Production of Hydrogen From Refinery Off-Gas

State of Libya
MINISTRY OF HIGHER EDUCATION AND SCINTIFIC RESEARCH
BRIGHT STAR UNIVERSITY - EL-BREGA
Faculty of technical engineering

Chemical engineering department
Production of hydrogen from refinery

off-gas
Project N.O. : CHE 2016 002 A 019

A Project Submitted in Partial Fulfillment of the Requirements for the
Degree of (B.Sc.) in Chemical Engineering.
Prepared by:
1. Adeal Ali Salem Aswiri 13172

2. Ahmed Abdallah Ali Abdaljabar 21161060
3. Mohmmed Hessan Mohammed Althahir 13314
4. Abdalfatah Ebrahem MuftahAlhaj Ahmed 13238
Supervised by:
Dr.OmarAlshrif
Spring 2017
‫د‪ٌٚ‬خ ٌ‪١‬ج‪١‬ب‬
‫‪ٚ‬سارح اٌزؼٍ‪ ُ١‬اٌؼبٌ‪ ٚ ٟ‬اٌجذث اٌؼٍّ‪ٟ‬‬
‫جبِؼخ إٌجُ اٌسبطغ – اٌجز‪٠‬مخ‬
‫كلية الهندسة التقنية‬

‫قسم الهندسة الكيميائية‬
‫إٔزبج اٌ‪١ٙ‬ذر‪ٚ‬ج‪ ِٓ ٓ١‬اٌغبساد اٌغ‪١‬ز ِصٕؼخ ِٓ اٌّصفبح‬
‫رلُ اٌّشز‪ٚ‬ع ‪CHE 2016 002 A 019:‬‬
‫إػذاد‪:‬‬
‫‪13122‬‬ ‫‪ .1‬ػبدي ػٍ‪ ٟ‬سبٌُ اٌص‪٠ٛ‬ز‪ٜ‬‬

‫‪21111010‬‬ ‫‪ .2‬أدّذ ػجذهللا ػٍ‪ ٟ‬ػجذ اٌججبر‬
‫‪13314‬‬ ‫‪ِ .3‬ذّذ دس‪ِ ٓ١‬ذّذ اٌطب٘ز‬
‫‪13233‬‬ ‫‪ .4‬ػجذاٌفزبح إثزا٘‪ِ ُ١‬فزبح اٌذبج أدّذ‬
‫إشزاف‪:‬‬
‫د‪ .‬ػّز اٌشز‪٠‬ف‬
‫رث‪١‬غ ‪2012‬‬
CERTIFICATE
This project entitled
Hydrogen production from refinery off-gas
Which is being submitted by:
1. Adeal Ali Salem Aswiri 13172
2. Ahmed Abdallah Ali Abdaljabar 21161060
3. MohmmadHosainMohmmadAlthahir 13314
4. AbdalfatahEbrahemMuftahAlhaj Ahmed 13238
In the partial fulfillment of requirement for the award of the degree in chemical
engineering has been discussed by us and all the suggested recommendations
during the discussion are carried out.
1stExaminer( The supervisor 2ndExaminer (The co-supervisor)

