinery. © BP p.l.c Old Dutch Refining Company in Muskegon, Michigan.
In the years since then, many other versions of the pro-
Catalytic reforming is a chemical process used to con-
cess have been developed by some of the major oil com-
vert petroleum refinery naphthas distilled from crude oil
panies and other organizations. Today, the large majority
(typically having low octane ratings) into high-octane
of gasoline produced worldwide is derived from the cat-
liquid products called reformates, which are premium
alytic reforming process.
blending stocks for high-octane gasoline. The process
converts low-octane linear hydrocarbons (paraffins) into To name a few of the other catalytic reforming versions
branched alkanes (isoparaffins) and cyclic naphthenes, that were developed, all of which utilized a platinum
which are then partially dehydrogenated to produce high- and/or a rhenium catalyst:
octane aromatic hydrocarbons. The dehydrogenation
also produces significant amounts of byproduct hydrogen • Rheniforming: Developed by Chevron Oil Com-
gas, which is fed into other refinery processes such as pany.
hydrocracking. A side reaction is hydrogenolysis, which
• Powerforming: Developed by Esso Oil Company,
produces light hydrocarbons of lower value, such as
currently known as ExxonMobil.
methane, ethane, propane and butanes.
In addition to a gasoline blending stock, reformate is the • Magnaforming: Developed by Engelhard and
main source of aromatic bulk chemicals such as benzene, Atlantic Richfield Oil Company.
toluene, xylene and ethylbenzene which have diverse • Ultraforming: Developed by Standard Oil of Indi-
uses, most importantly as raw materials for conversion ana, now a part of the British Petroleum Company.
into plastics. However, the benzene content of reformate
makes it carcinogenic, which has led to governmental reg- • Houdriforming: Developed by the Houdry Process
ulations effectively requiring further processing to reduce Corporation.
its benzene content. • CCR Platforming: A Platforming version, designed
This process is quite different from and not to be for continuous catalyst regeneration, developed by
confused with the catalytic steam reforming process UOP.
23
24 CHAPTER 5. CATALYTIC REFORMING
• Octanizing: A catalytic reforming version developed The table just below lists some fairly typical straight-
by Axens, a subsidiary of Institut francais du petrole run heavy naphtha feedstocks, available for catalytic re-
(IFP), designed for continuous catalyst regeneration. forming, derived from various crude oils. It can be seen
that they differ significantly in their content of paraffins,
naphthenes and aromatics:
5.2 Chemistry .....
Some refinery naphthas include olefinic hydrocarbons,
Before describing the reaction chemistry of the catalytic such as naphthas derived from the fluid catalytic crack-
reforming process as used in petroleum refineries, the ing and coking processes used in many refineries. Some
typical naphthas used as catalytic reforming feedstocks refineries may also desulfurize and catalytically reform
will be discussed. those naphthas. However, for the most part, catalytic re-
forming is mainly used on the straight-run heavy naph-
thas, such as those in the above table, derived from the
5.2.1 Typical naphtha feedstocks
distillation of crude oils.
A petroleum refinery includes many unit operations and
unit processes. The first unit operation in a refinery 5.2.2 The reaction chemistry
is the continuous distillation of the petroleum crude oil
being refined. The overhead liquid distillate is called There are many chemical reactions that occur in the cat-
naphtha and will become a major component of the re- alytic reforming process, all of which occur in the pres-
finery’s gasoline (petrol) product after it is further pro- ence of a catalyst and a high partial pressure of hydrogen.
cessed through a catalytic hydrodesulfurizer to remove Depending upon the type or version of catalytic reform-
sulfur-containing hydrocarbons and a catalytic reformer ing used as well as the desired reaction severity, the reac-
to reform its hydrocarbon molecules into more complex tion conditions range from temperatures of about 495 to
molecules with a higher octane rating value. The naphtha 525 °C and from pressures of about 5 to 45 atm.[10]
is a mixture of very many different hydrocarbon com-
pounds. It has an initial boiling point of about 35 °C The commonly used catalytic reforming catalysts con-
and a final boiling point of about 200 °C, and it contains tain noble metals such as platinum and/or rhenium,
paraffin, naphthene (cyclic paraffins) and aromatic hydro- which are very susceptible to poisoning by sulfur and
carbons ranging from those containing 4 carbon atoms to nitrogen compounds. Therefore, the naphtha feedstock
those containing about 10 or 11 carbon atoms. to a catalytic reformer is always pre-processed in a
hydrodesulfurization unit which removes both the sulfur
The naphtha from the crude oil distillation is often further and the nitrogen compounds. Most catalysts require both
distilled to produce a “light” naphtha containing most (but sulphur and nitrogen content to be lower than 1 ppm.
not all) of the hydrocarbons with 6 or fewer carbon atoms
[11]
and a “heavy” naphtha containing most (but not all) of the The four major catalytic reforming reactions are:
hydrocarbons with more than 6 carbon atoms. The heavy
naphtha has an initial boiling point of about 140 to 150 1: The dehydrogenation of naphthenes to con-
°C and a final boiling point of about 190 to 205 °C. The vert them into aromatics as exemplified in the
naphthas derived from the distillation of crude oils are conversion methylcyclohexane (a naphthene)
referred to as “straight-run” naphthas. to toluene (an aromatic), as shown below:
It is the straight-run heavy naphtha that is usually pro-
cessed in a catalytic reformer because the light naphtha
has molecules with 6 or fewer carbon atoms which, when + 3 H2
reformed, tend to crack into butane and lower molecular
weight hydrocarbons which are not useful as high-octane
gasoline blending components. Also, the molecules with
6 carbon atoms tend to form aromatics which is undesir-
able because governmental environmental regulations in a 2: The isomerization of normal paraffins to
number of countries limit the amount of aromatics (most isoparaffins as exemplified in the conversion
particularly benzene) that gasoline may contain.[3][4][5] of normal octane to 2,5-Dimethylhexane (an
isoparaffin), as shown below:
It should be noted that there are a great many petroleum
crude oil sources worldwide and each crude oil has its
own unique composition or “assay”. Also, not all refiner-
ies process the same crude oils and each refinery produces
its own straight-run naphthas with their own unique ini-
tial and final boiling points. In other words, naphtha is a
generic term rather than a specific term.
5.3. PROCESS DESCRIPTION 25
3: The dehydrogenation and aromatization of once each 6 to 24 months. Such a unit is referred to as a
paraffins to aromatics (commonly called dehy- semi-regenerative catalytic reformer (SRR).
drocyclization) as exemplified in the conver- Some catalytic reforming units have an extra spare or
sion of normal heptane to toluene, as shown swing reactor and each reactor can be individually iso-
below: lated so that any one reactor can be undergoing in situ
regeneration while the other reactors are in operation.
When that reactor is regenerated, it replaces another re-
actor which, in turn, is isolated so that it can then be re-
generated. Such units, referred to as cyclic catalytic re-
formers, are not very common. Cyclic catalytic reformers
serve to extend the period between required shutdowns.
The latest and most modern type of catalytic reform-
ers are called continuous catalyst regeneration (CCR) re-
formers. Such units are characterized by continuous in-
4: The hydrocracking of paraffins into smaller
situ regeneration of part of the catalyst in a special regen-
molecules as exemplified by the cracking of
erator, and by continuous addition of the regenerated cat-
normal heptane into isopentane and ethane, as
alyst to the operating reactors. As of 2006, two CCR ver-
shown below:
sions available: UOP’s CCR Platformer process[13] and
Axens’ Octanizing process.[14] The installation and use of
CCR units is rapidly increasing.
Many of the earliest catalytic reforming units (in the
1950s and 1960s) were non-regenerative in that they did
not perform in situ catalyst regeneration. Instead, when
needed, the aged catalyst was replaced by fresh catalyst
The hydrocracking of paraffins is the only one of the and the aged catalyst was shipped to catalyst manufac-
above four major reforming reactions that consumes hy- turers to be either regenerated or to recover the platinum
drogen. The isomerization of normal paraffins does not content of the aged catalyst. Very few, if any, catalytic
consume or produce hydrogen. However, both the de- reformers currently in operation are non-regenerative.
hydrogenation of naphthenes and the dehydrocyclization The process flow diagram below depicts a typical semi-
of paraffins produce hydrogen. The overall net produc- regenerative catalytic reforming unit.
tion of hydrogen in the catalytic reforming of petroleum
naphthas ranges from about 50 to 200 cubic meters of
hydrogen gas (at 0 °C and 1 atm) per cubic meter of
liquid naphtha feedstock. In the United States custom-
ary units, that is equivalent to 300 to 1200 cubic feet of
hydrogen gas (at 60 °F and 1 atm) per barrel of liquid
naphtha feedstock.[12] In many petroleum refineries, the
net hydrogen produced in catalytic reforming supplies a
significant part of the hydrogen used elsewhere in the re-
finery (for example, in hydrodesulfurization processes).
The hydrogen is also necessary in order to hydrogenolyze
any polymers that form on the catalyst. Schematic diagram of a typical semi-regenerative catalytic re-
In practice, the higher the content of naphtenes in the former unit in a petroleum refinery
naphtha feedstock, the better will be the quality of the
reformate and the higher the production of hydrogen. The liquid feed (at the bottom left in the diagram) is
Crude oils containing the best naphtha for reforming are pumped up to the reaction pressure (5–45 atm) and is
typically from Western Africa or the North Sea, such as joined by a stream of hydrogen-rich recycle gas. The re-
Bonny light or Troll. sulting liquid–gas mixture is preheated by flowing through
a heat exchanger. The preheated feed mixture is then to-
tally vaporized and heated to the reaction temperature
(495–520 °C) before the vaporized reactants enter the
5.3 Process description first reactor. As the vaporized reactants flow through the
fixed bed of catalyst in the reactor, the major reaction is
The most commonly used type of catalytic reforming unit the dehydrogenation of naphthenes to aromatics (as de-
has three reactors, each with a fixed bed of catalyst, and scribed earlier herein) which is highly endothermic and
all of the catalyst is regenerated in situ during routine cat- results in a large temperature decrease between the in-
alyst regeneration shutdowns which occur approximately let and outlet of the reactor. To maintain the required
26 CHAPTER 5. CATALYTIC REFORMING
reaction temperature and the rate of reaction, the vapor- 5.4 Catalysts and mechanisms
ized stream is reheated in the second fired heater before it
flows through the second reactor. The temperature again Most catalytic reforming catalysts contain platinum or
decreases across the second reactor and the vaporized rhenium on a silica or silica-alumina support base, and
stream must again be reheated in the third fired heater be- some contain both platinum and rhenium. Fresh catalyst
fore it flows through the third reactor. As the vaporized is chlorided (chlorinated) prior to use.
stream proceeds through the three reactors, the reaction
rates decrease and the reactors therefore become larger. The noble metals (platinum and rhenium) are consid-
At the same time, the amount of reheat required between ered to be catalytic sites for the dehydrogenation reac-
the reactors becomes smaller. Usually, three reactors are tions and the chlorinated alumina provides the acid sites
all that is required to provide the desired performance of needed for isomerization, cyclization and hydrocracking
the catalytic reforming unit. reactions.[11] The biggest care has to be exercised dur-
ing the chlorination. Indeed if not chlorinated (or in-
Some installations use three separate fired heaters as sufficiently chlorinated) the platinum and rhenium in the
shown in the schematic diagram and some installations catalyst would be reduced almost immediately to metal-
use a single fired heater with three separate heating coils. lic state by the hydrogen in the vapour phase. On the
The hot reaction products from the third reactor are par- other an excessive chlorination could depress excessively
tially cooled by flowing through the heat exchanger where the activity of the catalyst.
the feed to the first reactor is preheated and then flow The activity (i.e., effectiveness) of the catalyst in a semi-
through a water-cooled heat exchanger before flowing regenerative catalytic reformer is reduced over time dur-
through the pressure controller (PC) into the gas sepa- ing operation by carbonaceous coke deposition and chlo-
rator. ride loss. The activity of the catalyst can be periodically
Most of the hydrogen-rich gas from the gas separator ves- regenerated or restored by in situ high temperature ox-
sel returns to the suction of the recycle hydrogen gas com- idation of the coke followed by chlorination. As stated
pressor and the net production of hydrogen-rich gas from earlier herein, semi-regenerative catalytic reformers are
the reforming reactions is exported for use in the other regenerated about once per 6 to 24 months. The higher
refinery processes that consume hydrogen (such as hy- the severity of the reacting conditions (temperature), the
drodesulfurization units and/or a hydrocracker unit). higher is the octane of the produced reformate but also
the shorter will be the duration of the cycle between two
The liquid from the gas separator vessel is routed into a
regenerations. Catalyst’s cycle duration is also very de-
fractionating column commonly called a stabilizer. The
pendent on the quality of the feedstock. However, in-
overhead offgas product from the stabilizer contains the
dependently of the crude oil used in the refinery, all cata-
byproduct methane, ethane, propane and butane gases
lysts require a maximum final boiling point of the naphtha
produced by the hydrocracking reactions as explained
feedstock of 180 °C.
in the above discussion of the reaction chemistry of a
catalytic reformer, and it may also contain some small Normally, the catalyst can be regenerated perhaps 3 or
amount of hydrogen. That offgas is routed to the refin- 4 times before it must be returned to the manufacturer
ery’s central gas processing plant for removal and recov- for reclamation of the valuable platinum and/or rhenium
ery of propane and butane. The residual gas after such content.[11]
processing becomes part of the refinery’s fuel gas system.
The bottoms product from the stabilizer is the high-
octane liquid reformate that will become a component of 5.5 Economics
the refinery’s product gasoline. Reformate can be blended
directly in the gasoline pool but often it is separated in
two or more streams. A common refining scheme con-
5.6 References
sists in fractionating the reformate in two streams, light
and heavy reformate. The light reformate has lower oc- [1] A Biographical Memoir of Vladimir Haensel written by
tane and can be used as isomerization feedstock if this Stanley Gembiki, published by the National Academy of
Sciences in 2006.
unit is available. The heavy reformate is high in octane
and low in benzene, hence it is an excellent blending com- [2] Platforming described on UOP’s website
ponent for the gasoline pool.
[3] Canadian regulations on benzene in gasoline
Benzene is often removed with a specific operation to re-
duce the content of benzene in the reformate as the fin- [4] United Kingdom regulations on benzene in gasoline
ished gasoline has often an upper limit of benzene content
(in the UE this is 1% volume). The benzene extracted can [5] USA regulations on benzene in gasoline
be marketed as feedstock for the chemical industry. [6] Barrow Island crude oil assay
28
6.1. FLOW DIAGRAM AND PROCESS DESCRIPTION 29
• Axens / Stone & Webster Process Technology — The hot catalyst (at about 715 °C) leaving the regenerator
currently owned by Technip flows into a catalyst withdrawal well where any entrained
combustion flue gases are allowed to escape and flow back
• Universal Oil Products (UOP) — currently fully into the upper part to the regenerator. The flow of regen-
owned subsidiary of Honeywell erated catalyst to the feedstock injection point below the
catalyst riser is regulated by a slide valve in the regener-
Stacked configuration: ated catalyst line. The hot flue gas exits the regenerator
after passing through multiple sets of two-stage cyclones
that remove entrained catalyst from the flue gas,
• Kellogg Brown & Root (KBR)
The amount of catalyst circulating between the regen-
Each of the proprietary design licensors claims to have erator and the reactor amounts to about 5 kg per kg of
unique features and advantages. A complete discussion of feedstock, which [1][7]
is equivalent to about 4.66 kg per litre
the relative advantages of each of the processes is beyond of feedstock. Thus, an FCC unit processing 75,000
the scope of this article. Suffice it to say that all of the barrels per day (11,900 m3 /d) will circulate about 55,900
licensors have designed and constructed FCC units that tonnes per day of catalyst.
have operated quite satisfactorily.
tors produce a light cracked naphtha and a heavy cracked The flue gas is finally processed through an electrostatic
naphtha. The terminology light and heavy in this context precipitator (ESP) to remove residual particulate matter
refers to the product boiling ranges, with light products to comply with any applicable environmental regulations
having a lower boiling range than heavy products. regarding particulate emissions. The ESP removes par-
The bottom product oil from the main fractionator con- ticulates in the size range of 2 to 20 µm from the flue
tains residual catalyst particles which were not completely gas.[3] Particulate filter systems, known as Fourth Stage
removed by the cyclones in the top of the reactor. For that Separators (FSS) are sometimes required to meet partic-
reason, the bottom product oil is referred to as a slurry oil. ulate emission limits. These can replace the ESP when
particulate emissions are the only concern.