Signature:Signature :
Name : Name :
Date: / / 2017 Date: / / 2017
3rd Examiner
Signature:
Name :
Date: / / 2017
4th Examiner
Signature:
Name :
Date: / / 2017
‫اإلهداء‬
‫إٌ‪ ِٓ ٝ‬ثٍغ اٌزسبٌخ ‪ٚ‬أد‪ ٜ‬األِبٔخ ‪ٔٚ ..‬صخ األِخ ‪ ..‬إٌ‪ٔ ٝ‬ج‪ ٟ‬اٌزدّخ ‪ٛٔٚ‬ر اٌؼبٌّ‪ٓ١‬‬
‫"س‪١‬ذٔب ِذّذ صٍ‪ ٝ‬هللا ػٍ‪ٚ ٗ١‬سٍُ"‬
‫إٌ‪ ِٓ ٝ‬وٍٍٗ هللا ثبٌ‪١ٙ‬جخ ‪ٚ‬اٌ‪ٛ‬لبر ‪ ..‬إٌ‪ ِٓ ٝ‬ػٍّٕ‪ ٟ‬اٌؼطبء ثذ‪ ْٚ‬أزظبر ‪ ..‬إٌ‪ٝ‬‬
‫ِٓ أدًّ أسّٗ ثىً افزخبر ‪ ..‬أرج‪ ِٓ ٛ‬هللا أْ ‪ّ٠‬ذ ف‪ ٟ‬ػّزن ٌزز‪ ٜ‬ثّبرا لذ دبْ‬
‫لطبف‪ٙ‬ب ثؼذ ط‪ٛ‬ي أزظبر ‪ٚ‬سزجم‪ ٝ‬وٍّبره ٔج‪ َٛ‬أ٘زذ‪ ٞ‬ث‪ٙ‬ب اٌ‪ٚ َٛ١‬ف‪ ٟ‬اٌغذ‬
‫‪ٚ‬إٌ‪ ٝ‬األثذ‪ٚ ..‬اٌذ‪ ٞ‬اٌؼش‪٠‬ش‬
‫إٌ‪ِ ٝ‬الو‪ ٟ‬ف‪ ٟ‬اٌذ‪١‬بح ‪ ..‬إٌ‪ِ ٝ‬ؼٕ‪ ٝ‬اٌذت ‪ٚ‬إٌ‪ِ ٝ‬ؼٕ‪ ٝ‬اٌذٕبْ ‪ ٚ‬اٌزفبٔ‪ٟ‬‬
‫إٌ‪ ٝ‬ثسّخ اٌذ‪١‬بح ‪ٚ‬سز اٌ‪ٛ‬ج‪ٛ‬د‬
‫إٌ‪ ِٓ ٝ‬وبْ دػبئ‪ٙ‬ب سز ٔجبد‪ٚ ٟ‬دٕبٔ‪ٙ‬ب ثٍسُ جزاد‪ ٟ‬إٌ‪ ٝ‬أغٍ‪ ٝ‬اٌذجب‪٠‬ت‪ ...‬أِ‪ ٟ‬اٌذج‪١‬جخ‬
‫إٌ‪ ِٓ ٝ‬رافمزٕ‪ِٕ ٟ‬ذ أْ دٍّٕب دمبئت صغ‪١‬زح ‪ِٚ‬ؼه سزد اٌذرة خط‪ٛ‬ح ثخط‪ٛ‬ح‬
‫‪ِٚ‬ب رشاي رزافمٕ‪ ٟ‬دز‪ ٝ‬ا‪.. ْ٢‬إٌ‪ ٝ‬شّؼخ ِزمذح رٕ‪١‬ز ظٍّخ د‪١‬بر‪ ....ٟ‬أخز‪ٟ‬‬
‫إٌ‪ ٝ‬أخ‪ٚ ٟ‬رف‪١‬ك درث‪ ٟ‬ف‪٘ ٟ‬ذٖ اٌذ‪١‬بح ‪ِ ،‬ؼه أو‪ ْٛ‬أٔب ‪ ٚ‬ثذ‪ٔٚ‬ه أو‪ِ ْٛ‬ثً‬
‫أ‪ ٞ‬ش‪ٟ‬ء ‪ ،‬إٌ‪ ِٓ ٝ‬أر‪ ٜ‬اٌزفبؤي ثؼ‪ٚ ٕٗ١‬اٌسؼبدح ف‪ ٟ‬ضذىزٗ ‪ ..‬ف‪ٙٔ ٟ‬ب‪٠‬خ‬
‫ِش‪ٛ‬ار‪ ٞ‬أر‪٠‬ذ أْ أشىز ن ػٍ‪ِٛ ٝ‬الفه إٌج‪ٍ١‬خ إٌ‪ ِٓ ٝ‬رطٍؼذ ٌٕجبد‪ ٟ‬ثٕظزاد‬
‫األًِ‪ .....‬أخ‪ٟ‬‬
‫إٌ‪ ٝ‬اإلخ‪ٛ‬ح ‪ ٚ‬األخ‪ٛ‬اد ‪ ،‬إٌ‪ ِٓ ٝ‬رذٍ‪ ٛ‬ثبإلخبء ‪ٚ‬رّ‪١‬ش‪ٚ‬ا ثبٌ‪ٛ‬فبء ‪ٚ‬اٌؼطبء إٌ‪ٕ٠ ٝ‬بث‪١‬غ‬
‫اٌصذق اٌصبف‪ ٟ‬إٌ‪ِ ِٓ ٝ‬ؼ‪ ُٙ‬سؼذد ‪ٚ ،‬ثزفمز‪ ُٙ‬ف‪ ٟ‬در‪ٚ‬ة اٌذ‪١‬بح اٌذٍ‪ٛ‬ح‬
‫‪ٚ‬اٌذش‪ٕ٠‬خ سزد إٌ‪ ِٓ ٝ‬وبٔ‪ٛ‬ا ِؼ‪ ٟ‬ػٍ‪ ٝ‬طز‪٠‬ك إٌجبح ‪ٚ‬اٌخ‪١‬ز‬
‫إٌ‪ ِٓ ٝ‬ػزفذ و‪١‬ف أجذُ٘ ‪ٚ‬ػٍّ‪ ٟٔٛ‬أْ ال أض‪١‬ؼ‪ ......ُٙ‬أصذلبئ‪ٟ‬‬
‫شكر و تقدير‬
‫ثسُ هللا اٌزدّٓ اٌزد‪ُ١‬‬
‫(ألْ شىزرُ ألس‪٠‬ذٔىُ)‬
‫اٌٍ‪ٌ ُٙ‬ه اٌذّذ ‪ ٚ‬اٌشىز دز‪ ٝ‬رزض‪ ٚ ٝ‬أْ رض‪١‬ذ ‪ ٚ‬ثؼذ اٌزض‪ ، ٝ‬دّذا وث‪١‬زا ‪١ٍ٠‬ك ثجّبي‬
‫‪ٚ‬ج‪ٙ‬ه ‪ ٚ‬ػظ‪ ُ١‬سٍطبٔه اٌ‪ٛ‬ادذ‪.‬‬
‫‪ٚ‬ثؼذ ‪٠‬سزٔب أْ ٔزمذَ ثخبٌص شىزٔب ‪ ٚ‬جش‪ ً٠‬ػزفٕٕب ‪ ٚ‬ػظ‪ ُ١‬إِزٕبٕٔب إٌ‪ ٝ‬وً ِٓ وبٔ‪ٛ‬ا سججب ف‪ٟ‬‬
‫إرّبَ ‪ٚ‬ص‪ٌٕٛ‬ب إٌ‪٘ ٝ‬ذٖ اٌّزدٍخ س‪ٛ‬ا أثبرب أ‪ ٚ‬أِ‪ٙ‬برٕب أ‪ ٚ‬إخ‪ٛ‬إٔب أ‪ ٚ‬أصذلبئٕب أ‪ ٚ‬أدجبثٕب أ‪ٚ‬‬
‫أسبرذرٕب‬
‫‪ٔ ٚ‬خص ثبٌذوز اٌذوز‪ٛ‬ر اٌفبضً ‪ /‬ػّزاٌشز‪٠‬ف‬
‫‪ ٚ‬اٌذ‪ ٞ‬أشزف ػٍ‪ ٝ‬إرّبَ ٘ذا اٌّشز‪ٚ‬ع ‪ ٚ‬لذَ ٌٕب ‪٠‬ذ اٌؼ‪ ٚ ْٛ‬اٌّش‪ٛ‬رح ‪ ٚ‬سخز ٌٕب لذرارٗ‬
‫اٌؼٍّ‪١‬خ ‪ ٚ‬اٌؼٍّ‪١‬خ ف‪ ٟ‬سج‪ ً١‬إٔجبدٗ ‪ ٚ‬إثزاسٖ إٌ‪ ٝ‬د‪١‬ش اٌ‪ٛ‬ج‪ٛ‬د ٌٗ ِٕب أسّ‪ ٝ‬أ‪٠‬بد اٌشىز ‪ٚ‬‬
‫اٌزمذ‪٠‬ز‬
‫وّب ٔزمذَ ثبٌشىز اٌجش‪ ً٠‬إٌ‪ ٝ‬وبفخ أػضبء ٘‪١‬ئخ اٌزذر‪٠‬س ف‪ ٟ‬لسُ اٌ‪ٕٙ‬ذسخ اٌى‪١ّ١‬بئ‪١‬خ اٌذ‪ٞ‬‬
‫أسؼذٔب اٌذع أْ ٔززٍّذ ػٍ‪ ٝ‬أ‪٠‬ذ‪ٔ ٚ ُٙ٠‬سزّذ ِٓ ػٍّ‪ِ ُٙ‬ب ‪١ٕ٠‬ز طز‪٠‬مٕب‬
‫وّب ٔشىز وً ِٓ سبُ٘ ِؼٕب ػٍ‪ ٝ‬إرّبَ ٘ذا اٌّشز‪ٚ‬ع أ‪ِ ٚ‬ذ ‪٠‬ذ اٌؼ‪ٌٕ ْٛ‬ب س‪ٛ‬اء ثبٌّؼٍ‪ِٛ‬خ‬
‫اٌّف‪١‬ذح أ‪ ٚ‬إٌص‪١‬ذخ اٌجٕبءح أ‪ ٚ‬ثبٌذػ‪ٛ‬اد اٌصبدلخ أ‪ ٚ‬دز‪ ٝ‬ثبالثزسبِخ اٌٍط‪١‬فخ ‪ٔ ٚ‬خص ثبٌذوز ‪:‬‬
‫األخ‪ٛ‬ح ِ‪ٛ‬اظف‪ ٓ١‬شزوخ سزد ٌزصٕ‪١‬غ إٌفع ‪ ٚ‬اٌغبس ‪ ٚ‬اٌشزوخ اٌٍ‪١‬ج‪١‬خ إٌز‪ٚ‬ج‪١‬خ ٌصٕبػخ‬
‫األسّذح اٌى‪١ّ١‬بئ‪١‬خ‪.‬‬
‫‪ُ١‬‬ ‫س ُِ ه‬
‫هللاِ اٌ هز ْد َّ ِٓ اٌ هز ِد ِ‬ ‫ثِ ْ‬
‫‪ٚ‬ح ِِْٓ أَ ِْ ِز َرثِّ‪َِ َٚ ٟ‬ب أُ‪ِ ٚ‬ر‪١‬زُُ ِِّٓ ا ٌْ ِؼ ٍْ ُِ إِاله لَ ٍِ‪١‬ال﴾‬ ‫‪ٚ‬ح لُ ًِ ُّ‬
‫اٌز ُ‬ ‫سأٌَُ‪َ َٔٛ‬ه َػ ِٓ ُّ‬
‫اٌز ِ‬ ‫﴿ َ‪ْ َ٠ٚ‬‬
‫ا‪٠٢‬خ( ‪) 85‬‬ ‫س‪ٛ‬رح اإلسزاء‬
CONTENTS
PAGE NO.
Abstract vii
List of Tables iv
List of Figures iii
List of Symbols v-vi
CHAPTER 1: 1.1 Introduction 1-2

1.2 Physical properties of hydrogen
1.3 Uses of hydrogen 2
1.4 Refinery off-gas stream 3
1.4.1 Refinery off-gas composition 3
1.5 Steam-reforming 4
1.6.1 Industrial reforming 4
1.7 Shift Reactor 5
1.8 Pressure swing adsorption 6
1.9 Various methods of hydrogen production 7
1.9.1 Steam methane reforming 7
1.9.2 Coal gasification 8
1.9.3 Partial Oxidation of Hydrocarbon 8
1.9.4 Biomass gasification 8-9
1.9.5 Electrolysis 9
1.9.6 Thermochemical 10
1.9.7 Photo-biological 10
CHAPTER 2: Process Description

2.1 Introduction 11
2.2 Process Description 12-13
CHAPTER 3: Material Balance

3.1 Basis 14
3.2 Refinery off-gas required 14
3.3 Material balance of individual equipment 15
3.3.1 Desulfurizer 15
3.3.2 Reformer 16-20
3.3.3 Shift reactor 21
3.3.4 CO2 absorber 22
3.3.5 Pressure swing adsorption 23-25
i
CHAPTER 4: Energy balance
4.1 Energy balance at individual equipment 26
4.1.1 Energy balance at steam reformer 26
4.1.2 Energy balance at steam generator 27
4.1.3 Energy balance at shift reactor 27-28
4.1.4 Energy balance at CO2 Absorber 28-29
4.1.5 Energy balance at PSA 29-30
4.1.6 Off –gas temperature calculation 30
CHAPTER 5: Equipment Design
5.1 CO2 Absorption column design 31-32
5.1.1 Calculation of tray or column diameter 33
5.1.2 Calculation of column height 34-37
5.1.3 Shell design 38
5.1.4 Head design 39-40
5.1.5 Support design 40-46
CHAPTER 6: Process control
6. Measurement and control devices 47
6.1. Purpose of using measurement and control
47
Devices
6.2. How to make a plan for measurement and
47
control devices
6. 3. Models of measurement and control systems 48
CHAPTER 7: Safety and prevention loss

7.1 Safety and prevention loss 50
7. 2. Aims of industrial security 50
7. 3. Methods of treating and disposing of industrial
53
Debris
7. 4. Dangers associated with material used
in manufacturing and methods of protection against 54
them
Conclusion 55
References 56
ii
LIST OF FIGURES
Figure. No. Title Page No.
1 Temperature vs. exit carbon monoxide 6

2 Simplified process diagram of H2 production 13
3 Inlet gas composition of reformer 16
4 Output of the reformer 20
5 Output of shift reactor 21
6 Output of CO2 Absorber 22
7 Output of PSA unit 23
8 Material balance flow sheet of hydrogen production 24
9 CO2 Absorption column 31
10 Operating line and equilibrium line graph 34
11 The graph between y and f(y) 37
12 Torispherical head 39
13 Cylindrical skirt support 40
iii
LIST OF TABLES
Table No. Title Page No.
1 Refinery off-gas composition 3