Part of that slurry oil is recycled back into the main frac-
tionator above the entry point of the hot reaction product The steam turbine in the flue gas processing system
vapors so as to cool and partially condense the reaction (shown in the above diagram) is used to drive the regener-
product vapors as they enter the main fractionator. The ator’s combustion air compressor during start-ups of the
remainder of the slurry oil is pumped through a slurry set- FCC unit until there is sufficient combustion flue gas to
tler. The bottom oil from the slurry settler contains most take over that task.
of the slurry oil catalyst particles and is recycled back into
the catalyst riser by combining it with the FCC feedstock
oil. The so-called clarified slurry oil or decant oil is with- 6.2 Chemistry
drawn from the top of slurry settler for use elsewhere in
the refinery, as a heavy fuel oil blending component, or
Before delving into the chemistry involved in catalytic
as carbon black feedstock.
cracking, it will be helpful to briefly discuss the compo-
sition of petroleum crude oil.
Petroleum crude oil consists primarily of a mixture of
6.1.3 Regenerator flue gas hydrocarbons with small amounts of other organic com-
pounds containing sulfur, nitrogen and oxygen. The crude
Depending on the choice of FCC design, the combustion oil also contains small amounts of metals such as copper,
in the regenerator of the coke on the spent catalyst may or iron, nickel and vanadium.[2]
may not be complete combustion to carbon dioxide CO
The elemental composition ranges of crude oil are sum-
2. The combustion air flow is controlled so as to pro-
marized in Table 1 and the hydrocarbons in the crude oil
vide the desired ratio of carbon monoxide (CO) to carbon
can be classified into three types:[1][2]
dioxide for each specific FCC design.[1][4]
In the design shown in Figure 1, the coke has only been • Paraffins or alkanes: saturated straight-chain or
partially combusted to CO branched hydrocarbons, without any ring structures
2. The combustion flue gas (containing CO and CO
2) at 715 °C and at a pressure of 2.41 barg is routed • Naphthenes or cycloalkanes: saturated hydrocar-
through a secondary catalyst separator containing swirl bons having one or more ring structures with one
tubes designed to remove 70 to 90 percent of the or more side-chain paraffins
particulates in the flue gas leaving the regenerator.[8] This
is required to prevent erosion damage to the blades in the • Aromatics: hydrocarbons having one or more un-
turbo-expander that the flue gas is next routed through. saturated ring structures such as benzene or unsatu-
rated polycyclic ring structures such as naphthalene
The expansion of flue gas through a turbo-expander pro- or phenanthrene, any of which may also have one or
vides sufficient power to drive the regenerator’s combus- more side-chain paraffins.
tion air compressor. The electrical motor-generator can
consume or produce electrical power. If the expansion of
the flue gas does not provide enough power to drive the Olefins or alkenes, which are unsaturated straight-chain
air compressor, the electric motor/generator provides the or branched hydrocarbons, do not occur naturally in crude
needed additional power. If the flue gas expansion pro- oil.
vides more power than needed to drive the air compres- In plain language, the fluid catalytic cracking pro-
sor, than the electric motor/generator converts the excess cess breaks large hydrocarbon molecules into smaller
power into electric power and exports it to the refinery’s molecules by contacting them with powdered catalyst at
electrical system.[3] a high temperature and moderate pressure which first va-
The expanded flue gas is then routed through a steam- porizes the hydrocarbons and then breaks them. The
generating boiler (referred to as a CO boiler) where the cracking reactions occur in the vapor phase and start im-
carbon monoxide in the flue gas is burned as fuel to pro- mediately when the feedstock is vaporized in the catalyst
vide steam for use in the refinery as well as to comply with riser.
any applicable environmental regulatory limits on carbon Figure 2 is a very simplified schematic diagram
monoxide emissions.[3] that exemplifies how the process breaks high boiling,
6.2. CHEMISTRY 31
6.2.1 Catalysts
• High activity
The binder and filler components provide the physical 6.3 History
strength and integrity of the catalyst. The binder is usu-
ally silica sol and the filler is usually a clay (kaolin).
Nickel, vanadium, iron, copper and other metal contami- The first commercial use of catalytic cracking occurred in
nants, present in FCC feedstocks in the parts per million 1915 when Almer M. McAfee of Gulf Refining Company
range, all have detrimental effects on the catalyst activity developed a batch process using aluminum chloride (a
and performance. Nickel and vanadium are particularly Friedel Crafts catalyst known since 1877) to catalytically
troublesome. There are a number of methods for miti- crack heavy petroleum oils. However, the prohibitive cost
gating the effects of the contaminant metals:[11][12] of the catalyst prevented the widespread use of McAfee’s
process at that time.[2][14]
In 1922, a French mechanical engineer named Eugene
• Avoid feedstocks with high metals content: This
Jules Houdry and a French pharmacist named E.A. Prud-
seriously hampers a refinery’s flexibility to process
homme set up a laboratory near Paris to develop a cat-
various crude oils or purchased FCC feedstocks.
alytic process for converting lignite coal to gasoline. Sup-
ported by the French government, they built a small
• Feedstock feed pretreatment: Hydrodesulfurization
demonstration plant in 1929 that processed about 60 tons
of the FCC feedstock removes some of the metals
per day of lignite coal. The results indicated that the pro-
and also reduces the sulfur content of the FCC prod-
cess was not economically viable and it was subsequently
ucts. However, this is quite a costly option.
shut down.[15][16][17]
• Increasing fresh catalyst addition: All FCC units Houdry had found that Fuller’s earth, a clay mineral con-
withdraw some of the circulating equilibrium cata- taining aluminosilicates, could convert oil derived from
lyst as spent catalyst and replaces it with fresh cata- the lignite to gasoline. He then began to study the cataly-
lyst in order to maintain a desired level of activity. sis of petroleum oils and had some success in converting
Increasing the rate of such exchange lowers the level vaporized petroleum oil to gasoline. In 1930, the Vacuum
of metals in the circulating equilibrium catalyst, but Oil Company invited him to come to the United States
this is also quite a costly option. and he moved his laboratory to Paulsboro, New Jersey.
In 1931, the Vacuum Oil Company merged with Standard
• Demetallization: The commercial proprietary Oil of New York (Socony) to form the Socony-Vacuum
Demet Process removes nickel and vanadium from Oil Company. In 1933, a small Houdry unit processed
the withdrawn spent catalyst. The nickel and 200 barrels per day (32 m3 /d) of petroleum oil. Because
vanadium are converted to chlorides which are of the economic depression of the early 1930s, Socony-
then washed out of the catalyst. After drying, the Vacuum was no longer able to support Houdry’s work and
demetallized catalyst is recycled into the circulating gave him permission to seek help elsewhere.
catalyst. Removals of about 95 percent nickel
removal and 67 to 85 percent vanadium have been In 1933, Houdry and Socony-Vacuum joined with Sun
reported. Despite that, the use of the Demet process Oil Company in developing the Houdry process. Three
has not become widespread, perhaps because of the years later, in 1936, Socony-Vacuum converted an older
high capital expenditure required. thermal cracking unit in their Paulsboro refinery in New
Jersey to a small demonstration unit using the Houdry
• Metals passivation: Certain materials can be used as process
3
to catalytically crack 2,000 barrels per day (320
additives which can be impregnated into the catalyst m /d) of petroleum oil.
or added to the FCC feedstock in the form of metal- In 1937, Sun Oil began operation of a new Houdry unit
organic compounds. Such materials react with the processing 12,000 barrels per day (1,900 m3 /d) in their
metal contaminants and passivate the contaminants Marcus Hook refinery in Pennsylvania. The Houdry pro-
by forming less harmful compounds that remain on cess at that time used reactors with a fixed bed of catalyst
the catalyst. For example, antimony and bismuth and was a semi-batch operation involving multiple reac-
are effective in passivating nickel and tin is effective tors with some of the reactors in operation while other
in passivating vanadium. A number of proprietary reactors were in various stages of regenerating the cata-
passivation processes are available and fairly widely lyst. Motor-driven valves were used to switch the reactors
used. between online operation and offline regeneration and a
cycle timer managed the switching. Almost 50 percent of
The major suppliers of FCC catalysts worldwide in- the cracked product was gasoline as compared with about
[15][16][17]
clude Albemarle Corporation, W.R. Grace Company and 25 percent from the thermal cracking processes.
BASF Catalysts (formerly Engelhard). The price for By 1938, when the Houdry process was publicly an-
lanthanum oxide used in fluid catalytic cracking has risen nounced, Socony-Vacuum had eight additional units un-
from $5 per kilogram in early 2010 to $140 per kilogram der construction. Licensing the process to other compa-
in June 2011.[13] nies also began and by 1940 there were 14 Houdry units
6.4. SEE ALSO 33
in operation processing 140,000 barrels per day (22,000 alytic cracking unit. Their U.S. Patent No. 2,451,804,
m3 /d). A Method of and Apparatus for Contacting Solids and
The next major step was to develop a continuous process Gases, describes their milestone invention. Based on their
rather than the semi-batch Houdry process. That step work, M. W. Kellogg Company constructed a large pilot
was implemented by advent of the moving-bed process plant in the Baton Rouge, Louisiana refinery of the Stan-
known as the Thermofor Catalytic Cracking (TCC) pro- dard Oil of New Jersey. The pilot plant began operation
cess which used a bucket conveyor-elevator to move the in May 1940.
catalyst from the regeneration kiln to the separate reac- Based on the success of the pilot plant, the first commer-
tor section. A small semicommercial demonstration TCC cial fluid catalytic cracking plant (known as the Model
unit was built in Socony-Vacuum’s Paulsboro refinery in I FCC) began processing 13,000 barrels per day (2,100
1941 and operated successfully, producing 500 barrels m3 /d) of petroleum oil in the Baton Rouge refinery on
per day (79 m3 /d). Then a full-scale commercial TCC May 25, 1942, just four years after the CRA consortium
unit processing 10,000 barrels per day (1,600 m3 /d) be- was formed and in the midst of World War II. A little
gan operation in 1943 at the Beaumont, Texas refinery of more than a month later, in July 1942, it was processing
Magnolia Oil Company, an affiliate of Socony-Vacuum. 17,000 barrels per day (2,700 m3 /d). In 1963, that first
By the end of World War II in 1945, the processing ca- Model I FCC unit was shut down after 21 years of oper-
pacity of the TCC units in operation was about 300,000 ation and subsequently dismantled.[15][16][17][18]
barrels per day (48,000 m3 /d). In the many decades since the Model I FCC unit be-
It is said that the Houdry and TCC units were a ma- gan operation, the fixed bed Houdry units have all been
jor factor in the winning of World War II by supply- shut down as have most of the moving bed units (such
ing the high-octane gasoline needed by the air forces of as the TCC units) while hundreds of FCC units have
Great Britain and the United States for the more efficient been built. During those decades, many improved FCC
higher compression ratio engines of the Spitfire and the designs have evolved and cracking catalysts have been
Mustang.[15][16][17] greatly improved, but the modern FCC units are essen-
In the years immediately after World War II, the Houdri- tially the same as that first Model I FCC unit.
flow process and the air-lift TCC process were developed Note: All of the refinery and company names in this his-
as improved variations on the moving-bed theme. Just tory section (with the exception of Universal Oil Prod-
like Houdry’s fixed-bed reactors, the moving-bed designs ucts) have changed over time by mergers and buyouts.
were prime examples of good engineering by developing Some have changed a number of times.
a method of continuously moving the catalyst between the
reactor and regeneration sections. The first air-lift TCC
unit began operation in October 1950 at the Beaumont,
Texas refinery.
6.4 See also
This fluid catalytic cracking process had first been investi-
• Oil refinery
gated in the 1920s by Standard Oil of New Jersey, but re-
search on it was abandoned during the economic depres- • Petroleum
sion years of 1929 to 1939. In 1938, when the success of
Houdry’s process had become apparent, Standard Oil of • Cracking (chemistry)
New Jersey resumed the project as part of a consortium
of that include five oil companies (Standard Oil of New • Catalysis
Jersey, Standard Oil of Indiana, Anglo-Iranian Oil, Texas
Oil and Dutch Shell), two engineering-construction com-
panies (M.W. Kellogg and Universal Oil Products) and
a German chemical company (I.G. Farben). The consor- 6.5 References
tium was called Catalytic Research Associates (CRA) and
its purpose was to develop a catalytic cracking process [1] James H. Gary and Glenn E. Handwerk (2001). Petroleum
which would not impinge on Houdry’s patents.[15][16][17] Refining: Technology and Economics (4th ed.). CRC
Press. ISBN 0-8247-0482-7.
Chemical engineering professors Warren K. Lewis and
Edwin R. Gilliland of the Massachusetts Institute of [2] James. G. Speight (2006). The Chemistry and Technology
Technology (MIT) suggested to the CRA researchers that of Petroleum (4th ed.). CRC Press. ISBN 0-8493-9067-2.
a low velocity gas flow through a powder might “lift” it
enough to cause it to flow in a manner similar to a liquid. [3] Reza Sadeghbeigi (2000). Fluid Catalytic Cracking Hand-
Focused on that idea of a fluidized catalyst, researchers book (2nd ed.). Gulf Publishing. ISBN 0-88415-289-8.
Donald Campbell, Homer Martin, Eger Murphree and
Charles Tyson of the Standard Oil of New Jersey (now [4] David S.J. Jones and Peter P. Pujado (Editors) (2006).
Handbook of Petroleum Processing (First ed.). Springer.
Exxon-Mobil Company) developed the first fluidized cat-
ISBN 1-4020-2819-9.
34 CHAPTER 6. FLUID CATALYTIC CRACKING
[5] U.S. Downstream Processing of Fresh Feed Input by Cat- • North American Catalysis Society
alytic Cracking Units (Energy Information Administra-
tion, U.S. Dept. of Energy) • Fluid Catalytic Cracking (University of British
Columbia, Quak Foo, Lee )
[6] Editorial Staff (November 2002). “Refining Processes
2002”. Hydrocarbon Processing: 108–112. ISSN 0887- • CFD Simulation of a Full-Scale Commercial FCC
0284. Regenerator
[7] Fluid Catalytic Cracking
[18] Eger Murphree and the Four Horsemen: FCC, Fluid Cat-
alytic Cracking (North American Catalysis Society web-
site)
Cracking (chemistry)
In petroleum geology and chemistry, cracking is the 7.1 History and patents
process whereby complex organic molecules such as
kerogens or heavy hydrocarbons are broken down into
Among several variants of thermal cracking methods
simpler molecules such as light hydrocarbons, by the
(variously known as the "Shukhov cracking process",
breaking of carbon-carbon bonds in the precursors. The
"Burton cracking process", “Burton-Humphreys crack-
rate of cracking and the end products are strongly de-
ing process”, and “Dubbs cracking process”) Vladimir
pendent on the temperature and presence of catalysts.