2 Refinery off-gas composition at reformer inlet 16
3 Output from reformer 20
4 Output of shift reactor 21
5 Outlet composition of PSA 23
6 Material balance of hydrogen production 25
7 Inlet gas properties of reformer 26
8 Outlet gas properties of reformer 26
9 Inlet gas properties of shift reactor 27
10 Outlet gas properties of shift reactor 28
11 Inlet gas properties of CO2 Absorber 28
12 Outlet gas properties of CO2 Absorber 29
13 Inlet gas properties of PSA 29
14 Out gas properties of PSA 30
15 Vapour liquid equilibrium data 34
16 Data between y and f(y) 36
17 Component required for design 46
18 Specification of CO2 Absorption column 46
iv
NOMENCLATURE
E1 - steam generator
E2 - preheater for boiler feed water
HC - hydrocarbon
SR - steam reformer
FH2, Fstm- mass flow rate of hydrogen/export steam from the unit.
(H/C)in- recycle hydrogen to carbon molar ratio in the feed
Q- Rate of heat flow
CP- specific heat at constant pressure
VS- Volume of the reactor
FAo - feed flow rate
G1- feed gas rate
Y1- feed concentration
GS- feed gas rate on salute free basis
LS- Liquid flow rate
Usfl- superficial velocity
Csb- Souder’s Brown flooding constant
-Vapour and liquid density
σ - Surface tension
Flv -flow parameter

US- operating velocity
Aa- active tray area
AT- tower cross-section
Dc- column diameter
h- Height of tower
HtG- height of gas phase transfer unit
NtG- number of gas phase unit
E- Modulus of elasticity
j- Welding joint efficiency
f- Allowable stress
v
U- out of roundness in %
tsk- thickness of skirt
Wa- weight of attachment
Wl- weight of liquid content
WS- weight of shell
Wins- weight of insulation
T- Period of vibration
C- Stress concentration factor
vi
ABSTRACT
Steam methane reforming (SMR) is one of the most promising processes for hydrogen
production. Several studies have demonstrated its advantages from the economic viewpoint.
Nowadays process development is based on technical and economic aspects, however, in the
near future; the environmental impact will play a significant role in the design of such processes.
In this paper, an SMR process is studied from the viewpoint of overall environmental impact,
using an exergoenvironmental analysis. This analysis presents the combination of exergy
analysis and life cycle assessment. Components where chemical reactions occur are the most
important plant components from the exergoenvironmental point of view, because, in general,
there is a high environmental impact associated with these components. This is mainly caused by
the energy destruction within the components, and this in turn is mainly due to the chemical
reactions. The obtained results show that the largest potential for reducing the overall
environmental impact is associated with the combustion reactor, the steam reformer, the
hydrogen separation unit and the major heat exchangers. The environmental impact in these
components can mainly be reduced by improving their exergetic efficiency. A sensitivity
analysis for some important exergoenvironmental variables is also presented in the paper.
Keywords: Hydrogen production, Steam methane reforming process, Exergy analysis;
vii
Chapter 1
1.1 Introduction:
Hydrogen is a chemical element with symbol H and atomic number 1 with an atomic weight of
1.00794u, hydrogen is the lightest element and its monatomic form (H) is the most abundant
chemical substance, constituting roughly 75% of the Universe's baryonic mass.Non-remnant
starts are mainly composed of hydrogen in its plasma state. At standard temperature and pressure
hydrogen is a colorless, odorless, nontoxic, nonmetallic, highly combustible diatomic gas with
the molecular formula H2.Naturally occurring atomic hydrogen is rare on Earth because
hydrogen readily forms covalent compounds with most elements and is present in the water
molecule and in most organic compounds. Hydrogen plays a particularly important role in acid-
base chemistry with many reactions exchanging protons between soluble molecules. The latter
cation is written as though composed of a bare proton, but in reality, hydrogen cations in ionic
compounds always occur as more complex species. The most common isotope of hydrogen is
1
protium (name rarely used, symbol H) with a single proton and no neutrons. As the simplest
atom known, the hydrogen atom has been of theoretical use. For example, as the only neutral
atom with an analytic solution to the Schrödinger equation, the study of the energetic and
bonding of the hydrogen atom played a key role in the development of quantum mechanics.
Hydrogen gas was first artificially produced in the early 16th century, via the mixing of metals
with strong acids. In 1766–81, Henry Cavendish was the first to recognize that hydrogen gas was
a discrete substance, and that it produces water when burned, a property which later gave it its
name: in Greek, hydrogen means "water-former".
Industrial production is mainly from the steam reforming of natural gas, and less often from
more energy-intensive hydrogen production methods like the electrolysis of water. Most
hydrogen is employed near its production site, with the two largest uses being fossil fuel
processing (e.g., hydro cracking) and ammonia production, mostly for the fertilizer market.
Hydrogen is a concern in metallurgy as it can embitter many metals, complicating the design of
pipelines and storage tanks.
Hydrogen can be produced from a variety of feedstock’s. These include fossil resources, such as
natural gas and coal, as well as renewable resources, such as biomass and water with input from
renewable energy sources (e.g. sunlight, wind, wave or hydro-power). A variety of process.
PRODUCTION OF HYDROGEN 1 CHEMICAL ENGINEERING DEPARTMENT

CHAPTER-1 INTRODUCTION
technologies can be used, including chemical, biological, electrolytic, photolytic and thermo-
chemical. Each technology is in a different stage of development, and each offers unique
opportunities, benefits and challenges. Local availability of feedstock, the maturity of the
technology, market applications and demand, policy issues, and costs will all influence the
choice and timing of the various options for hydrogen production. High to ultra-high purity
hydrogen may be needed for the durable and efficient operation of fuel cells, consumption in
different process plants, in semiconductor industry and as an energy carrier. Impurities are
believed to cause various problems in the current state-of-the-art fuel cell designs, including
catalyst poisoning and membrane failure. As such, additional process steps may be required to
purify the hydrogen to meet industry quality standards.
1.2 PHYSICAL PROPERTIES OF HYDROGEN:

 At room temperature hydrogen is a gas.
 It is a colorless, tasteless and odorless gas.
 It is the lightest gas.
 It is insoluble in water.
 It is highly inflammable and burns with blue flame forming water.
 Liquefaction temperature of hydrogen is -252oC.
 Bond energy of H-H is 431 Kj/mole.
 Electro negativity of hydrogen is 2.1.
 Ionization potential of hydrogen gas is 13.54 electron volt.
1.3 USES OF HYDROGEN

 It is used as a fuel.
 It is used for the manufacturing of fertilizers.
 It is used in the preparation of vegetable ghee.
 It is used as rocket fuel.
 It is used in the preparation of ammonia (NH3) and methanol (CH3OH).
 It is used in the preparation of oxy-hydrogen flame which is used in welding due to
production of high temperature.
 It is used in filling weather balloons.
 It is used to prepare tungsten filament.
 It is used to prepare low temperature in liquid state.