Shukhov, a Russian engineer, invented and patented the
Cracking is the breakdown of a large alkane into smaller,
first in 1891 (Russian Empire, patent no. 12926, Novem-
more useful alkanes and alkenes. Simply put, hydrocar-
ber 27, 1891).[1] One installation was used to a lim-
bon cracking is the process of breaking a long-chain of
ited extent in Russia, but development was not followed
hydrocarbons into short ones.
up. In the first decade of the 20th century the Amer-
More loosely, outside the field of petroleum chemistry, ican engineers William Merriam Burton and Robert E.
the term “cracking” is used to describe any type of split- Humphreys independently developed and patented a sim-
ting of molecules under the influence of heat, catalysts ilar process as U.S. patent 1,049,667 on June 8, 1908.
and solvents, such as in processes of destructive distilla- Among its advantages was the fact that both the condenser
tion or pyrolysis. and the boiler were continuously kept under pressure.[2]
Fluid catalytic cracking produces a high yield of gasoline In its earlier versions however, it was a batch process,
and LPG, while hydrocracking is a major source of jet rather than continuous, and many patents were to follow
fuel, Diesel fuel, naphtha, and LPG. in the USA and Europe, though not all were practical.[1]
In 1924, a delegation from the American Sinclair Oil Cor-
poration visited Shukhov. Sinclair Oil apparently wished
to suggest that the patent of Burton and Humphreys, in
use by Standard Oil, was derived from Shukhov’s patent
for oil cracking, as described in the Russian patent. If that
could be established, it could strengthen the hand of rival
American companies wishing to invalidate the Burton-
Humphreys patent. In the event Shukhov satisfied the
Americans that in principle Burton’s method closely re-
sembled his 1891 patents, though his own interest in the
matter was primarily to establish that “the Russian oil in-
dustry could easily build a cracking apparatus according
to any of the described systems without being accused by
the Americans of borrowing for free”.[3]
At that time, just a few years after the Russian Revolu-
tion, Russia was desperate to develop industry and earn
foreign exchange, so their oil industry eventually did ob-
tain much of their technology from foreign companies,
largely American.[3] At about that time however, fluid
catalytic cracking was being explored and developed and
soon replaced most of the purely thermal cracking pro-
Refinery using the Shukhov cracking process, Baku, Soviet Union, cesses in the fossil fuel processing industry. The replace-
1934. ment was however not complete; many types of crack-
ing, including pure thermal cracking, still are in use, de-
pending on the nature of the feedstock and the products
35
36 CHAPTER 7. CRACKING (CHEMISTRY)
required to satisfy market demands. Thermal cracking CH3 CH2 • + CH2 =CH2 →
remains important however, for example in producing CH3 CH2 CH2 CH2 •
naphtha, gas oil, and coke, and more sophisticated forms
of thermal cracking have been developed for various pur-
poses. These include visbreaking, steam cracking, and 7.2.5 Termination
coking.[4]
In these reactions two free radicals react with each other
to produce products that are not free radicals. Two com-
mon forms of termination are recombination, where the
7.2 Chemistry two radicals combine to form one larger molecule, and
disproportionation, where one radical transfers a hydro-
A large number of chemical reactions take place during gen atom to the other, giving an alkene and an alkane.
the cracking process, most of them based on free radi-
cals. Computer simulations aimed at modeling what takes CH3 • + CH3 CH2 • → CH3 CH2 CH3
place during steam cracking have included hundreds or
even thousands of reactions in their models. The main CH3 CH2 • + CH3 CH2 • → CH2 =CH2 +
reactions that take place include: CH3 CH3
In these reactions a single molecule breaks apart into two There are three places where a butane molecule (CH3 -
free radicals. Only a small fraction of the feed molecules CH2 -CH2 -CH3 ) might be split. Each has a distinct like-
actually undergo initiation, but these reactions are neces- lihood:
sary to produce the free radicals that drive the rest of the
reactions. In steam cracking, initiation usually involves • 48%: break at the CH3 -CH2 bond.
breaking a chemical bond between two carbon atoms,
rather than the bond between a carbon and a hydrogen CH3 * / *CH2 -CH2 -CH3
atom.
Ultimately this produces an alkane and an
alkene: CH4 + CH2 =CH-CH3
CH3 CH3 → 2 CH3 •
• 38%: break at a CH2 -CH2 bond.
7.2.2 Hydrogen abstraction
CH3 -CH2 * / *CH2 -CH3
In these reactions a free radical removes a hydrogen atom Ultimately this produces an alkane and an
from another molecule, turning the second molecule into alkene of different types: CH3 -CH3 +
a free radical. CH2 =CH2
CH3 • + CH3 CH3 → CH4 + CH3 CH2 • • 14%: break at a terminal C-H bond
highly endothermic, the large positive entropy change re- depend on the composition of the feed, the hydrocarbon-
sulting from the fragmentation of one large molecule into to-steam ratio, and on the cracking temperature and fur-
several smaller pieces, together with the extremely high nace residence time.[7]
temperature, makes T∆S° term larger than the ∆H° term, In steam cracking, a gaseous or liquid hydrocarbon feed
thereby favoring the cracking reaction. like naphtha, LPG or ethane is diluted with steam and
briefly heated in a furnace without the presence of oxy-
Thermal cracking gen. Typically, the reaction temperature is very high, at
around 850°C, but the reaction is only allowed to take
Modern high-pressure thermal cracking operates at ab- place very briefly. In modern cracking furnaces, the res-
solute pressures of about 7,000 kPa. An overall pro- idence time is reduced to milliseconds to improve yield,
cess of disproportionation can be observed, where “light”, resulting in gas velocities faster than the speed of sound.
hydrogen-rich products are formed at the expense of After the cracking temperature has been reached, the gas
heavier molecules which condense and are depleted of hy- is quickly quenched to stop the reaction in a transfer line
drogen. The actual reaction is known as homolytic fission heat exchanger or inside a quenching header using quench
and produces alkenes, which are the basis for the econom- oil.
ically important production of polymers. The products produced in the reaction depend on the
Thermal cracking is currently used to “upgrade” very composition of the feed, the hydrocarbon to steam ratio
heavy fractions or to produce light fractions or distil- and on the cracking temperature and furnace residence
lates, burner fuel and/or petroleum coke. Two ex- time. Light hydrocarbon feeds such as ethane, LPGs
tremes of the thermal cracking in terms of product range or light naphtha give product streams rich in the lighter
are represented by the high-temperature process called alkenes, including ethylene, propylene, and butadiene.
“steam cracking” or pyrolysis (ca. 750 °C to 900 °C or Heavier hydrocarbon (full range and heavy naphthas as
higher) which produces valuable ethylene and other feed- well as other refinery products) feeds give some of these,
stocks for the petrochemical industry, and the milder- but also give products rich in aromatic hydrocarbons and
temperature delayed coking (ca. 500 °C) which can pro- hydrocarbons suitable for inclusion in gasoline or fuel oil.
duce, under the right conditions, valuable needle coke, a A higher cracking temperature (also referred to as sever-
highly crystalline petroleum coke used in the production ity) favors the production of ethene and benzene, whereas
of electrodes for the steel and aluminium industries. lower severity produces higher amounts of propene, C4-
The first thermal cracking method, the Shukhov crack- hydrocarbons and liquid products. The process also re-
ing process, was invented by Russian engineer Vladimir sults in the slow deposition of coke, a form of carbon,
Shukhov, in the Russian empire, Patent No. 12926, on the reactor walls. This degrades the efficiency of the
November 27, 1891.[5] reactor, so reaction conditions are designed to minimize
this. Nonetheless, a steam cracking furnace can usually
William Merriam Burton developed one of the earliest only run for a few months at a time between de-cokings.
thermal cracking processes in 1912 which operated at Decokes require the furnace to be isolated from the pro-
700–750 °F (371–399 °C) and an absolute pressure of cess and then a flow of steam or a steam/air mixture is
90 psi (620 kPa) and was known as the Burton process. passed through the furnace coils. This converts the hard
Shortly thereafter, in 1921, C.P. Dubbs, an employee of solid carbon layer to carbon monoxide and carbon diox-
the Universal Oil Products Company, developed a some- ide. Once this reaction is complete, the furnace can be
what more advanced thermal cracking process which op- returned to service.
erated at 750–860 °F (399–460 °C) and was known as
the Dubbs process.[6] The Dubbs process was used ex-
tensively by many refineries until the early 1940s when
catalytic cracking came into use.
7.3.2 Catalytic methods
7.5 References
[1] M. S. Vassiliou (2 March 2009). Historical Dictionary of
the Petroleum Industry. Scarecrow Press. pp. 459–. ISBN
978-0-8108-6288-3.
Visbreaker
40
8.4. ECONOMICS 41
8.2.4 Soaker visbreaking versus coil vis- 8.3.3 Fuel oil stability
breaking
The severity of visbreaker operation is normally lim-
From the standpoint of yield, there is little or nothing to ited by the need to produce a visbreaker tar that can be
choose between the two approaches. However, each of- blended to make a stable fuel oil.
fers significant advantages in particular situations: Stability in this case is taken to mean the tendency of a
fuel oil to produce sediments when stored. These sed-
• De-coking: The cracking reaction forms petroleum
iments are undesirable as they can quickly foul the fil-
coke as a byproduct. In coil visbreaking, this de-
ters of pumps used to move the oil necessitating time-
posits in the tubes of the furnace and will eventu-
consuming maintenance.
ally lead to fouling or blocking of the tubes. The
same will occur in the drum of a soaker visbreaker, Vacuum residue fed to a visbreaker can be considered to
though the lower temperatures used in the soaker be composed of the following:
drum lead to fouling at a much slower rate. Coil vis-
breakers therefore require frequent de-coking. This • Asphaltenes: large polycyclic molecules that are
is quite labour-intensive, but can be developed into a suspended in the oil in a coloidal form
routine where tubes are de-coked sequentially with-
out the need to shutdown the visbreaking operation. • Resins: also polycyclic but of a lower molecular
Soaker drums require far less frequent attention but weight than asphaltenes
their being taken out of service normally requires a
complete halt to the operation. Which is the more • Aromatic hydrocarbons: derivatives of benzene,
disruptive activity will vary from refinery to refinery. toluene and xylenes
• Fuel Economy: The lower temperatures used in the • Parafinic hydrocarbons: alkanes
soaker approach mean that these units use less fuel.
In cases where a refinery buys fuel to support process Visbreaking preferentially cracks aliphatic compounds
operations, any savings in fuel consumption could be which have relatively low sulphur contents, low density
extremely valuable. In such cases, soaker visbreak- and high viscosity and the effect of their removal can be
ing may be advantageous. clearly seen in the change in quality between feed and
product. A too severe cracking in a visbreaker will lead to
the asphaltene colloid becoming metastable. Subsequent
8.3 Quality and yields addition of a diluent to manufacture a finished fuel oil can
cause the colloid to break down, precipitating asphaltenes
8.3.1 Feed quality and product quality as a sludge. It has been observed that a paraffinic diluent
is more likely to cause precipitation than an aromatic one.
The quality of the feed going into a visbreaker will vary Stability of fuel oil is assessed using a number of propri-
considerably with the type of crude oil that the refinery etary tests (for example “P” value and SHF tests).
is processing. The following is a typical quality for the
vacuum distillation residue of Arabian light (a crude oil
from Saudi Arabia and widely refined around the world): 8.4 Economics
Once this material has been run through a visbreaker
(and, again, there will be considerable variation from vis- 8.4.1 Viscosity blending
breaker to visbreaker as no two will operate under ex-
actly the same conditions) the reduction in viscosity is The viscosity blending of two or more liquids having
dramatic: different viscosities is a three-step procedure. The first
42 CHAPTER 8. VISBREAKER
step is to calculate the Viscosity Blending Index (VBI) of oil manufacture. For example, if the cutter stock is taken
each component of the blend using the following equation to have a value of $300 per tonne and fuel oil $150 per
(known as a Refutas equation): [2][4] ton (oil prices naturally change quickly, but these prices,
and more importantly the differences between them, are
(1) VBN = 14.534 × ln[ln(v + 0.8)] + 10.975 not unrealistic), it is a simple matter to calculate the value
of the different residues in this example as being:
where v is the viscosity in square millimeters per second Virgin residue: $93.1 per tonne
(mm²/s) or centistokes (cSt) and ln is the natural loga- Visbroken residue: $127.0 per tonne
rithm (logₑ). It is important that the viscosity of each
component of the blend be obtained at the same temper-
ature.
8.5 References
The next step is to calculate the VBN of the blend, using
this equation: [1] James H. Gary and Glenn E. Handwerk (1984). Petroleum
Refining Technology and Economics (2nd Edition ed.).
(2) VBNB ₑ = [wA × VBNA] + [wB × Marcel Dekker, Inc. ISBN 0-8247-7150-8.
VBNB] + ... + [wX × VBNX] [2] Robert E. Maples (2000). Petroleum Refinery Process
Economics (2nd Edition ed.). Pennwell Books. ISBN 0-
where w is the weight fraction (i.e., % ÷ 100) of each 87814-779-9.
component of the blend.
[3] James G. Speight (2006). The Chemistry and Technology
Once the viscosity blending number of a blend has been of Petroleum (4th Edition ed.). CRC Press. ISBN 0-8493-
calculated using equation (2), the final step is to determine 9067-2.
the viscosity of the blend by using the invert of equation
[4] C.T. Baird (1989), Guide to Petroleum Product Blending,
(1):
HPI Consultants, Inc. HPI website
(VBN - 10.975) ÷ 14.534
(3) v = ee − 0.8
8.6 External links
where VBN is the viscosity blending number of the blend
and e is the transcendental number 2.71828, also known • Foster Wheeler Visbreaking Overview
as Euler’s number.
• Shell Thermal Conversion
A marketable fuel oil, such as for fueling a power station, • Shell Thermal Gasoil Unit (TGU)
might be required to have a viscosity of 40 centistokes at
100 °C. It might be prepared using either the virgin or • Fuel Oil Stability Testing
visbroken residue described above combined with a dis- • Bunkerworld: “Sediment Stability and Compatibil-
tillate diluent (“cutter stock”). Such a cutter stock could ity - The Structure of Fuel Oil”
typically have a viscosity at 100 °C of 1.3 centistokes.
Rearranging equation (2) above for a simple two compo-
nent blend shows that the percentage of cutterstock re-
quired in the blend is found by:
(4) %cutter stock = [VBN40 − VBNᵣₑ ᵢ ᵤₑ] ÷ [VBN ᵤ ₑᵣ
ₒ − VBNᵣₑ ᵢ ᵤₑ]
Using the viscosities quoted in the tables above for the
residues from Arab Light crude oil and calculating VBNs
according to equation (1) gives:
For virgin residue (i.e., the unconverted feed to the vis-
breaker): 27.5% cutter stock in the blend
For visbroken residue: 13.3% cutter stock in the blend.
As middle distillates have a far higher value in the market
place than fuel oils, it can be seen that the use of a vis-
breaker will considerably improve the economics of fuel
Chapter 9
Merox
43
44 CHAPTER 9. MEROX
9.2 Conventional Merox for ex- naphtha) feedstock enters the prewash vessel and flows
upward through a batch of caustic which removes any
tracting mercaptans from LPG H2 S that may be present in the feedstock. The coalescer
at the top of the prewash vessel prevents caustic from be-
The conventional Merox process for extraction and re- ing entrained and carried out of the vessel.
moval of mercaptans from liquefied petroleum gases
(LPG), such as propane, butanes and mixtures of propane The feedstock then enters the mercaptan extractor and
and butanes, can also be used to extract and remove mer- flows upward through the contact trays where the LPG
captans from light naphthas.[2] It is a two-step process. In intimately contacts the downflowing Merox caustic that
the first step, the feedstock LPG or light naphtha is con- extracts the mercaptans from the LPG. The sweetened
tacted in the trayed extractor vessel with an aqueous caus- LPG exits the tower and flows through: a caustic settler
tic solution containing UOP’s proprietary liquid catalyst. vessel to remove any entrained caustic, a water wash ves-
The caustic solution reacts with mercaptans and extracts sel to further remove any residual entrained caustic and
them. The reaction that takes place in the extractor is: a vessel containing a bed of rock salt to remove any en-
trained water. The dry sweetened LPG exits the Merox
2RSH + 2 NaOH → 2NaSR + 2 H O unit.
2
The caustic solution leaving the bottom of the mercaptan
In the above reaction, RSH is a mercaptan and R signifies extractor (“rich” Merox caustic) flows through a control
an organic group such as a methyl, ethyl, propyl or other valve which maintains the extractor pressure needed to
group. For example, the ethyl mercaptan (ethanethiol) keep the LPG liquified. It is then injected with UOP’s
has the formula C2 H5 SH. proprietary liquid catalyst (on an as needed basis), flows
The second step is referred to as regeneration and it in- through a steam-heated heat exchanger and is injected
volves heating and oxidizing of the caustic solution leav- with compressed air before entering the oxidizer vessel
ing the extractor. The oxidations results in converting the where the extracted mercaptans are converted to disul-
extracted mercaptans to organic disulfides (RSSR) which fides. The oxidizer vessel has a packed bed to keep
are liquids that are water-insoluble and are then separated the aqueous caustic and the water-insoluble disulfide well
and decanted from the aqueous caustic solution. The re- contacted and well mixed.
action that takes place in the regeneration step is: The caustic-disulfide mixture then flows into the separa-
tor vessel where it is allowed to form a lower layer of
4NaSR + O2 + 2H2 O → 2RSSR + 4NaOH “lean” Merox caustic and an upper layer of disulfides. The
vertical section of the separator is for the disengagement
After decantation of the disulfides, the regenerated “lean” and venting of excess air and includes a Raschig ring sec-
caustic solution is recirculated back to the top of the ex- tion to prevent entrainment of any disulfides in the vented
tractor to continue extracting mercaptans. air. The disulfides are withdrawn from the separator and
routed to fuel storage or to a hydrotreater unit. The re-
The net overall Merox reaction covering the extraction
generated lean Merox caustic is then pumped back to the
and the regeneration step may be expressed as:
top of the extractor for reuse.
4 RSH + O2 → 2RSSR + 2H2 O
H2 S + NaOH → NaSH + H2 O
9.3 Conventional Merox for sweet- The pressure maintained in the reactor is chosen so that
the injected air will completely dissolve in the feedstock
ening jet fuel or kerosene at the operating temperature.
Coker unit
• Delayed coker
• Burton process
• Visbreaker
• Petroleum coke
47
Chapter 11
Alkylation
Alkylation is the transfer of an alkyl group from one use of organometallic compounds such as Grignard
molecule to another. The alkyl group may be trans- (organomagnesium), organolithium, organocopper, and
ferred as an alkyl carbocation, a free radical, a carbanion organosodium reagents. These compounds typically can
or a carbene (or their equivalents).[1] Alkylating agents add to an electron-deficient carbon atom such as at a
are widely used in chemistry because the alkyl group is carbonyl group. Nucleophilic alkylating agents can also
probably the most common group encountered in organic displace halide substituents on a carbon atom. In the pres-
molecules. Many biological target molecules or their syn- ence of catalysts, they also alkylate alkyl and aryl halides,
thetic precursors are composed of an alkyl chain with spe- as exemplified by Suzuki couplings.
cific functional groups in a specific order. Selective alky-
lation, or adding parts to the chain with the desired func-
tional groups, is used, especially if there is no commonly 11.1.2 Electrophilic alkylating agents
available biological precursor. Alkylation with only one
carbon is termed methylation. Electrophilic alkylating agents deliver the equivalent of
an alkyl cation. Examples include the use of alkyl halides
In oil refining contexts, alkylation refers to a particular with a Lewis acid catalyst to alkylate aromatic substrates
alkylation of isobutane with olefins. For upgrading of in Friedel-Crafts reactions. Alkyl halides can also react
petroleum, alkylation produces synthetic C7 –C8 alkylate, directly with amines to form C-N bonds; the same holds
which is a premium blending stock for gasoline.[2] true for other nucleophiles such as alcohols, carboxylic
In medicine, alkylation of DNA is used in chemotherapy acids, thiols, etc.
to damage the DNA of cancer cells. Alkylation is accom- Electrophilic, soluble alkylating agents are often very
plished with the class of drugs called alkylating antineo- toxic, due to their ability to alkylate DNA. They should be
plastic agents. handled with proper PPE. This mechanism of toxicity is
also responsible for the ability of some alkylating agents
to perform as anti-cancer drugs in the form of alkylating
antineoplastic agents, and also as chemical weapons such
as mustard gas. Alkylated DNA either does not coil or
uncoil properly, or cannot be processed by information-
decoding enzymes. This results in cytotoxicity with the
Benzene Friedel-Crafts alkylation. effects of inhibition the growth of the cell, initiation of
programmed cell death or apoptosis. However, mutations
are also triggered, including carcinogenic mutations, ex-
plaining the higher incidence of cancer after exposure.
11.1 Alkylating agents
Alcohols and phenols can be alkylated to give alkyl ethers:
“Alkylating agent” redirects here. For the class R-OH + R'-X → R-O-R' + H-X
of drugs, see alkylating antineoplastic agent.
The produced acid HX is removed with a base, or, al-
Alkylating agents are classified according to their ternatively, the alcohol is deprotonated first to give an
nucleophilic or electrophilic character. alkoxide or phenoxide. For example, dimethyl sulfate
alkylates the sodium salt of phenol to give anisole, the
methyl ether of phenol. The dimethyl sulfate is dealky-
11.1.1 Nucleophilic alkylating agents lated to sodium methylsulfate.[3]
Nucleophilic alkylating agents deliver the equivalent Ph-O– Na+ + Me2 SO4 → Ph-O-Me + Na+
of an alkyl anion (carbanion). Examples include the MeSO4 –
48
11.3. OIL REFINING 49
Trimethyloxonium tetrafluoroborate and triethyloxonium The product is called alkylate and is composed of
tetrafluoroborate belong to one of these categories. a mixture of high-octane, branched-chain paraffinic
hydrocarbons (mostly isoheptane and isooctane). Alky-
late is a premium gasoline blending stock because it has
exceptional antiknock properties and is clean burning.
11.2 In biology Alkylate is also a key component of avgas. The octane
number of the alkylate depends mainly upon the kind
Main article: methylation of alkenes used and upon operating conditions. For ex-
ample, isooctane results from combining butylene with
Methylation is the most common type of alkylation, being isobutane and has an octane rating of 100 by definition.
associated with the transfer of a methyl group. Methy- There are other products in the alkylate, so the octane
lation is distinct from alkylation in that it is specifically rating will vary accordingly.
the transfer of one carbon, whereas alkylation can re- Since crude oil generally contains only 10 to 40 per-
fer to the transfer of long chain carbon groups. Methy- cent of hydrocarbon constituents in the gasoline range,
lation in nature is typically effected by vitamin B12- refineries use a fluid catalytic cracking process to con-
derived enzymes, where the methyl group is carried by vert high molecular weight hydrocarbons into smaller and
cobalt. In methanogenesis, coenzyme M is methylated more volatile compounds, which are then converted into
by tetrahydromethanopterin. liquid gasoline-size hydrocarbons. Alkylation processes
Electrophilic compounds may alkylate different nucle- transform low molecular-weight alkenes and iso-paraffin
ophiles in the body. The toxicity, carcinogenity, and molecules into larger iso-paraffins with a high octane
paradoxically, cancer cell-killing abilities of different number.
DNA alkylating agents are an example. Combining cracking, polymerization, and alkylation can
result in a gasoline yield representing 70 percent of
the starting crude oil. More advanced processes, such
11.3 Oil refining as cyclicization of paraffins and dehydrogenation of
naphthenes forming aromatic hydrocarbons in a catalytic
Main article: alkylation unit reformer, have also been developed to increase the oc-
In a standard oil refinery process, isobutane is alkylated tane rating of gasoline. Modern refinery operation can
with low-molecular-weight alkenes (primarily a mixture be shifted to produce almost any fuel type with specified
of propene and butene) in the presence of a Bronsted acid performance criteria from a single crude feedstock.
catalyst, either sulfuric acid or hydrofluoric acid.[4] In an Refineries examine whether it makes sense economically
oil refinery it is referred to as a sulfuric acid alkylation to install alkylation units. Alkylation units are complex,
unit (SAAU) or a hydrofluoric alkylation unit, (HFAU). with substantial economy of scale. In addition to a suit-
Refinery workers may simply refer to it as the alky or able quantity of feedstock, the price spread between the
alky unit. The catalyst protonates the alkenes (propene, value of alkylate product and alternate feedstock disposi-
butene) to produce reactive carbocations, which alkylate tion value must be large enough to justify the installation.
50 CHAPTER 11. ALKYLATION
Alternative outlets for refinery alklylation feedstocks in- [2] Stefanidakis, G.; Gwyn, J.E. (1993). “Alkylation”. In
clude sales as LPG, blending of C4 streams directly into John J. McKetta. Chemical Processing Handbook. CRC
gasoline and feedstocks for chemical plants. Local mar- Press. pp. 80–138. ISBN 0-8247-8701-3.
ket conditions vary widely between plants. Variation in [3] G. S. Hiers and F. D. Hager (1941), “Anisole”, Org.
the RVP specification for gasoline between countries and Synth.; Coll. Vol. 1: 58
between seasons dramatically impacts the amount of bu-
tane streams that can be blended directly into gasoline. [4] Michael Röper, Eugen Gehrer, Thomas Narbeshuber,
The transportation of specific types of LPG streams can Wolfgang Siegel “Acylation and Alkylation” in Ull-
be expensive so local disparities in economic conditions mann’s Encyclopedia of Industrial Chemistry, Wiley-
are often not fully mitigated by cross market movements VCH, Weinheim, 2000. doi:10.1002/14356007.a01_185
of alkylation feedstocks. [5] Sulphur recovery; (2007). The Process Principles, de-
The availability of a suitable catalyst is also an important tails advances in sulphur recovery by the WSA process.
factor in deciding whether to build an alkylation plant. Denmark: Jens Kristen Laursen, Haldor Topsøe A/S.
Reprinted from Hydrocarbonengineering August 2007
If sulfuric acid is used, significant volumes are needed.
Access to a suitable plant is required for the supply of
fresh acid and the disposition of spent acid. If a sulfuric
acid plant must be constructed specifically to support an 11.6 External links
alkylation unit, such construction will have a significant
impact on both the initial requirements for capital and on- • Macrogalleria page on polycarbonate production
going costs of operation. Alternatively it is possible to in-
stall a WSA Process unit to regenerate the spent acid. No • Alkylating agents at the US National Library of
drying of the gas takes place. This means that there will Medicine Medical Subject Headings (MeSH)
be no loss of acid, no acidic waste material and no heat is
lost in process gas reheating. The selective condensation
in the WSA condenser ensures that the regenerated fresh
acid will be 98% w/w even with the humid process gas.
It is possible to combine spent acid regeneration with dis-
posal of hydrogen sulfide by using the hydrogen sulfide as
internal fuel in the refinery or elsewhere.[5]
The second main catalyst option is hydrofluoric acid. In
typical alkylation plants, rates of consumption for acid
are much lower than for sulfuric acid. These plants also
produce alkylate with better octane rating than do sulfuric
plants. However, due to its hazardous nature, HF acid is
produced at very few locations and transportation must be
managed rigorously.
• Transalkylation
• Friedel–Crafts reaction
• Category:Alkylating agents
• Category:Ethylating agents
• Category:Methylating agents
11.5 References
[1] March Jerry; (1985). Advanced Organic Chemistry re-
actions, mechanisms and structure (3rd ed.). New York:
John Wiley & Sons, inc. ISBN 0-471-85472-7
Chapter 12
Dimer (chemistry)
51
52 CHAPTER 12. DIMER (CHEMISTRY)
• Polymer
• Protein dimer
12.6 References
• “IUPAC “Gold Book” definition”. Retrieved 2009-
04-30.
Chapter 13
Isomerization
53
54 CHAPTER 13. ISOMERIZATION
• Epimerization
13.3 References
[1] IUPAC, Compendium of Chemical Terminology, 2nd ed.
(the “Gold Book”) (1997). Online corrected version:
(2006–) "isomerization".
Amine gas treating, also known as amine scrubbing, noethanolamine (MEA) denoted as RNH2 , the chemistry
gas sweetening and acid gas removal, refers to a may be expressed as:
group of processes that use aqueous solutions of various
alkylamines (commonly referred to simply as amines) to RNH2 + H2 S ⇔ RNH+
remove hydrogen sulfide (H2 S) and carbon dioxide (CO2 ) 3 + SH-
from gases.[1][2][3] It is a common unit process used
in refineries, and is also used in petrochemical plants, A typical amine gas treating process (as shown in the flow
natural gas processing plants and other industries. diagram below) includes an absorber unit and a regen-
Processes within oil refineries or chemical processing erator unit as well as accessory equipment. In the ab-
plants that remove hydrogen sulfide are referred to as sorber, the downflowing amine solution absorbs H2 S and
“sweetening” processes because the odor of the processed CO2 from the upflowing sour gas to produce a sweetened
products is improved by the absence of hydrogen sulfide. gas stream (i.e., a gas free of hydrogen sulfide and carbon
An alternative to the use of amines involves membrane dioxide) as a product and an amine solution rich in the
technology. However, membranes are less attractive absorbed acid gases. The resultant “rich” amine is then
since the relatively high capital and operation costs as well routed into the regenerator (a stripper with a reboiler) to
as other technical factors. [4] produce regenerated or “lean” amine that is recycled for
reuse in the absorber. The stripped overhead gas from the
Many different amines are used in gas treating: regenerator is concentrated H2 S and CO2 .
• Diethanolamine (DEA)
• Monoethanolamine (MEA)
• Methyldiethanolamine (MDEA)
• Diisopropanolamine (DIPA)
• Aminoethoxyethanol (Diglycolamine) (DGA)
14.1 Description of a typical amine Process flow diagram of a typical amine treating process used
treater in petroleum refineries, natural gas processing plants and other
industrial facilities.
55
56 CHAPTER 14. AMINE GAS TREATING
of an amine gas treating process. Depending on which of the 64,000,000 metric tons of sulfur produced world-
one of the following four amines the unit was designed to wide in 2005 was byproduct sulfur from refineries and
use and what gases it was designed to remove, these are other hydrocarbon processing plants.[6][7] Another sulfur-
some typical amine concentrations, expressed as weight removing process is the WSA Process which recovers sul-
percent of pure amine in the aqueous solution:[1] fur in any form as concentrated sulfuric acid. In some
plants, more than one amine absorber unit may share a
• Monoethanolamine: About 20 % for re- common regenerator unit. The current emphasis on re-
moving H2 S and CO2 , and about 32 % moving CO2 from the flue gases emitted by fossil fuel
for removing only CO2 . power plants has led to much interest in using amines for
• Diethanolamine: About 20 to 25 % for removing CO2 . (See also: Carbon capture and storage
removing H2 S and CO2 and Conventional coal-fired power plant.)
• Methyldiethanolamine: About 30 to 55% In the specific case of the industrial synthesis of
% for removing H2 S and CO2 ammonia, for the steam reforming process of hydrocar-
• Diglycolamine: About 50 % for remov- bons to produce gaseous hydrogen, amine treating is one
ing H2 S and CO2 of the commonly used processes for removing excess car-
bon dioxide in the final purification of the gaseous hydro-
The choice of amine concentration in the circulating gen.
aqueous solution depends upon a number of factors and
may be quite arbitrary. It is usually made simply on the
basis of experience. The factors involved include whether 14.4 See also
the amine unit is treating raw natural gas or petroleum
refinery by-product gases that contain relatively low con- • Ammonia production
centrations of both H2 S and CO2 or whether the unit • Hydrodesulfurization
is treating gases with a high percentage of CO2 such
as the offgas from the steam reforming process used • WSA Process
in ammonia production or the flue gases from power • Claus process
plants.[1]
• Selexol
Both H2 S and CO2 are acid gases and hence corrosive to
carbon steel. However, in an amine treating unit, CO2 is • Rectisol
the stronger acid of the two. H2 S forms a film of iron
• Amine
sulfide on the surface of the steel that acts to protect the
steel. When treating gases with a high percentage of CO2 , • Ionic liquids
corrosion inhibitors are often used and that permits the
• Solid sorbents for carbon capture
use of higher concentrations of amine in the circulating
solution.
Another factor involved in choosing an amine concentra- 14.5 References
tion is the relative solubility of H2 S and CO2 in the se-
lected amine.[1] The choice of the type of amine will af- [1] Arthur Kohl and Richard Nielson (1997). Gas Purification
fect the required circulation rate of amine solution, the (5th ed.). Gulf Publishing. ISBN 0-88415-220-0.
energy consumption for the regeneration and the ability
[2] Gary, J.H. and Handwerk, G.E. (1984). Petroleum Refin-
to selectively remove either H2 S alone or CO2 alone if
ing Technology and Economics (2nd ed.). Marcel Dekker,
desired. For more information about selecting the amine
Inc. ISBN 0-8247-7150-8.
concentration, the reader is referred to Kohl and Nielsen’s
book. [3] US 4080424, Loren N. Miller & Thomas S. Zawacki,
“Process for acid gas removal from gaseous mixtures”, is-
Activated MDEA or aMDEA uses piperazine as a catalyst sued 21 Mar 1978, assigned to Institute of Gas Technol-
to increase the speed of the reaction with CO2. It has ogy
been commercially successful.[5]
[4] Baker, R. W. “Future Directions of Membrane Gas Sepa-
ration Technology” Ind. Eng. Chem. Res. 2002, volume
41, pages 1393-1411. doi:10.1021/ie0108088
14.3 Uses
[5] “Piperazine – Why It’s Used and How It Works”. The
Contactor 2 (4). 2008. Retrieved 2013-10-23. |first1=
In oil refineries, that stripped gas is mostly H2 S, much missing |last1= in Authors list (help)
of which often comes from a sulfur-removing process
called hydrodesulfurization. This H2 S-rich stripped gas [6] Sulfur production report by the United States Geological
Survey
stream is then usually routed into a Claus process to con-
vert it into elemental sulfur. In fact, the vast majority [7] Discussion of recovered byproduct sulfur
14.6. EXTERNAL LINKS 57
Claus process
15.1 History
The process was invented by Carl Friedrich Claus, a
chemist working in England. A British patent was issued
to him in 1883. The process was later significantly mod-
Piles of sulfur produced in Alberta by the Claus process awaiting ified by a German company called IG Farben[6]
shipment at docks in Vancouver, Canada.
The Claus process is the most significant gas 15.2 Process description
desulfurizing process, recovering elemental sulfur
from gaseous hydrogen sulfide. First patented in 1883 by A schematic process flow diagram of a basic 2+1-reactor
the scientist Carl Friedrich Claus, the Claus process has (converter) SuperClaus unit is shown below:
become the industry standard.
The multi-step Claus process recovers sulfur from the
gaseous hydrogen sulfide found in raw natural gas and
from the by-product gases containing hydrogen sulfide
derived from refining crude oil and other industrial pro-
cesses. The by-product gases mainly originate from phys-
ical and chemical gas treatment units (Selexol, Rectisol,
Purisol and amine scrubbers) in refineries, natural gas
processing plants and gasification or synthesis gas plants.