1.4 refinery off-gas stream

Refinery gas is a mixture of gases generated during refinery processes which are used to process
crude oil into various petroleum products which can be traded or sold. The composition of
refinery gas varies, depending on the composition of the crude it originates from and the
processes it has been subjected to common components include butanes, butylenes, methane and
ethylene. Some products found in refinery gas are subject to control as a result of programs
which are designed to address climate change.
1.4.1 Refinery off-gas composition
Component Mol. % Mol. Wt.

CH4 0.8521 16
C2H6 0.0794 30
C3H8 0.0189 44
i-C4H10 0.0040 58
n-C4H10 0.0039 58
i-C5H12 0.0013 72
n-C5H12 0.0008 72
n-C6H14 0.0002 88
CO2 0.0269 44
N2 0.0125 28
S <3 PPM
Table-1 refinery off-gas composition

1.5. Steam reforming
Steam reforming, sometimes called Fossil fuel reforming is a method for hydrogen production or
other useful products from hydrocarbon fuels such as natural gas. This is achieved in a
processing device called a reformer which reacts steam at high temperature with the fossil fuel.
The steam methane reformer is widely used in industry to make hydrogen. There is an in
development of much smaller units based on similar technology produce hydrogen as a feedstock
for fuel cells. Small-scale steam reforming units to supply fuel cells are currently the subject of
research and development, typically involving the reforming of methanol or natural gas but other
fuels are also being considered as propane, gasoline, auto gas, and ethanol.
1.5.1 Industrial reforming

Steam reforming of natural gas or syngas sometimes referred to as steam methane reforming
(SMR) is the most common method of producing commercial bulk hydrogen as well as the
hydrogen used in the industrial synthesis of ammonia. It is also the least expensive method. At
high temperatures (700 – 1100 °C) and in the presence of a metal-based catalyst (nickel), steam
reacts with methane to yield carbon monoxide and hydrogen. These two reactions are reversible
in nature.
CH4+ H2O ⇌CO + 3 H2……………………………… (2.1)

Additional hydrogen can be recovered by a lower-temperature gas-shift reaction
with the carbon monoxide produced. The reaction is summarized by
CO + H2O → CO2+ H2……………………………………… (2.2)
The first reaction is strongly endothermic (consumes heat), the second reaction
is mildly exothermic (produces heat).The United States produces nine million tons of
hydrogen per year, mostly with steam reforming of natural gas. The worldwide ammonia
production, using hydrogen derived from steam reforming, was 109 million metric tons in
2004. This SMR process is quite different from and not to be confused with catalytic
reforming of naphtha, an oil refinery process that also produces significant amounts of
hydrogen along with high octane gasoline. The efficiency of the process is approximately (65
-75) %.

1.6. shift reactor

At the outlet of steam reformers, partial oxidation reactors or coke oven gas units the syngas
contains H2, CO, CO2, CH4 and water in chemical equilibrium at high temperatures in the range
of 700 to 1400 °C depending on the process pressure and the mixture of feed stock and process
steam or water. By means of the CO shift conversion an important portion of the CO content in
the cracked gas is used for additional hydrogen generation, which is following the chemical
reaction
CO + H2O→ H2 + CO2……………………….. (2.3)
This process is exothermic and is limited by the chemical equilibrium. There are three different
versions of CO shift conversion: High temperature (HT) CO shift conversion at about 300 to 450
°C down to approx. 2.5 % CO on dry basis at the reactor outlet Medium temperature (MT) CO
shift conversion or so-called isothermal shift conversion at about 220 to 270 °C down to approx.
0.5 % CO on dry basis at the reactor outlet. Low temperature (LT) CO shift conversion at about
180 to 250 °C down to approx. 0.2 % CO on dry basis at the reactor outlet for every process a
special catalyst will be used in a fixed bed reactor to get maximum yield of H2 product.
The use of HT CO shift conversion is state of the art in almost every hydrogen plant. The
application of the low temperature CO shift conversion is normally installed downstream of the
HT shift at already reduced CO content in the feed gas. The additional investment is considered
for plants having a capacity above approx. 40,000 Nm³/h H2 product. The catalyst of the LT shift
is very sensitive against sulphur, chlorine and liquid water and special attention is required
during start up and plant upset conditions. In former concepts the LT shift was important because
of the downstream mechanization of CO following the CO2 removal unit, to meet the product
purity at minimum H2 losses. After the implementation of the Pressure Swing Adsorption (PSA
unit) for H2 purification these process steps have become obsolete. The MT CO shift conversion
as isothermal reaction can be approximated in several adiabatic reactors with intercoolers or
better in an isothermal reactor with integrated steam generation for cooling of the process gas.
The temperature of the shift reaction is controlled easily by setting the pressure of the generated
steam.

Mol%
CO
Inlet temperature in
Fig-1 temperature vs. exit carbon monoxide
1.7. pressure swing adsorber

Adsorption process is designed in such a way that a gas mixture is fed to adsorber at ambient
temperature and increased pressure. At higher temperature, a smaller amount of impurities can
be adsorbed on any adsorbent. The regeneration at high temperature level T2 reduces the
loading L2 of adsorbent at adsorption pressure P1 and temperature T2 and reduced pressure
P2.PSA process works between two pressure levels: (1) Adsorption & (2) Regeneration. In
adsorption phase, adsorption of impurities is carried out at high pressure to increase the partial
pressure and thus increase loading of impurities on adsorbent. The raw feed gas flows through
an adsorber in upward direction and the impurities are selectively adsorbed on the surface of the
adsorbent in the order- water, hydrocarbons, CO and N2 from bottom to top. The purified
product gas leaves the adsorber at the outlet and flows to the product line.
The adsorbing capacity of one adsorber being limited, after certain time the impurities break
through at the outlet of the adsorber. First the impurities come in traces, but gradually their
concentration increases. To avoid this breakthrough, the adsorption step must be interrupted to
regenerate the loaded adsorber. For continuous product supply, at least two absorbers are
necessary. While the first one is regenerated, a second already regenerated one purifies the raw

feed gas. In the regeneration phase, the process is carried out at low pressure at approximately
the same temperature. During this phase, the adsorbed impurities are desorbed. The residual
impurities loading are reduced as much as possible in order to achieve high product purity and a
high H2 recovery.
Regeneration phase consist of several steps;
 Expansion to adsorption pressure, where the adsorbed components start to desorb

from the adsorbent.