These by-product gases may also contain hydrogen
cyanide, hydrocarbons, sulfur dioxide or ammonia. Schematic flow diagram of a straight-through, 3 reactor (con-
Gases with an H2 S content of over 25% are suitable for verter), Claus sulfur recovery unit.
the recovery of sulfur in straight-through Claus plants
The Claus technology can be divided into two process
while alternate configurations such as a split-flow set up
steps, thermal and catalytic.
or feed and air preheating can be used to process leaner
[1]
feeds.
Hydrogen sulfide produced, for example, in the hydro- 15.2.1 Thermal step
desulfurization of refinery naphthas and other petroleum
oils, is converted to sulfur in Claus plants.[2] The overall In the thermal step, hydrogen sulfide-laden gas reacts in a
main reaction equation is: substoichiometric combustion at temperatures above 850
°C [7] such that elemental sulfur precipitates in the down-
2 H2 S + O2 → 2 S + 2 H2 O stream process gas cooler.
The H2 S content and the concentration of other com-
In fact, the vast majority of the 64,000,000 metric tons bustible components (hydrocarbons or ammonia) deter-
of sulfur produced worldwide in 2005 was byproduct mine the location where the feed gas is burned. Claus
sulfur from refineries and other hydrocarbon processing gases (acid gas) with no further combustible contents
58
15.2. PROCESS DESCRIPTION 59
H2 S + CO2 → S=C=O + H2 O
The overall equation is:[5]
• Gas/gas exchangers: whereby the cooled gas from 15.3 Process performance
the process gas cooler is indirectly heated from the
hot gas coming out of an upstream catalytic reactor Using two catalytic stages, the process will typically yield
in a gas-to-gas exchanger. over 97% of the sulfur in the input stream. Over 2.6 tons
of steam will be generated for each ton of sulfur yield.
The physical properties of elemental sulfur obtained in
• Direct-fired heaters: fired reheaters utilizing acid the Claus process can differ from that obtained by other
gas or fuel gas, which is burned substoichiometri- processes.[5] Sulfur is usually transported as a liquid
cally to avoid oxygen breakthrough which can dam- (melting point 115 °C). In ordinary sulfur viscosity can
age Claus catalyst. increase rapidly at temperatures in excess of 160 °C due
to the formation of polymeric sulfur chains but not so in
Claus-sulfur. Another anomaly is found in the solubility
The typically recommended operating temperature of the of residual H2 S in liquid sulfur as a function of temper-
first catalyst stage is 315 °C to 330 °C (bottom bed tem- ature. Ordinarily the solubility of a gas decreases with
perature). The high temperature in the first stage also increasing temperature but now it is the opposite. This
helps to hydrolyze COS and CS2 , which is formed in means that toxic and explosive H2 S gas can build up in
the furnace and would not otherwise be converted in the the headspace of any cooling liquid sulfur reservoir. The
modified Claus process. explanation for this anomaly is the endothermic reaction
of sulfur with H2 S to polysulfane.
The catalytic conversion is maximized at lower temper-
atures, but care must be taken to ensure that each bed is
operated above the dew point of sulfur. The operating
temperatures of the subsequent catalytic stages are typi- 15.4 See also
cally 240 °C for the second stage and 200 °C for the third
stage (bottom bed temperatures). • Amine treating
In the sulfur condenser, the process gas coming from the • Hydro-desulfurization
catalytic reactor is cooled to between 150 and 130 °C.
The condensation heat is used to generate steam at the • Crystasulf
shell side of the condenser. • Hydrogenation
Before storage, liquid sulfur streams from the process gas
• Acid gas
cooler, the sulfur condensers and from the final sulfur sep-
arator are routed to the degassing unit, where the gases • Sour gas
(primarily H2 S) dissolved in the sulfur are removed.
The tail gas from the Claus process still containing com-
bustible components and sulfur compounds (H2 S, H2 and 15.5 References
CO) is either burned in an incineration unit or further
desulfurized in a downstream tail gas treatment unit. [1] Gas Processors Association Data Book, 10th Edition,
Volume II, Section 22
Hydrogen sulfide
Hydrogen sulfide is the chemical compound with the hydrogen sulfide in water, known as sulfhydric acid or
formula H hydrosulfuric acid, is initially clear but over time turns
2S. It is a colorless gas with the characteristic foul odor cloudy. This is due to the slow reaction of hydrogen sul-
of rotten eggs; it is heavier than air, very poisonous, cor-fide with the oxygen dissolved in water, yielding elemen-
rosive, flammable, and explosive. tal sulfur, which precipitates out. The sulfide dianion S2−
Hydrogen sulfide often results from the bacterial break- exists only in strongly alkaline aqueous solutions; it is ex-
ceptionally basic with a pKₐ > 14.
down of organic matter in the absence of oxygen gas,
such as in swamps and sewers; this process is commonly Hydrogen sulfide reacts with metal ions to form metal
known as anaerobic digestion. H sulfides, which may be considered the salts of hydrogen
2S also occurs in volcanic gases, natural gas, and in some sulfide. Some ores are sulfides. Metal sulfides often have
sources of well water. It is also present in natural halite a dark color. Lead(II) acetate paper is used to detect hy-
type rock salts, most notably in Himalayan Black Salt, drogen sulfide because it turns grey in the presence of the
which is mostly harvested from the mineral-rich “Salt gas as lead(II) sulfide is produced. Reacting metal sulfides
Range” mountains of Pakistan. The human body pro- with strong acid liberates hydrogen sulfide.
duces small amounts of H If gaseous hydrogen sulfide is put into contact with con-
2S and uses it as a signaling molecule. centrated nitric acid, it explodes.
Dissolved in water, hydrogen sulfide is known as hydro- Hydrogen sulfide reacts with alcohols to form thiols, an
sulfuric acid or sulfhydric acid, a weak acid.
important class of organosulfur compounds.
Swedish chemist Carl Wilhelm Scheele is credited with
having discovered hydrogen sulfide in 1777.
The British English spelling of this compound is hydro- 16.2 Production
gen sulphide, but this spelling is not recommended by the
International Union of Pure and Applied Chemistry nor Hydrogen sulfide is most commonly obtained by its sepa-
the Royal Society of Chemistry. ration from sour gas, which is natural gas with high con-
tent of H
2S. It can also be produced by reacting hydrogen gas with
16.1 Properties molten elemental sulfur at about 450 °C. Hydrocarbons
can replace hydrogen in this process.[7]
Hydrogen sulfide is slightly heavier than air; a mixture of Sulfate-reducing (resp. sulfur-reducing) bacteria gener-
H ate usable energy under low-oxygen conditions by using
2S and air is explosive. Hydrogen sulfide and oxygen burn sulfates (resp. elemental sulfur) to oxidize organic com-
with a blue flame to form sulfur dioxide (SO pounds or hydrogen; this produces hydrogen sulfide as a
2) and water. In general, hydrogen sulfide acts as a waste product.
reducing agent. The standard lab preparation is to react ferrous sulfide
At high temperature or in the presence of catalysts, sul- (FeS) with a strong acid in a Kipp generator:
fur dioxide can be made to react with hydrogen sulfide to
form elemental sulfur and water. This is exploited in the FeS + 2 HCl → FeCl2 + H2 S
Claus process, the main way to convert hydrogen sulfide
into elemental sulfur. A less well-known and more convenient alternative is to
[8]
Hydrogen sulfide is slightly soluble in water and acts as react aluminium sulfide with water:
a weak acid, giving the hydrosulfide ion HS− (pKₐ = 6.9
in 0.01-0.1 mol/litre solutions at 18 °C). A solution of 6 H2 O + Al2 S3 → 3 H2 S + 2 Al(OH)3
61
62 CHAPTER 16. HYDROGEN SULFIDE
This gas is also produced by heating sulfur with solid comes in contact with organic material, especially at high
organic compounds and by reducing sulfurated organic temperatures.
compounds with hydrogen. In 2011 it was reported that increased concentration of H
Hydrogen sulfide production can be costly because of the 2S, possibly due to oil field practices, was observed in
dangers involved in production. the Bakken formation crude and presented challenges
Water heaters can aid the conversion of sulfate in water to such as “health and environmental risks, corrosion of
wellbore, added expense with regard to materials han-
hydrogen sulfide gas. This is due to providing a warm en-
vironment sustainable for sulfur bacteria and maintaining dling and pipeline
[11]
equipment, and additional refinement
the reaction which interacts between sulfate in the water requirements”.
and the water heater anode, which is usually made from Besides living near a gas and oil drilling operations, ordi-
magnesium metal.[9] nary citizens can be exposed to hydrogen sulfide by being
near waste water treatment facilities, landfills and farms
with manure storage. Exposure occurs through breathing
16.3 Occurrence contaminated air or drinking contaminated water.[12]
16.4 Uses
Fe
2O 16.6 Removal from water
3(s) + H
2O(l) + 3 H
Hydrogen sulfide can be removed effectively from
2S(g) → Fe
drinking water and there are a number of processes de-
2S
signed for this purpose. However, the preferred method
3(s) + 4 H
can change according to the level of concentration in wa-
2O(l)
ter. Drinking water should be checked for hydrogen sul-
fide levels, especially if using ground water due to low
In order to regenerate iron(III) ox- dissolved oxygen levels.[16]
ide, the container must be taken out
of service, flooded with water and • Continuous Chlorination
aerated.
For levels up to 75 mg/L Chlorine is used in the pu-
2 Fe rification process as an oxidizing chemical to react with
2S hydrogen sulfide. This reaction yields insoluble solid
3(s) + 3 O sulfur. Usually the chlorine used is in the form of sodium
2(g) + 2 H hypochlorite.[17]
64 CHAPTER 16. HYDROGEN SULFIDE
Exposure to lower concentrations can result in eye irrita- • 800 ppm is the lethal concentration for 50% of hu-
tion, a sore throat and cough, nausea, shortness of breath, mans for 5 minutes exposure (LC50).
and fluid in the lungs (pulmonary edema).[20] These ef-
fects are believed to be due to the fact that hydrogen sul- • Concentrations over 1000 ppm cause immediate
fide combines with alkali present in moist surface tissues collapse with loss of breathing, even after inhalation
to form sodium sulfide, a caustic.[25] These symptoms of a single breath.
16.9. INVOLVEMENT IN DISEASES 65
16.7.2 Incidents ical signaling functions. (Only two other such gases are
currently known: nitric oxide (NO) and carbon monoxide
Hydrogen sulfide was used by the British Army as a chem- (CO).)
ical weapon during World War I. It was not considered to
The gas is produced from cysteine by the enzymes
be an ideal war gas, but, while other gases were in short
cystathionine beta-synthase and cystathionine gamma-
supply, it was used on two occasions in 1916.[31]
lyase. It acts as a relaxant of smooth muscle and as a
In 1975, a hydrogen sulfide release from an oil drilling vasodilator[40] and is also active in the brain, where it in-
operation in Denver City, Texas, killed nine people and creases the response of the NMDA receptor and facili-
caused the state legislature to focus on the deadly hazards tates long term potentiation,[41] which is involved in the
of the gas. State Representative E L Short took the lead formation of memory.
in endorsing an investigation by the Texas Railroad Com-
Eventually the gas is converted to sulfite in the
mission and urged that residents be warned “by knocking
mitochondria by thiosulfate reductase, and the sulfite is
on doors if necessary” of the imminent danger stemming
further oxidized to thiosulfate and sulfate by sulfite oxi-
from the gas. One may die from the second inhalation of
dase. The sulfates are excreted in the urine.[42]
the gas, and a warning itself may be too late.[32]
Due to its effects similar to nitric oxide (without its po-
A dump of toxic waste containing hydrogen sulfide is be-
tential to form peroxides by interacting with superoxide),
lieved to have caused 17 deaths and thousands of illnesses
hydrogen sulfide is now recognized as potentially protect-
in Abidjan, on the West African coast, in the 2006 Côte
ing against cardiovascular disease.[40] The cardioprotec-
d'Ivoire toxic waste dump.
tive role effect of garlic is caused by catabolism of the
In 2014, Levels of Hydrogen Sulfide as high as 83 ppm polysulfide group in allicin to H
have been detected at a recently built mall in Thailand 2S, a reaction that could depend on reduction mediated
called Siam Square One at the Siam Square area. Shop by glutathione.[43]
tenants at the mall reported health complications such as
Though both nitric oxide (NO) and hydrogen sulfide have
sinus inflammation, breathing difficulties and eye irrita-
been shown to relax blood vessels, their mechanisms
tion. After investigation it was determined that the large
of action are different: while NO activates the enzyme
amount of gas originated from imperfect treatment and
guanylyl cyclase, H
disposal of waste water in the building.[33]
2S activates ATP-sensitive potassium channels in smooth
In November 2014, a substantial amount of hydrogen sul- muscle cells. Researchers are not clear how the vessel-
fide gas shrouded the central, eastern and south-eastern relaxing responsibilities are shared between nitric oxide
parts of Moscow. Residents living in the area were urged and hydrogen sulfide. However there exists some evi-
to stay indoors by the emergencies ministry. Although the dence to suggest that nitric oxide does most of the vessel-
exact source of the gas was not known, blame had been relaxing work in large vessels and hydrogen sulfide is re-
placed on a Moscow oil refinery.[34] sponsible for similar action in smaller blood vessels.[44]
Recent findings suggest strong cellular crosstalk of NO
and H
16.7.3 Suicides
2S,[45] demonstrating that the vasodilatatory effects of
these two gases are mutually dependent. Additionally, H
The gas, produced by mixing certain household ingredi-
2S reacts with intracellular S-nitrosothiols to form the
ents, was used in a suicide wave in 2008 in Japan.[35] The
smallest S-nitrosothiol (HSNO), and a role of hydrogen
wave prompted staff at Tokyo’s suicide prevention center
sulfide in controlling the intracellular S-nitrosothiol pool
to set up a special hot line during "Golden Week", as they
has been suggested.[46]
received an increase in calls from people wanting to kill
themselves during the annual May holiday.[36] Like nitric oxide, hydrogen sulfide is involved in the re-
laxation of smooth muscle that causes erection of the
As of 2010, this phenomenon has occurred in a num-
penis, presenting possible new therapy opportunities for
ber of US cities, prompting warnings to those arriving
[37] erectile dysfunction.[47][48]
at the site of the suicide. These first responders, such
as emergency services workers or family members are at
risk of death from inhaling lethal quantities of the gas, or
by fire.[38][39] Local governments have also initiated cam- 16.9 Involvement in diseases
paigns to prevent such suicides.