 Purging supports this desorption process with some gas having very low partial
pressure of impurities.

 Pressurization to adsorption pressure.
1.8. various methods for hydrogen production
 
 Steam Methane Reforming
 
 Coal Gasification
 
 Partial Oxidation of Hydrocarbons
 
 Biomass Gasification
 
 Electrolysis
 
 Thermo chemical
 
Photo biological
2.9.1. Steam Methane Reforming
Steam reforming involves the endothermic conversion of methane and water vapour into
hydrogen and carbon monoxide (2.4). The heat is often supplied from the combustion of some of
the methane feed-gas. The process typically occurs at temperatures of 700 to 850 °C and
pressures of 3 to 25 bars. The product gas contains approximately 12 % CO, which can be
further converted to CO2 and H2 through the water-gas shift reaction (2.5).
CH4 + H2O + heat →CO + 3H2……………….. (2.4)

CO + H2O → CO2 + H2 + heat ……………....... (2.5)

1.9.2. Coal Gasification
Hydrogen can be produced from coal through a variety of gasification processes (e.g. fixedbed,
fluidized bed or entrained flow). In practice, high-temperature entrained flow processes are
favored to maximize carbon conversion to gas, thus avoiding the formation of significant
amounts of char, tars and phenols. A typical reaction for the process is given in equation (2.4), in
which carbon is converted to carbon monoxide and hydrogen
C(s) + H2O + heat → CO + H2
Since this reaction is endothermic, additional heat is required, as with methane reforming. The CO is
further converted to CO2 and H2 through the water-gas shift reaction, described in equation (2.5).
Hydrogen production from coal is commercially mature, but it is more complex than the production
of hydrogen from natural gas. The cost of the resulting hydrogen is also higher. But since coal is
plentiful in many parts of the world and will probably be used as an energy source regardless, it is
worthwhile to explore the development of clean technologies for its use.
1.9.3. Partial Oxidation of Hydrocarbons
Partial oxidation of natural gas is the process whereby hydrogen is produced through the partial
combustion of methane with oxygen gas to yield carbon monoxide and hydrogen (2.6). In this
process, heat is produced in an exothermic reaction, and hence a more compact design is possible
as there is no need for any external heating of the reactor. The CO produced is further converted
to H2 as described in equation (2.5).
CH4 + 1/2O2 →CO + 2H2 + heat………….. (2.6)
1.9.4. Biomass Gasification
In biomass conversion processes, a hydrogen-containing gas is normally produced in a manner

similar to the gasification of coal. However, no commercial plants exist to produce hydrogen
from biomass. Currently, the pathways followed are steam gasification (direct or indirect),
entrained flow gasification, and more advanced concepts such as gasification in supercritical
water, application of thermo-chemical cycles, or the conversion of intermediates (e.g. ethanol,

bio-oil ororrified wood). None of the concepts have reached a demonstration phase for hydrogen
production. Biomass gasification is an R&D area shared between H2 production and biofuels
production. Gasification and pyrolysis are considered the most promising medium-term
technologies for the commercialization of H2 production from biomass. A typical flow sheet for
the production of hydrogen
In terms of its energy requirements, the drying of biomass might not be justifiable; therefore,
other pathways based on wet biomass are being sought as well. Biomass feedstock’s are
unrefined products with inconsistent quality and poor quality control. The production methods
vary according to crop type, location and climatic variations. Erratic fuels have contributed to the
difficulties in technological innovation, since less homogenous and low quality fuels need more
sophisticated conversion systems. There is a need to rationalize the production and preparation of
fuel to produce more consistent, higher-quality fuels that can be described by common standards.
Large-scale systems tend to be suitable for cheaper and lower quality fuels, while smaller plants
tend to require higher levels of fuel quality and better fuel homogeneity. A better understanding
of this relationship, and the specific tolerances that each technology can accommodate, is
needed.
1.9.5. Electrolysis
Water electrolysis is the process whereby water is split into hydrogen and oxygen through the
application of electrical energy, as in equation (2.7). The total energy that is needed for water
Porous water-filled layer in the earth strata. Electrolysis is increasing slightly with temperature,
while the required electrical energy decreases. A high-temperature electrolysis process might,
therefore, be preferable when high-temperature heat is available as waste heat from other
processes. This is especially important globally, as most of the electricity produced is based on
fossil energy sources with relatively low efficiencies.
H2O + electricity → H2 + 1/2O2……………… (2.7)

1.9.6. Thermochemical
Thermo-chemical water splitting is the conversion of water into hydrogen and oxygen by a series
of thermally driven chemical reactions. Thermo-chemical water-splitting cycles have been
known for the past 35 years. They were extensively studied in the late 1970s and 1980s, but have
been of little interest in the past 10 years. While there is no question about the technical
feasibility and the potential for high efficiency, cycles with proven low cost and high efficiency
have yet to be developed commercially. An example of a thermo-chemical process is the
iodine/sulphur cycle. For this process, the research and development needs are to capture the
thermally split H2, to avoid side reactions and to eliminate the use of noxious substances. The
corrosion problems associated with the handling of such materials are likely to be extremely
serious.
H2SO4 →SO2 + H2O + 1/2O2………………. (2.8)
I2 + SO2 + 2H2O → H2SO4 + 2HI………… (2.9)
2HI → I2 + H2……………………………… (2.10)
H2O →H2 + 1/2O2…………………………. (2.11)
1.9.7. Photobiological
Photo-biological production of hydrogen is based on two steps: photosynthesis (2.12) and

hydrogen production catalyzed by hydrogen gases (2.13) in, for example, green algae and
cyanobacteria. Long term basic and applied research is needed in this area, but if successful, a
long-term solution for renewable hydrogen production will result. It is of vital importance to
understand the natural processes and the genetic regulations of H2 production. Metabolic and
genetic engineering maybe used to demonstrate the process in larger bioreactors. Another option
is to reproduce the two steps using artificial photosynthesis.
Photosynthesis: 2H2O → 4H+ + 4e– + O2 …… …… (2.12)
Hydrogen Production: 4H+ + 4e– →2H2 …………………… (2.13)