16.9.1 Hydrogen sulfide deficiency after
heart attack
16.8 Function in the body
A hydrogen sulfide (H2S) deficiency can be detrimen-
Hydrogen sulfide is produced in small amounts by some tal to the vascular function after an acute myocardial in-
cells of the mammalian body and has a number of biolog- farction (AMI).[49] AMIs can lead to cardiac dysfunc-
66 CHAPTER 16. HYDROGEN SULFIDE
tion through two distinct changes; increased oxidative centration was found to be reduced, and administering
stress via free radical accumulation and decreased NO hydrogen sulfide alleviated the condition.[55] In trisomy
bioavailability.[50] Free radical accumulation occurs due 21 (Down syndrome) the body produces an excess of hy-
to increased electron transport uncoupling at the active drogen sulfide.[42] Hydrogen sulfide is also involved in the
site of endothelial nitric oxide synthase (eNOS), an en- disease process of type 1 diabetes. The beta cells of the
zyme involved in converting L-arginine to NO.[49][50] pancreas in type 1 diabetes produce an excess of the gas,
During an AMI, oxidative degradation of tetrahydro- leading to the death of these cells and to a reduced pro-
biopterin (BH4), a cofactor in NO production, limits BH4 duction of insulin by those that remain.[44]
availability and limits NO productionby eNOS.[50] In-
stead, eNOS reacts with oxygen, another cosubstrates in-
volved in NO production. The products of eNOS are re-
duced to superoxides, increasing free radical production
and oxidative stress within the cells.[49] A H2S deficiency 16.10 Induced hypothermia and
impairs eNOS activity by limiting Akt activation and in- suspended animation
hibiting Akt phosphorylation of the eNOSS1177 activa-
tion site.[49][51] Instead, Akt activity is increased to phos-
phorylate the eNOST495 inhibition site, downregulating In 2005, it was shown that mice can be put into a state of
eNOS production of NO.[49][51] suspended animation-like hypothermia by applying a low
dosage of hydrogen sulfide (81 ppm H
H2S therapy uses a H2S donor, such as diallyl trisulfide
2S) in the air. The breathing rate of the animals sank
(DATS), to increase the supply of H2S to an AMI pa-
from 120 to 10 breaths per minute and their temperature
tient. H2S donors reduce myocardial injury and reper-
fell from 37 °C to just 2 °C above ambient temperature
fusion complications.[49] Increased H2S levels within the
(in effect, they had become cold-blooded). The mice sur-
body will react with oxygen to produce sulfane sulfur, a
vived this procedure for 6 hours and afterwards showed
storage intermediate for H2S.[49] H2S pools in the body
no negative health consequences.[56] In 2006 it was shown
attracts oxygen to react with excess H2S and eNOS to
that the blood pressure of mice treated in this fashion with
increase NO production.[49] With increased use of oxy-
hydrogen sulfide did not significantly decrease.[57]
gen to produce more NO, less oxygen is available to re-
act with eNOS to produce superoxides during an AMI, A similar process known as hibernation occurs naturally
ultimately lowering the accumulation of reactive oxygen in many mammals and also in toads, but not in mice.
species (ROS).[49] Furthermore, decreased accumulation (Mice can fall into a state called clinical torpor when food
of ROS lowers oxidative stress in vascular smooth muscle shortage occurs). If the H
cells, decreasing oxidative degeneration of BH4.[50] In- 2S-induced hibernation can be made to work in hu-
creased BH4 cofactor contributes to increased production mans, it could be useful in the emergency management
of NO within the body.[50] Higher concentrations of H2S of severely injured patients, and in the conservation of
directly increase eNOS activity through Akt activation donated organs. In 2008, hypothermia induced by hydro-
to increase phosphorylation of the eNOSS1177 activa- gen sulfide for 48 hours was shown to reduce the extent of
tion site, and decrease phosphorylation of the eNOST495 brain damage caused by experimental stroke in rats.[58]
inhibition site.[49][51] This phosphorylation process up- As mentioned above, hydrogen sulfide binds to
regulates eNOS activity, catalyzing more conversion of cytochrome oxidase and thereby prevents oxygen
L-arginine to NO.[49][51] Increased NO production en- from binding, which leads to the dramatic slowdown
ables soluble guanylyl cyclase (sGC) activity, leading to of metabolism. Animals and humans naturally produce
an increased conversion of guanosine triphosphate (GTP) some hydrogen sulfide in their body; researchers have
to 3’,5’-cyclic guanosine monophosphate (cGMP).[52] In proposed that the gas is used to regulate metabolic
H2S therapy immediately following an AMI, increased activity and body temperature, which would explain the
cGMP triggers an increase in protein kinase G (PKG) above findings.[59]
activity.[53] PKG reduces intracellular Ca2+ in vascular
smooth muscle to increase smooth muscle relaxation and Two recent studies cast doubt that the effect can be
promote blood flow.[53] PKG also limits smooth mus- achieved in larger mammals. A 2008 study failed to re-
cle cell proliferation, reducing intima thickening follow- produce the effect in pigs, concluding that the effects seen
ing AMI injury, ultimately decreasing myocardial infarct in mice were not present in larger mammals.[60] Likewise
size.[49][52] a paper by Haouzi et al. noted that there is no induction
of hypometabolism in sheep, either.[61]
At the February 2010 TED conference, Mark Roth an-
16.9.2 Other diseases nounced that hydrogen sulfide induced hypothermia in
humans had completed Phase I clinical trials.[62] The clin-
In Alzheimer’s disease the brain’s hydrogen sulfide con- ical trials commissioned by the company he helped found,
centration is severely decreased.[54] In a certain rat model Ikaria, were however withdrawn or terminated by August
of Parkinson’s disease, the brain’s hydrogen sulfide con- 2011.[63][64]
16.12. MASS EXTINCTIONS 67
The purple sulfur bacteria and the green sulfur bacteria • Gasotransmitters
use hydrogen sulfide as electron donor in photosynthesis,
thereby producing elemental sulfur. (In fact, this mode of
photosynthesis is older than the mode of cyanobacteria, 16.14 References
algae, and plants, which uses water as electron donor and
liberates oxygen.) [1] “Hydrogen Sulfide - PubChem Public Chemical
68 CHAPTER 16. HYDROGEN SULFIDE
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[3] Bruckenstein, S.; Kolthoff, I.M., in Kolthoff, I.M.; Elving,
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94690-X. 2007). “Acute hydrogen sulfide poisoning in a
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[7] Jacques Tournier-Lasserve “Hydrogen Sulfide” in Ull- [23] Belley R, Bernard N, Côté M, Paquet F, Poitras J (July
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[8] McPherson, William (1913). Laboratory manual. nure”. CJEM 7 (4): 257–61. PMID 17355683. Retrieved
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70 CHAPTER 16. HYDROGEN SULFIDE
[58] Florian B, Vintilescu R, Balseanu AT, Buga A-M, Grisk 16.16 External links
O, Walker LC, Kessler C, Popa-Wagner A (2008). “Long-
term hypothermia reduces infarct volume in aged rats after • International Chemical Safety Card 0165
focal ischemia”. Neuroscience Letters 438 (2): 180–185.
doi:10.1016/j.neulet.2008.04.020. PMID 18456407. • Concise International Chemical Assessment Docu-
ment 53
[59] Mark B. Roth and Todd Nystul. Buying Time in Sus-
pended Animation. Scientific American, 1 June 2005 • National Pollutant Inventory - Hydrogen sulfide fact
sheet
[60] Li, Jia; Zhang, Gencheng; Cai, Sally; Redington,
Andrew N (January 2008). “Effect of inhaled hydro- • NIOSH Pocket Guide to Chemical Hazards
gen sulfide on metabolic responses in anesthetized,
paralyzed, and mechanically ventilated piglets”. • NACE (National Association of Corrosion Epal)
Pediatric Critical Care Medicine 9 (1): 110–112.
doi:10.1097/01.PCC.0000298639.08519.0C. PMID
18477923. Retrieved 2008-02-07. H2 S does not appear
to have hypometabolic effects in ambiently cooled
large mammals and conversely appears to act as a
hemodynamic and metabolic stimulant.
[66] “Impact From the Deep” in the October 2006 issue of Sci-
entific American.
Cooling tower
71
72 CHAPTER 17. COOLING TOWER
alent ton is defined as the heat rejection in cooling 3 US supplied to the plant. Furthermore, discharging large
gallons/minute (1,500 pound/hour) of water 10 °F (6 °C), amounts of hot water may raise the temperature of the
which amounts to 15,000 BTU/hour, assuming a chiller receiving river or lake to an unacceptable level for the lo-
coefficient of performance (COP) of 4.0. This COP is cal ecosystem. Elevated water temperatures can kill fish
equivalent to an energy efficiency ratio (EER) of 14. and other aquatic organisms (see thermal pollution), or
Cooling towers are also used in HVAC systems that have can also cause an increase in undesirable organisms such
multiple water source heat pumps that share a common as invasive species of Zebra mussels or algae. A cooling
piping water loop. In this type of system, the water cir- tower serves to dissipate the heat into the atmosphere in-
stead and wind and air diffusion spreads the heat over a
culating inside the water loop removes heat from the con-
denser of the heat pumps whenever the heat pumps are much larger area than hot water can distribute heat in a
body of water. Some coal-fired and nuclear power plants
working in the cooling mode, then the externally mounted
cooling tower is used to remove heat from the water loop located in coastal areas do make use of once-through
ocean water. But even there, the offshore discharge water
and reject it to the atmosphere. By contrast, when the
heat pumps are working in heating mode, the condensers outlet requires very careful design to avoid environmental
problems.
draw heat out of the loop water and reject it into the space
to be heated. When the water loop is being used pri- Petroleum refineries also have very large cooling tower
marily to supply heat to the building, the cooling tower systems. A typical large refinery processing 40,000 met-
is normally shut down (and may be drained or winterized ric tonnes of crude oil per day (300,000 barrels (48,000
to prevent freeze damage), and heat is supplied by other m3 ) per day) circulates about 80,000 cubic metres of wa-
means, usually from separate boilers. ter per hour through its cooling tower system.
The world’s tallest cooling tower is the 202 metres (663
ft) tall cooling tower of Kalisindh Thermal Power Plant
17.2.2 Industrial cooling towers in Jhalawar, Rajasthan, India.[12]
17.3.1 Package type is drawn past a flow of water, a small portion of the wa-
ter evaporates, and the energy required to evaporate that
This type of cooling towers are factory preassembled, and portion of the water is taken from the remaining mass of
can be simply transported on trucks as they are compact water, thus reducing its temperature. Approximately 970
machines. The capacity of package type towers is limited BTU of heat energy is absorbed for each pound of evap-
and for that reason, they are usually preferred by facilities orated water. Evaporation results in saturated air condi-
with low heat rejection requirements such as food pro- tions, lowering the temperature of the water processed by
cessing plants, textile plants, some chemical processing the tower to a value close to wet-bulb temperature, which
plants, or buildings like hospitals, hotels, malls, automo- is lower than the ambient dry-bulb temperature, the dif-
tive factories etc. ference determined by the initial humidity of the ambient
air.
Due to their frequent use in or near residential areas,
sound level control is a relatively more important issue To achieve better performance (more cooling), a medium
for package type cooling towers. called fill is used to increase the surface area and the time
of contact between the air and water flows. Splash fill
consists of material placed to interrupt the water flow
17.3.2 Field erected type causing splashing. Film fill is composed of thin sheets
of material (usually PVC) upon which the water flows.
Facilities such as power plants, steel processing plants, Both methods create increased surface area and time of
petroleum refineries, or petrochemical plants usually in- contact between the fluid (water) and the gas (air), to im-
stall field erected type cooling towers due to their greater prove heat transfer.
capacity for heat rejection. Field erected towers are usu-
ally much larger in size compared to the package type
cooling towers.
17.5 Air flow generation methods
A typical field erected cooling tower has a pultruded fiber-
reinforced plastic (FRP) structure, FRP cladding, a me-
chanical unit for air draft, drift eliminator, and fill.
• wet cooling towers (or open circuit cooling tow- Access stairs at the base of a massive hyperboloid cooling tower
ers) operate on the principle of evaporative cooling. give a sense of its scale (UK)
The working fluid and the evaporated fluid (usually
water) are one and the same. With respect to drawing air through the tower, there are
three types of cooling towers:
• fluid coolers (or closed circuit cooling towers) are
hybrids that pass the working fluid through a tube • Natural draft — Utilizes buoyancy via a tall chim-
bundle, upon which clean water is sprayed and a fan- ney. Warm, moist air naturally rises due to the den-
induced draft applied. The resulting heat transfer sity differential compared to the dry, cooler outside
performance is much closer to that of a wet cooling air. Warm moist air is less dense than drier air at the
tower, with the advantage provided by a dry cooler same pressure. This moist air buoyancy produces an
of protecting the working fluid from environmental upwards current of air through the tower.
exposure and contamination.
• Mechanical draft — Uses power-driven fan motors
In a wet cooling tower (or open circuit cooling tower), the to force or draw air through the tower.
warm water can be cooled to a temperature lower than the
ambient air dry-bulb temperature, if the air is relatively • Induced draft — A mechanical draft tower
dry (see dew point and psychrometrics). As ambient air with a fan at the discharge (at the top) which
17.6. CATEGORIZATION BY AIR-TO-WATER FLOW 75
pulls air up through the tower. The fan in- Warm, moist
air out Fan
duces hot moist air out the discharge. This pro- Hot water in
duces low entering and high exiting air veloc-
ities, reducing the possibility of recirculation
Distribution basin
in which discharged air flows back into the air
Dry air in
intake. This fan/fin arrangement is also known
as draw-through.
• Forced draft — A mechanical draft tower Fill material
with a blower type fan at the intake. The fan Cold water out
Collection basin
forces air into the tower, creating high enter-
ing and low exiting air velocities. The low ex-
iting velocity is much more susceptible to re-
circulation. With the fan on the air intake, the
fan is more susceptible to complications due
to freezing conditions. Another disadvantage
is that a forced draft design typically requires
more motor horsepower than an equivalent in-
duced draft design. The benefit of the forced
draft design is its ability to work with high
static pressure. Such setups can be installed
in more-confined spaces and even in some in-
door situations. This fan/fill geometry is also
known as blow-through.
Hyperboloid (sometimes incorrectly known as Mechanical draft crossflow cooling tower used in an HVAC ap-
hyperbolic) cooling towers have become the design plication
standard for all natural-draft cooling towers because of
their structural strength and minimum usage of material. A distribution or hot water basin consisting of a deep pan
The hyperboloid shape also aids in accelerating the up- with holes or nozzles in its bottom is located near the
ward convective air flow, improving cooling efficiency. top of a crossflow tower. Gravity distributes the water
These designs are popularly associated with nuclear through the nozzles uniformly across the fill material.
power plants. However, this association is misleading,
as the same kind of cooling towers are often used at Advantages of the crossflow design:
large coal-fired power plants as well. Conversely, not
all nuclear power plants have cooling towers, and some • Gravity water distribution allows smaller pumps and
instead cool their heat exchangers with lake, river or maintenance while in use.
ocean water. • Non-pressurized spray simplifies variable flow.
• Typically lower initial and long-term cost, mostly
due to pump requirements.
17.6 Categorization by air-to-
water flow Disadvantages of the crossflow design:
Warm, moist • The air, now saturated with water vapor, is dis-
air out charged from the top of the cooling tower.
Fan
Hot water in
Distribution system • A collection or cold water basin is used to collect and
Spray nozzles contain the cooled water after its interaction with the
air flow.
Fill material
17.6.3 Common aspects Since the evaporated water (E) has no salts, a chloride
balance around the system is:[14]
Common aspects of both designs:
XC M M Relationship between
E cycles of concentration and flow rates in a
= concentration of Cycles = = = 1+
XM (D + W ) (M − E)
cooling tower
(D + W )
From a simplified heat balance around the cooling tower: As the cycles of concentration increase, the water may
not be able to hold the minerals in solution. When the
solubility of these minerals have been exceeded they can
C∆T cp precipitate out as mineral solids and cause fouling and
E= heat exchange problems in the cooling tower or the heat
HV
exchangers. The temperatures of the recirculating wa-
Windage (or drift) losses (W) is the amount of total tower ter, piping and heat exchange surfaces determine if and
water flow that is evaporated into the atmosphere. From where minerals will precipitate from the recirculating
large-scale industrial cooling towers, in the absence of water. Often a professional water treatment consultant
manufacturer’s data, it may be assumed to be: will evaluate the make-up water and the operating condi-
tions of the cooling tower and recommend an appropriate
range for the cycles of concentration. The use of water
W = 0.3 to 1.0 percent of C for a natural draft treatment chemicals, pretreatment such as water soften-
cooling tower without windage drift elimina- ing, pH adjustment, and other techniques can affect the
tors acceptable range of cycles of concentration.
W = 0.1 to 0.3 percent of C for an induced Concentration cycles in the majority of cooling towers
draft cooling tower without windage drift elim- usually range from 3 to 7. In the United States, many wa-
inators ter supplies use well water which has significant levels of
dissolved solids. On the other hand, one of the largest wa-
W = about 0.005 percent of C (or less) if the ter supplies, for New York City, has a surface rainwater
cooling tower has windage drift eliminators source quite low in minerals; thus cooling towers in that
W = about 0.0005 percent of C (or less) if city are often allowed to concentrate to 7 or more cycles
the cooling tower has windage drift eliminators of concentration.
and uses sea water as make-up water. Since higher cycles of concentration represent less make-
78 CHAPTER 17. COOLING TOWER
up water, water conservation efforts may focus on in- French researchers found that Legionella bacteria trav-
creasing cycles of concentration.[15] Highly treated recy- elled up to 6 kilometres (3.7 mi) through the air from a
cled water may be an effective means of reducing cool- large contaminated cooling tower at a petrochemical plant
ing tower consumption of potable water, in regions where in Pas-de-Calais, France. That outbreak killed 21 of the
potable water is scarce.[16] 86 people who had a laboratory-confirmed infection.[19]
Drift (or windage) is the term for water droplets of the
process flow allowed to escape in the cooling tower dis-
17.7.2 Water treatment charge. Drift eliminators are used in order to hold drift
rates typically to 0.001–0.005% of the circulating flow
See also: Industrial water treatment rate. A typical drift eliminator provides multiple direc-
tional changes of airflow to prevent the escape of water
Besides treating the circulating cooling water in large in- droplets. A well-designed and well-fitted drift eliminator
dustrial cooling tower systems to minimize scaling and can greatly reduce water loss and potential for Legionella
fouling, the water should be filtered to remove particu- or water treatment chemical exposure.
lates, and also be dosed with biocides and algaecides to Many governmental agencies, cooling tower manufactur-
prevent growths that could interfere with the continuous ers and industrial trade organizations have developed de-
flow of the water.[13] Under certain conditions, a biofilm sign and maintenance guidelines for preventing or con-
of micro-organisms such as bacteria, fungi and algae can trolling the growth of Legionella in cooling towers. Below
grow very rapidly in the cooling water, and can reduce is a list of sources for such guidelines:
the heat transfer efficiency of the cooling tower. Biofilm
can be reduced or prevented by using chlorine or other
• Centers for Disease Control and Prevention (CDC)
chemicals.