Chapter 2
Process description
2.1 Introduction
Steam reforming of hydrocarbons has established itself as the most economic and preferred
process for the production of hydrogen and synthesis gas. In view of the large value addition
involved in the process and its high energy consumption coupled with increasing energy cost, the
optimal operation of such units is of utmost concern to the industry. The choice of feedstock for
steam reforming is largely determined by location, availability, and the local energy policy. Two
Common feedstocks range from natural gas to heavy naphtha. Because even the simplest of these
feedstocks contains many components (natural gas contains mainly methane but also ethane,
propane, butane, and other higher hydrocarbons), a multitude of chemical reactions occur in the
steam reformer, making it impractical to account for all of them. Reformation experiments
carried out with hydrocarbons such as propane, butane, hexane, and benzene suggest methane to
be the primary product of the reaction. Based on this observation, many published works3-5 on
steam reforming with heavier hydrocarbons assume that all hydrocarbons heavier than methane
hydrocrack to methane instantaneously at the reformer inlet. As a result, the reaction system
within the reformer can be reduced to that for the steam-methane reaction regardless of the
feedstock used. This simplifying assumption gained wide acceptance because it was found to be
satisfactory for predicting the gas composition at the reformer outlet. This is primarily because
the reforming reactions are thermodynamically and not kinetically controlled. However, axial
conversion profiles in an ammonia plant steam reformer suggest that methanation is completed
between 2 and 6 m from the reformer.

CHAPTER-2 PROCESS DESCRIPTION
2.2 Process Description
Figure 2 shows a simplified flow diagram of the industrial hydrogen unit considered in this
study. The feed to the reformer furnace is comprised of refinery off gas, mixed with suitable
quantities of recycle H2 and steam, which are required to maintain the reformer catalyst in its
active state and to prevent carbon formation, respectively. The reactions occurring in the
reformer are steam-methane reforming reactions. The six reforming reactions (eqs 3.1-3.6) occur
mainly in the steam reformer, while thermodynamics favor the shift reaction (eq 3.7) in the high-
temperature (HT) shift converter. (An additional low-temperature shift converter may be present
in some plants to achieve additional CO conversion, but it is absent in the industrial unit
modeled.) The surplus heat in the process gas at the reformer outlet is recovered (in E1) and used
to generate very high pressure (VHP) steam. Part of this steam is mixed with feed, while the
remainder is exported outside the unit. The shift reaction (eq 3.5) occurring in the HT shift
converter produces additional H2. The hot syngas leaving the shift converter is used to preheat
boiler feed water (in E2) before it is further cooled and flashed to remove entrained steam as
condensate, which is recycled back to the process. The H2-rich stream then enters a pressure-
swing adsorber (PSA), which separates H2 from off-gases. The PSA off gas is used to
supplement external fuel for combustion in the reformer furnace. The general equations are given
below:
For the methane reforming the following reaction take place
CH4 + H2O  CO + 3H2 --- (3.1)
C2H6 + 2H2O  2CO + 5H2 --- (3.2)
C3H8 + 3H2O  3CO + 7H2 --- (3.3)
C4H10 + 4H2O 4CO + 9H2 --- (3.4)
C5H12 + 5H2O 5CO +11H2 --- (3.5)
C6H14 + 6H2O 6CO +13H2 --- (3.6)
CO + H2O CO2 + H2 --- (3.7)

CHAPTER-2 PROCESS DESCRIPTION
Fig-2 simplified process diagram of H2 production

Chapter 3
Material balance
Material balances are the basis of process design. A material balance taken over complete
process will determine the quantities of raw materials required and products produced. Balances
over Individual process until set the process stream flows and compositions. The general
conservation equation for any process can be written as;
Material out = material in + accumulation
For a steady state process the accumulation term is zero. If a chemical reaction is taking place a
particular chemical species may be formed or consumed. But if there is no chemical reaction, the
steady state balance reduces to:
Material out = Material in
A balance equation can be written for each separately identifiable species present, elements,
compounds and for total material
3.1 basis
500 T/days of hydrogen gas produced
(500*1000)/ (24*2) = 10,500 kg mol/hr hydrogen produced
3.2 refinery off-gases required

The reactions involved are as followed:
CH4 + H2O  CO + 3H2 ………………………….…… (4.1)
C2H6 + 2H2 O  2 CO + 5H2 ………………………..… (4.2)
C3H8 + 3H2O  3 CO + 7H2…………………………... (4.3)
C4H10 + 4H2O  4 CO + 9H2 ………………………..…. (4.4)
C5H12 + 5H2O  4 CO + 11H2 …………………………. (4.5)
C6H14 + 6H2O  6 CO + 13H2 …………………………. (4.6)
CO + H2O CO2+ H2…………………………….… (4.7)

CHAPTER-3 MATERIAL BALANCE
IF x kg mol / hr of refinery off-gas be supplied then the H2 content as based on the refinery off-
gas composition is given by:
= (3*0.8521 + 5*0.0794 + 7*0.0189 + 9*0.004 + 9*0.0039 + 11*0.0013 + 11*0.0008 +

13*0.0003 ) * X
= 3.1824X
Hence,
3.1824 X = 10,500 kg mol/hr
 X = 3299.367 kg-mol / hr
Hence, refinery off-gas required = 3299.367 kg-mol / hr.
3.3 material balance of individual equipment
3.3.1 Desulfurizer
In the desulfurizer, there is removal of sulfur, since, the concentration of the sulfur being
encountered is less than 3 ppm, we can say that for the desulfurizer.
Input = 3299.367 kg-mol / hr of the refinery off-gas
Output = 3299.367 kg-mol / hr of the refinery off-gas.
Both the input and output have the same composition and this composition is seen in the
table for feed to the primary reformer.