PDF (1.35 MB) - Procedure for Cleaning Cooling
Towers and Related Equipment (pages 225 and 226)
• Cooling Technology Institute PDF (240 KB) - Best
17.8 Legionnaires’ disease Practices for Control of Legionella, July, 2006
• Association of Water Technologies PDF (964 KB)
- Legionella 2003: An Update and Statement
• California Energy Commission PDF (194 KB) -
Cooling Water Management Program Guidelines
For Wet and Hybrid Cooling Towers at Power Plants
• SPX Cooling Technologies PDF (119 KB) - Cooling
Towers Maintenance Procedures
• SPX Cooling Technologies PDF (789 KB) -
ASHRAE Guideline 12-2000 - Minimizing the Risk
of Legionellosis
• SPX Cooling Technologies PDF (83.1 KB) - Cool-
Legionella pneumophila (5000x magnification) ing Tower Inspection Tips {especially page 3 of 7}
• Tower Tech Modular Cooling Towers PDF (109
Further information: Legionellosis and Legionella KB) - Legionella Control
• GE Infrastructure Water & Process Technologies
Another very important reason for using biocides in cool-
Betz Dearborn PDF (195 KB) - Chemical Wa-
ing towers is to prevent the growth of Legionella, includ-
ter Treatment Recommendations For Reduction of
ing species that cause legionellosis or Legionnaires’ dis-
Risks Associated with Legionella in Open Recircu-
ease, most notably L. pneumophila,[17] or Mycobacterium
lating Cooling Water Systems
avium.[18] The various Legionella species are the cause
of Legionnaires’ disease in humans and transmission is
via exposure to aerosols—the inhalation of mist droplets
containing the bacteria. Common sources of Legionella 17.9 Terminology
include cooling towers used in open recirculating evapo-
rative cooling water systems, domestic hot water systems, • Windage or Drift — Water droplets that are carried
fountains, and similar disseminators that tap into a public out of the cooling tower with the exhaust air. Drift
water supply. Natural sources include freshwater ponds droplets have the same concentration of impurities
and creeks. as the water entering the tower. The drift rate is
17.9. TERMINOLOGY 79
filter the cooling tower basin water at a rate equiva- adds more water to the air, saturated air with liquid wa-
lent to 10% of the total circulation flow rate. For ex- ter droplets can be discharged, which is seen as fog. This
ample, if the total flow of a system is 1,200 gal/min phenomenon typically occurs on cool, humid days, but is
(a 400-ton system), a 120 gal/min side-stream sys- rare in many climates.
tem is specified. This phenomenon can be prevented by decreasing the
• Cycle of concentration — Maximum allowed mul- relative humidity of the saturated discharge air. For
tiplier for the amount of miscellaneous substances in that purpose, in hybrid towers, saturated discharge air
circulating water compared to the amount of those is mixed with heated low relative humidity air. Some
substances in make-up water. air enters the tower above drift eliminator level, passing
through heat exchangers. The relative humidity of the
• Treated timber — A structural material for cooling dry air is even more decreased instantly as being heated
towers which was largely abandoned about 10 years while entering the tower. The discharged mixture has a
ago. It is still used occasionally due to its low initial relatively lower relative humidity and the fog is invisible.
costs, in spite of its short life expectancy. The life of
treated timber varies a lot, depending on the oper-
ating conditions of the tower, such as frequency of
shutdowns, treatment of the circulating water, etc. 17.11 Salt emission pollution
Under proper working conditions, the estimated life
of treated timber structural members is about 10 When wet cooling towers with seawater make-up are in-
years. stalled in various industries located in or near coastal ar-
eas, the drift of fine droplets emitted from the cooling
• Leaching — The loss of wood preservative chem- towers contain nearly 6% sodium chloride which deposits
icals by the washing action of the water flowing on the nearby land areas. This deposition of sodium
through a wood structure cooling tower. salts on the nearby agriculture/vegetative lands can con-
• Pultruded FRP — A common structural mate- vert them into sodic saline or sodic alkaline soils depend-
rial for smaller cooling towers, fibre-reinforced plas- ing on the nature of the soil. The salt deposition prob-
tic (FRP) is known for its high corrosion-resistance lem from such cooling towers aggravates where national
capabilities. Pultuded FRP is produced using pollution control standards are not imposed or not imple-
pultrusion technology, and has become the most mented to minimize the drift emissions from wet cooling
[20]
common structural material for small cooling tow- towers using seawater make-up.
ers. It offers lower costs and requires less main- Respirable suspended particulate matter, of less than 10
tenance compared to reinforced concrete, which is micrometers (µm) in size, can be present in the drift from
still in use for large structures. cooling towers. Larger particles above 10 µm in size are
generally filtered out in the nose and throat via cilia and
mucus but particulate matter smaller than 10 µm, referred
17.10 Fog production to as PM10 , can settle in the bronchi and lungs and cause
health problems. Similarly, particles smaller than 2.5
µm, (PM₂.₅), tend to penetrate into the gas exchange re-
gions of the lung, and very small particles (less than 100
nanometers) may pass through the lungs to affect other
organs. Though the total particulate emissions from wet
cooling towers with fresh water make-up is much less,
they contain more PM10 and PM₂.₅ than the total emis-
sions from wet cooling towers with sea water make-up.
This is due to lesser salt content in fresh water drift (be-
low 2,000 ppm) compared to the salt content of sea water
drift (60,000 ppm).[20]
Fog clouds produced by Eggborough Power Plant (UK) At some modern power stations equipped with flue
gas purification, such as the Power Station Staudinger
Under certain ambient conditions, plumes of water va- Grosskrotzenburg and the Power Station Rostock, the
por (fog) can be seen rising out of the discharge from a cooling tower is also used as a flue-gas stack (industrial
cooling tower, and can be mistaken as smoke from a fire. chimney), thus saving the cost of a separate chimney
If the outdoor air is at or near saturation, and the tower structure. At plants without flue gas purification, prob-
17.13. OPERATION IN FREEZING WEATHER 81
lems with corrosion may occur, due to reactions of raw • Do not operate the tower without a heat load. Basin
flue gas with water to form acids. heaters may be used to keep the water in the tower
pan at an above-freezing temperature. Heat trace
Sometimes, natural draft cooling towers are constructed
(“heating tape”) is a resistive heating element that
with structural steel in place of concrete (RCC) when the
is installed along water pipes to prevent freezing in
construction time of natural draft cooling tower is ex-
cold climates .
ceeding the construction time of the rest of the plant or
the local soil is of poor strength to bear the heavy weight • Maintain design water flow rate over the tower fill.
of RCC cooling towers or cement prices are higher at a
site to opt for cheaper natural draft cooling towers made • Manipulate or reduce airflow to maintain water tem-
of structural steel. perature above freezing point.[22]
82 CHAPTER 17. COOLING TOWER
• Spray pond
Cooling towers constructed in whole or in part of com-
bustible materials can support internal fire propagation. • Water cooling
Such fires can become very intense, due to the high
surface-volume ratio of the towers, and fires can be • Willow Island disaster
further intensified by natural convection or fan-assisted
draft. The resulting damage can be sufficiently severe
to require the replacement of the entire cell or tower 17.17 References
structure. For this reason, some codes and standards[23]
recommend that combustible cooling towers be provided [1] CleanEnergy Footprints (cleanenergy.org). Identifying
with an automatic fire sprinkler system. Fires can prop- Nuclear Reactors in Google Earth Retrieved 5/19/2014
agate internally within the tower structure when the cell
is not in operation (such as for maintenance or construc- [2] International Correspondence Schools (1902). A Text-
tion), and even while the tower is in operation, especially book on Steam Engineering. Scranton, Pa.: International
those of the induced-draft type, because of the existence Textbook Co. 33-34 of Section 29:"Condensers”.
of relatively dry areas within the towers.[24] [3] Terrell Croft, ed. (1922). Steam-Engine Principles and
Practice. New York: McGraw-Hill. pp. 283–286.
17.15 Structural stability [4] Heck, Robert Culbertson Hays (1911). The Steam Engine
and Turbine: A Text-Book for Engineering Colleges. New
York: D. Van Nostrand. pp. 569–570.
Being very large structures, cooling towers are suscepti-
ble to wind damage, and several spectacular failures have [5] “Power plant and allied industries”. The Engineer (with
occurred in the past. At Ferrybridge power station on Which is Incorporated Steam Engineering) (Chicago: Tay-
1 November 1965, the station was the site of a major lor Publishing Co.) 43 (1): 69–72. 1 Jan 1906.
structural failure, when three of the cooling towers col- [6] Snow, Walter B. (1908). The Steam Engine: A Practical
lapsed owing to vibrations in 85 mph (137 km/h) winds. Guide to the Construction, Operation, and care of Steam
Although the structures had been built to withstand higher Engines, Steam Turbines, and Their Accessories. Chicago:
wind speeds, the shape of the cooling towers caused west- American School of Correspondence. pp. 43–46.
erly winds to be funnelled into the towers themselves, cre-
ating a vortex. Three out of the original eight cooling tow- [7] UK Patent No. 108,863
ers were destroyed, and the remaining five were severely [8] “Power Plant Cooling Towers Like Big Milk Bottle” Pop-
damaged. The towers were later rebuilt and all eight cool- ular Mechanics, February 1930 bottom-left of pg 201
ing towers were strengthened to tolerate adverse weather
conditions. Building codes were changed to include im- [9] U.S. Environmental Protection Agency (EPA).
proved structural support, and wind tunnel tests were in- (1997). Profile of the Fossil Fuel Electric Power
troduced to check tower structures and configuration. Generation Industry (Report). Washington, D.C.
http://www.epa.gov/compliance/resources/publications/
assistance/sectors/notebooks/fossil.html. Document No.
EPA/310-R-97-007. p. 79.
17.16 See also
[10] Cooling System Retrofit Costs EPA Workshop on Cooling
Water Intake Technologies, John Maulbetsch, Maulbetsch
• Alkali soils
Consulting, May 2003
• Architectural engineering [11] Thomas J. Feeley, III, Lindsay Green, James T. Mur-
phy, Jeffrey Hoffmann, and Barbara A. Carney (2005).
• Deep lake water cooling
“Department of Energy/Office of Fossil Energy’s Power
• Evaporative cooler Plant Water Management R&D Program.” U.S. Depart-
ment of Energy, July 2005.
• Evaporative cooling
[12] Comansa Jie builds the world’s highest cooling towers
• Fossil fuel power plant
[13] Beychok, Milton R. (1967). Aqueous Wastes from
• Heating, ventilating and air conditioning Petroleum and Petrochemical Plants (1st Edition ed.).
John Wiley and Sons. LCCN 67019834. (available in
• Hyperboloid structure many university libraries)
[21] http://spxcooling.com/library/detail/
cooling-tower-fundamentals SPX Cooling Tech-
nologies MARLEY, Cooling Tower Fundamentals Page
73 (75 of 119) Column 2, Last Paragraph
Steam
For the software distribution platform, see Steam (soft- Superheated steam is steam at a temperature higher than
ware). For other uses, see Steam (disambiguation). its boiling point for the pressure, which only occurs where
all liquid water has evaporated or has been removed from
the system.[5]
Steam is the technical term for the gaseous phase of
water, which is formed when water boils. Technically Steam tables [6] contain thermodynamic data for wa-
speaking, in terms of the chemistry and physics, steam ter/steam and are often used by engineers and scientists
is invisible and cannot be seen; however, in common lan- in design and operation of equipment where thermody-
guage it is often used to refer to the visible mist or aerosol namic cycles involving steam are used. Additionally,
of water droplets formed as this water vapor condenses in thermodynamic phase diagrams for water/steam, such
the presence of (cooler) air. At lower pressures, such as in as a temperature-entropy diagram or a Mollier diagram
the upper atmosphere or at the top of high mountains wa- shown in this article, may be useful. Steam charts are
ter boils at a lower temperature than the nominal 100 °C also used for analysing thermodynamic cycles.
(212 °F) at standard temperature and pressure. If heated
further it becomes superheated steam.
The enthalpy of vaporization is the energy required to 18.2 Uses
turn water into the gaseous form when it increases in
volume by 1,700 times at standard temperature and 18.2.1 Agricultural
pressure; this change in volume can be converted into
mechanical work by steam engines such as reciprocating In agriculture, steam is used for soil sterilization to avoid
piston type engines and steam turbines, which are a sub- the use of harmful chemical agents and increase soil
group of steam engines. Piston type steam engines played health.
a central role to the Industrial Revolution and modern
steam turbines are used to generate more than 80% of
the world’s electricity. If liquid water comes in contact 18.2.2 Domestic
with a very hot substance (such as lava, or molten metal)
it can create a steam explosion. Steam explosions have Steam’s capacity to transfer heat is also used in the home:
been responsible for many foundry accidents, and may for cooking vegetables, steam cleaning of fabric and car-
also have been responsible for much of the damage to the pets, and heating buildings. In each case, water is heated
plant in the Chernobyl disaster. in a boiler, and the steam carries the energy to a target ob-
ject. "Steam showers" are actually low-temperature mist-
generators, and do not actually use steam.
18.1 Types of steam and conver- 18.2.3 Electricity generation (and cogener-
sion ation)
Steam is traditionally created by heating a boiler via burn- About 90% of all electricity is generated using steam as
ing coal and other fuels, but it is also possible to create the working fluid, nearly all by steam turbines.[7]
steam with solar energy.[1][2][3] Water vapor that includes In electric generation, steam is typically condensed at the
water droplets is described as wet steam. As wet steam end of its expansion cycle, and returned to the boiler for
is heated further, the droplets evaporate, and at a high re-use. However in cogeneration, steam is piped into
enough temperature (which depends on the pressure) all buildings through a district heating system to provide
of the water evaporates and the system is in vapor–liquid heat energy after its use in the electric generation cy-
equilibrium.[4] cle. The world’s biggest steam generation system is the
84
18.3. SEE ALSO 85
New York City steam system, which pumps steam into work. The ability to return condensed steam as water-
100,000 buildings in Manhattan from seven cogeneration liquid to the boiler at high pressure with relatively little ex-
plants.[8] penditure of pumping power is important. Condensation
of steam to water often occurs at the low-pressure end
of a steam turbine, since this maximizes the energy ef-
18.2.4 Energy storage ficiency, but such wet-steam conditions must be limited
to avoid excessive turbine blade erosion. Engineers use
an idealised thermodynamic cycle, the Rankine cycle, to
model the behavior of steam engines. Steam turbines are
often used in the production of electricity.
18.2.7 Sterilization
An autoclave, which uses steam under pressure, is used
in microbiology laboratories and similar environments for
sterilization.
Steam, especially dry (highly superheated) steam, may be
used for antimicrobial cleaning even to the levels of ster-
ilization. Steam is a non-toxic antimicrobial agent.[10] [11]
• Live steam
• Mass production
• Nuclear power—and power plants use steam to gen-
erate electricity
• Oxyhydrogen
• Psychrometrics—moist air/vapor mixtures, humidity
and air conditioning
• Steam locomotive
18.4 References
[1] Taylor, Robert A.; Phelan, Patrick E.; Adrian, Ronald J.;
Gunawan, Andrey; Otanicar, Todd P. (2012). “Charac-
terization of light-induced, volumetric steam generation
in nanofluids”. International Journal of Thermal Sciences
56: 1–11. doi:10.1016/j.ijthermalsci.2012.01.012.
Boiler
87
88 CHAPTER 19. BOILER
19.3 Configurations
Boilers can be classified into the following configurations:
• Fire-tube boiler with Water-tube firebox. Some- • Easy adjustment of air / fuel ratio
times the two above types have been combined • Suitability of components for specific fuel charac-
in the following manner: the firebox contains an teristics
assembly of water tubes, called thermic siphons.
The gases then pass through a conventional firetube • Low power consumption and preheating of air
boiler. Water-tube fireboxes were installed in many
Hungarian locomotives, but have met with little suc- • Provision for various safety interlocks
cess in other countries.
Types of burners Based on mode of atomisation 1. Pres-
• Sectional boiler. In a cast iron sectional boiler, sure jet 2. Rotary cup
sometimes called a “pork chop boiler” the water is
contained inside cast iron sections. These sections Type of modulation 1. High / low 2. 3 stage modulation
are assembled on site to create the finished boiler. 3. Stepless modulation
Based on fuel fired 1. Gas fired 2. Oil fired 3. Dual fired
Also Boilers can be classified as Package Boiler Based on construction 1. Monoblock 2. Dual block
• The package boiler is so called because it comes as a Based on Air to Fuel Ratio Control 1. Linkage Type/ Me-
complete package. Once delivered to site it requires only chanical Compound Regulation 2. Electronic Compound
the steam, water pipe work, fuel supply and electrical con- Regulation
nections to be made for it to become operational.
• What is not a Package Boiler - When work needs to be
done at site, which is classified under “erection”: 19.4 Safety
19.5.1 Supercritical steam generator ically by way of radiators, baseboard heaters or through
the floors. The fluid can be heated by any means...gas,
wood, fuel oil, etc., but in built-up areas where piped gas
is available, natural gas is currently the most economical
and therefore the usual choice. The fluid is in an enclosed
system and circulated throughout by means of a pump.
The name “boiler” can be a misnomer in that, except for
systems using steam radiators, the water in a properly
functioning hydronic boiler never actually boils. Some
new systems are fitted with condensing boilers for greater
efficiency. These boilers are referred to as condensing
boilers because they are designed to extract the heat of
vaporization of the flue gas water vapor. As a result of
the lower flue gas temperatures, flue gas water vapor con-
denses to liquid and with dissolved carbon dioxide forms
carbonic acid. The carbonic acid would damage a typi-
cal boiler by corroding the flue and fireside boiler heating
surfaces. Condensing boilers solve this problem by rout-
ing the carbonic acid down a drain and by making the
flue exposed to the corrosive flue gas of stainless steel or
PVC. Although condensing boilers are becoming more
Boiler for a power plant.
popular, they are still less common than other types of
hydronic boilers as they are more expensive.
Main article: Supercritical steam generator
Hydronic systems are being used more and more in
new construction in North America for several reasons.
Supercritical steam generators are frequently used for the
Among those are:
production of electric power. They operate at supercrit-
ical pressure. In contrast to a “subcritical boiler”, a su-
percritical steam generator operates at such a high pres- • They are more efficient and more economical than
sure (over 3,200 psi or 22 MPa) that the physical tur- forced-air systems (although initial installation can
bulence that characterizes boiling ceases to occur; the be more expensive, because of the cost of the copper
fluid is neither liquid nor gas but a super-critical fluid. and aluminum).
There is no generation of steam bubbles within the water,
• The baseboard copper pipes and aluminum fins take
because the pressure is above the critical pressure point
up less room and use less metal than the bulky steel
at which steam bubbles can form. As the fluid expands
ductwork required for forced-air systems.
through the turbine stages, its thermodynamic state drops
below the critical point as it does work turning the tur- • They provide more even, less fluctuating temper-
bine which turns electrical generator from which power atures than forced-air systems. The copper base-
is ultimately extracted. The fluid at that point may be board pipes hold and release heat over a longer pe-
a mix of steam and liquid droplets as it passes into the riod of time than air does, so the furnace does not
condenser. This results in slightly less fuel use and there- have to switch off and on as much. (Hydronic sys-
fore less greenhouse gas production. The term “boiler” tems heat mostly through conduction and radiation,
should not be used for a supercritical pressure steam gen- whereas forced-air heats mostly through forced con-
erator, as no “boiling” actually occurs in this device. vection. Air has much lower thermal conductivity
and volumetric heat capacity than copper, so the
conditioned space warms up and cools down more
19.6 Hydronic boilers quickly than with hydronic. See also thermal mass.)
Forced-air heating does have some advantages, however. • Low- water cutoff: It is a mechanical means (usu-
See forced-air heating. ally a float switch) that is used to turn off the burner
or shut off fuel to the boiler to prevent it from run-
ning once the water goes below a certain point. If
19.7 Accessories a boiler is “dry-fired” (burned without water in it) it
can cause rupture or catastrophic failure.
19.7.1 Boiler fittings and accessories • Surface blowdown line: It provides a means for re-
moving foam or other lightweight non-condensible
• Pressuretrols to control the steam pressure in the substances that tend to float on top of the water in-
boiler. Boilers generally have 2 or 3 pressuretrols: side the boiler.
An manual-reset pressuretrol, which functions as a
safety by setting the upper limit of steam pressure, • Circulating pump: It is designed to circulate water
the Operating pressuretrol, which controls when the back to the boiler after it has expelled some of its
boiler fires to maintain pressure, and for boilers heat.
equipped with a modulating burner, a modulating • Feedwater check valve or clack valve: A non-
pressuretrol which controls the amount of fire. return stop valve in the feedwater line. This may be
• Safety valve: It is used to relieve pressure and pre- fitted to the side of the boiler, just below the water
vent possible explosion of a boiler. level, or to the top of the boiler.[7]
• Water level indicators: They show the operator the • Top feed: In this design for feedwater injection, the
level of fluid in the boiler, also known as a sight glass, water is fed to the top of the boiler. This can reduce
water gauge or water column is provided. boiler fatigue caused by thermal stress. By spray-
ing the feedwater over a series of trays the water is
• Bottom blowdown valves: They provide a means quickly heated and this can reduce limescale.
for removing solid particulates that condense and lie
• Desuperheater tubes or bundles: A series of tubes
on the bottom of a boiler. As the name implies, this
or bundles of tubes in the water drum or the steam
valve is usually located directly on the bottom of the
drum designed to cool superheated steam, in order
boiler, and is occasionally opened to use the pressure
to supply auxiliary equipment that does not need, or
in the boiler to push these particulates out.
may be damaged by, dry steam.
• Continuous blowdown valve: This allows a small
• Chemical injection line: A connection to add
quantity of water to escape continuously. Its pur-
chemicals for controlling feedwater pH.
pose is to prevent the water in the boiler becoming
saturated with dissolved salts. Saturation would lead
to foaming and cause water droplets to be carried 19.7.2 Steam accessories
over with the steam - a condition known as priming.
Blowdown is also often used to monitor the chem- • Main steam stop valve:
istry of the boiler water.
• Steam traps:
• Flash Tank: High-pressure blowdown enters this
vessel where the steam can 'flash' safely and be used • Main steam stop/Check valve: It is used on multi-
in a low-pressure system or be vented to atmosphere ple boiler installations.
while the ambient pressure blowdown flows to drain.
A fuel-heated boiler must provide air to oxidize its fuel. • Dealkalization of water
Early boilers provided this stream of air, or draught,
through the natural action of convection in a chimney • Draft (boiler)
connected to the exhaust of the combustion chamber.
• Electric water boiler (for drinking water)
Since the heated flue gas is less dense than the ambient air
surrounding the boiler, the flue gas rises in the chimney,
• External combustion engine
pulling denser, fresh air into the combustion chamber.
Most modern boilers depend on mechanical draught • Firebox (used by railway locomotives)
rather than natural draught. This is because natural
draught is subject to outside air conditions and tempera- • Fossil fuel power plant
ture of flue gases leaving the furnace, as well as the chim-
ney height. All these factors make proper draught hard to • Furnace
attain and therefore make mechanical draught equipment
much more reliable and economical. • Geothermal power plant
Types of draught can also be divided into induced • Heating
draught, where exhaust gases are pulled out of the boiler;
forced draught, where fresh air is pushed into the boiler; • Heat-only boiler station
and balanced draught, where both effects are employed.
Natural draught through the use of a chimney is a type • Heat recovery steam generator
of induced draught; mechanical draught can be induced,
forced or balanced. • Hot water reset
There are two types of mechanical induced draught. The
first is through use of a steam jet. The steam jet oriented • Hydronics
in the direction of flue gas flow induces flue gasses into
• Internally rifled boiler tubes (also known as Serve
the stack and allows for a greater flue gas velocity increas-
tubes)
ing the overall draught in the furnace. This method was
common on steam driven locomotives which could not
• Lancashire boiler
have tall chimneys. The second method is by simply us-
ing an induced draught fan (ID fan) which removes flue
• Natural circulation boiler
gases from the furnace and forces the exhaust gas up the
stack. Almost all induced draught furnaces operate with • Power plant and Power station
a slightly negative pressure.
Mechanical forced draught is provided by means of a fan • Pulverized coal-fired boiler
forcing air into the combustion chamber. Air is often
passed through an air heater; which, as the name suggests, • Radiator
heats the air going into the furnace in order to increase the
overall efficiency of the boiler. Dampers are used to con- • Recovery boiler
trol the quantity of air admitted to the furnace. Forced
draught furnaces usually have a positive pressure. • Steam generator (nuclear power)
Balanced draught is obtained through use of both induced • Thermal power station
and forced draught. This is more common with larger
boilers where the flue gases have to travel a long distance • Thermoelectric
through many boiler passes. The induced draught fan
works in conjunction with the forced draught fan allow- • Thermostat
ing the furnace pressure to be maintained slightly below
atmospheric. • Water heater
94 CHAPTER 19. BOILER
19.10 References
[1] Frederick M. Steingress (2001). Low Pressure Boilers (4th
Edition ed.). American Technical Publishers. ISBN 0-
8269-4417-5.
An API oil-water separator is a device designed to sep- to the bottom of the separator as a sediment layer, the oil
arate gross amounts of oil and suspended solids from will rise to top of the separator, and the wastewater will
the wastewater effluents of oil refineries, petrochemical be the middle layer between the oil on top and the solids
plants, chemical plants, natural gas processing plants on the bottom.[2]
and other industrial sources. The name is derived from Typically, the oil layer is skimmed off and subsequently
the fact that such separators are designed according to
re-processed or disposed of, and the bottom sediment
standards published by the American Petroleum Institute layer is removed by a chain and flight scraper (or simi-
(API). [1][2]
lar device) and a sludge pump. The water layer is sent
to further treatment consisting usually of a dissolved air
flotation (DAF) unit for further removal of any residual
20.1 Description of the design and oil and then to some type of biological treatment unit for
removal of undesirable dissolved chemical compounds.
operation
95
96 CHAPTER 20. API OIL-WATER SEPARATOR
• Wastewater
20.5 References
[1] American Petroleum Institute (API) (February 1990).
Management of Water Discharges: Design and Opera-
tions of Oil-Water Separators (1st Edition ed.). American
Petroleum Institute.
Modern DAF units using parallel plate technology are quite com-
pact.
Picture shows a 225 m³/h DAF.
97
98 CHAPTER 21. DISSOLVED AIR FLOTATION
Some DAF unit designs utilize parallel plate packing ma- 21.5 External links
terial, lamellas, to provide more separation surface and
therefore to enhance the separation efficiency of the unit. • Treatment and Disposal of Ship-Generated Solid
DAF systems can be categorized as circular (more effi- and Liquid Wastes (REMPEC Regional Marine Pol-
cient) and rectangular (more residence time). The former lution Emergency Response Centre for the Mediter-
type requires just 3 minutes; an example is a Wockoliver ranean Sea, Project MED.B4.4100.97.0415.8,
DAF system. The rectangular type requires 20 to 30 min- April 2004)
utes; a typical example is a Syskill DAF system. One
of the bigger advantages of the circular type is its spiral
scoop.
• Flotation process
21.4 References
[1] Beychok, Milton R. (1967). Aqueous Wastes from
Petroleum and Petrochemical Plants (1st ed.). John Wi-
ley & Sons. LCCN 67019834.
[4] Edzwald, James K., ed. (2011). Water Quality and Treat-
ment. 6th Edition. New York:McGraw-Hill. pp. 9.46.
ISBN 978-0-07-163011-5
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dustri, Jeyakumarjohn, Wiki13, Yannick Lu-Cotrelle, Emmanuelxp, Webmasterpct, BattyBot, GinGin-1995, HzimmermanMSP, Chris-
Gualtieri, Keesvliet, Schilzm, Hmainsbot1, Expertseeker90, Rafa3040, Frosty, Marcionist, Dan Coday, Regional planner, Laluthoms, Re-
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DocWatson42, Karn, Foobar, H Padleckas, Icairns, Vsmith, Adam850, Roybb95, Alistair1978, *drew, Art LaPella, RoyBoy, Robotje,
QTxVi4bEMRbrNqOorWBV, Nk, Pearle, Linuxlad, Ranveig, Velella, HenkvD, Randy Johnston, Gene Nygaard, Redvers, Isfisk, Tiger-
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DVD R W, Luk, Shoy, Markus Schweiss, Bmearns, Kopaka649, Edgar181, Ohnoitsjamie, Bluebot, Persian Poet Gal, Ce1984, MK8,
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tor, Kelly, Emok, Ronhjones, KorinoChikara, Couposanto, MrOllie, Jasper Deng, Tide rolls, Tressor, Teles, Senator Palpatine, Fraggle81,
, AnomieBOT, Jim1138, Galoubet, Accuruss, Trotnixon777, Celtis123, The High Fin Sperm Whale, Citation bot, Wikivendett,
Mike Dill, Muion, PeterEastern, Krish Dulal, I dream of horses, Calmer Waters, Full-date unlinking bot, Thrissel, کاشف عقیل, Yunshui,
The goatlama, சதீஷ், JeepdaySock, Vaypertrail, Woolly wombat, Карма2, Wikipelli, K6ka, Ipwnedx, Macempty, Quondum, Erianna,
Cedric88, Somewhere12, ClueBot NG, Astatine211, Jack Greenmaven, Satellizer, O.Koslowski, Boblehest, Widr, MerlIwBot, Helpful
Pixie Bot, SchroCat, TheRealSteveJ, KillzHuman, Achowat, Raccoon5r, Urmom5r, Tutelary, Jonnyz007, Boblonam, Ks.magi, Rhys-
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102 CHAPTER 21. DISSOLVED AIR FLOTATION
21.6.2 Images
• File:API_Separator.png Source: http://upload.wikimedia.org/wikipedia/commons/9/9c/API_Separator.png License: CC-BY-SA-3.0
Contributors: Originally from en.wikipedia; description page is/was here. Original artist: Original uploader was Mbeychok at en.wikipedia
• File:AlbertaSulfurAtVancouverBC.jpg Source: http://upload.wikimedia.org/wikipedia/commons/f/fa/AlbertaSulfurAtVancouverBC.
jpg License: CC SA 1.0 Contributors: English Wikipedia, original upload 10 July 2005 by Leonard G. Original artist: Leonard G.
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License: CC-BY-SA-3.0 Contributors: Own work Original artist: Walter Siegmund (talk)
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License: CC-BY-SA-3.0 Contributors: Own work Original artist: Walter Siegmund (talk)
• File:BP_PLANT_EXPLOSION-1_lowres2.jpg Source: http://upload.wikimedia.org/wikipedia/commons/7/71/BP_PLANT_
EXPLOSION-1_lowres2.jpg License: Public domain Contributors: http://www.csb.gov/assets/news/image/BP_PLANT_
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• File:Barnard’{}s_fanless_self-cooling_tower.jpg Source: http://upload.wikimedia.org/wikipedia/commons/8/86/Barnard%27s_
fanless_self-cooling_tower.jpg License: Public domain Contributors: Illustration from A Textbook on Steam Engineering. Scranton, PA:
International Textbook Company. Sectionb 29: p. 39. Digital scan at http://archive.org/details/textbookonsteame04inteiala Original artist:
Unsigned engraving; book by International Textbook Company
• File:Benzene_Friedel-Crafts_alkylation-diagram.svg Source: http://upload.wikimedia.org/wikipedia/commons/f/f4/Benzene_
Friedel-Crafts_alkylation-diagram.svg License: CC BY 3.0 Contributors: Own work Original artist: Pen1234567
• File:Buckminsterfullerene-perspective-3D-balls.png Source: http://upload.wikimedia.org/wikipedia/commons/0/0f/
Buckminsterfullerene-perspective-3D-balls.png License: Public domain Contributors: ? Original artist: ?
• File:Carboxylic_acid_dimers.png Source: http://upload.wikimedia.org/wikipedia/commons/c/c9/Carboxylic_acid_dimers.png License:
Public domain Contributors: ? Original artist: ?
• File:CatReformer.png Source: http://upload.wikimedia.org/wikipedia/commons/2/21/CatReformer.png License: CC-BY-SA-3.0 Con-
tributors: I drew this flow diagram myself and currently I own all rights to it. I used Microsoft’s Paint program to draw it. I am User:mbeychok
and the date is December 5, 2006. Original artist: User:mbeychok
• File:CatReformerEq4.png Source: http://upload.wikimedia.org/wikipedia/commons/6/63/CatReformerEq4.png License: CC-BY-SA-
3.0 Contributors: ? Original artist: ?
21.6. TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES 103