3.3.2 Reformer:
Refinery off-gas Composition at Reformer Inlet

Component Mol. % kg mol / hr Mol. Wt. Kg/hr
CH4 85.21 2811.416 16 44982.656
C2H6 7.94 261.972 30 7859.16
C3H8 1.89 62.3586 44 2743.7784
i-C4H10 0.40 13.1976 58 765.4608
n-C4H10 0.39 12.8676 58 746.3208
i-C5H12 0.13 4.2892 72 308.8224
n-C5H12 0.08 2.6395 72 205.881
n-C6H14 0.02 0.66 88 58.08
CO2 2.69 88.7538 44 3905.1672
N2 1.25 41.2424 28 1154.7872
TOTAL 100 3299.3967 62730.1138
Table-2 refinery off-gas composition at reformer inlet
Now the above data can be plotted in pie chart given below
CO2
C3H8 3%
2%
C2H6
8%
CH4
85%
fig-3 reformer inlet gas composition
Total carbon in ROG = (0.8521 * 1) + (0.0794 * 2) + (0.0189 * 3) + (0.004 * 4) + (0.0039*4) +

(0.0013*5) + (0.0008*5) + (0.0002*6) + (0.0269*1) = 1.1378

Here taking the steam to carbon mole ratio is 3:1 we have.
Steam=3 *1.1378 * 3299.3967
= 11262.1607 kg mol/hr = 202718.8926Kg/hr
Total feed to reformer = ROG+ steam
= 3299.3967 + 11262.1607 = 14561.5574 kgmol / hr
For the methane reforming the following reaction take place

CH4 + H2O  CO + 3H2 --- (4.8)
C2H6 + 2H2O  2CO + 5H2 --- (4.9)
C3H8 + 3H2O  3CO + 7H2 --- (4.10)
C4H10 + 4H2O 4CO + 9H2 --- (4.11)
C5H12 + 5H2O 5CO +11H2 --- (4.12)
C6H14 + 6H2O 6CO +13H2 --- (4.13)
CO + H2O CO2 + H2 --- (4.14)
Assume: (1) 80% conversion of the first reaction 4.8.
(2) 100% conversion of 4.9, 4.10, 4.11, 4.12 and 4.13reaction.
(3) 57% conversion of reaction 4.10
From the reaction -1
CH4 consumed = 0.8 * 2811.416 = 2249.1328 kg mol / hr
CH4 unconverted = 2811.416 – 2249.1328 = 562.2832 kg mol / hr
H2O consumed = 2249.1328 kg mol / hr
H2 produced = 3*2249.1328 = 6747.3984mol / hr
CO produced = 2249.1328 kg mol / hr

From the reaction-2
C2H6 consumed = 261.972 kg mol / hr
H2O Consumed = 2*261.972 = 523.944 kg mol / hr
H2 produced = 5* 261.972= 1309.86 kg mol / hr
From reaction -3
C3H8 consumed = 62.3586 kg mol / hr
H2O consumed = 3*62.3586 = 187.0758 kg mol / hr
H2 produced = 7 * 62.3586 = 436.5102 kg mol / hr
From reaction -4
i-C4H10 consumed = 13.1976 kg mol / hr
H2O consumed = 4 * 13.1976 = 52.7907 kg mol / hr
n-C4H10 consumed = 12.8676 kg mol / hr
From reaction -5
i-C5H12 consumed = 4.2892 kg mol / hr

From reaction -6
Total CO produced from the first four reactions

= 2249.1328 + 523.944 + 187.0758 + 52.7904 + 51.4704 + 21.446 + 13.1975 + 3.96
=3103.0169 kg mol/hr
Total H2 produced
= 6747.3984 + 1309.86 + 436.5102 + 118.7784 + 115.8084 + 47.1812 + 29.0345 + 8.5787
= 8813.1498 kg mol/hr
Total H2O consumed
= 2249.1328 + 523.944 + 187.0758 + 52.7904 + 51.4704 + 21.446 + 13.1975 + 3.96
=3103.0169 kg mol/hr
H2O remaining
= 11262.1607– 3103.0169
= 8159.1438 kg mol / hr

N2 is used as an inert gas
So, N2 Input = N2 Output= 41.2424 kg mol/ hr
Output from Reformer

Component kg mol / hr Mol% Mol. Wt. Kg/hr
CH4 562.2832 2.707 16 8996.5312
H2O 8159.1438 39.28 18 146864.5884
CO 3103.0169 14.94 28 86884.4732
H2 8813.1498 42.44 2 17626.2996
CO2 88.7538 0.43 44 3905.1672
N2 41.2424 0.2 28 1154.7872
TOTAL 20767.5899 100 265431.8468
Table-3 output of the reformer
The above data are plotted in pie chart given below
N2
0%
H2O H2
39% 42%
CO
CH4 15%
3%
CO2
1%
fig-4 output of the reformer

3.3.3 Shift Reactor:
CO + H2O  CO2 + H2…………………………. (4.14)
CO inlet = 3103.0163 kg mol/hr.
.CO consume = 0.56 * 3103.0169 = 1737.6895kg mol/hr.
CO outlet = 3103.0169 – 1737.6895 = 1365.3274 kg mol/hr.
H2O consumed = 1737.6895 kg mol/ hr.
H2O outlet = 8159.1438 – 1737.6895 = 6421.4543 kg mol/ hr
H2 produced = 1737.6895 kg mol/hr.
CO2 produced = 1737.6895 kg mol/hr
Output of shift reactor

CH4 562.2832 2.7115 16 8996.5312
H2O 6421.4543 30.9668 18 15586.1774
CO 1334.297 6.4345 28 37360.316
H2 10550.8393 50.8804 2 21101.6786
CO2 1826.4433 8.8078 44 80363.5052
N2 41.2424 0.1989 28 1154.7872
TOTAL 20736.5595 100 164562.9956
Table-4 output of shift reactor

The above data can be plotted in pie chart given below
N2
0%
H2O
31%
H2
CH4 51%
3%
CO2
9%
CO
6% fig-5 output of shift reactor
3.3.4 CO2 Absorber
The absorption of CO2 is done by MDEA solution.
CO2 inlet = 1826.4433 kg mol/ hr
Assume efficiency of CO2 absorber is 99%.
CO2 outlet (remaining) = (0.01 *1826.4433) = 18.2644 kg mol/hr.
N2
0%
H2O
34%
H2
56%
CH4
3% CO2
0% CO
7%
fig-6 output of co2 Absorber

3.3.5 Pressure Swing Adsorber
Assume that 99.9% of CO, CO2& CH4 are get adsorbed.
Assume that 100% H2O & 0.5% H2 get adsorbed in PSA unit.
CO outlet = 0.001 * 1334.297 = 1.3343 kg mol/ hr.
CO2 outlet = 0.001 * 18.2644 = 0.01826kg mol/ hr.
CH4 outlet = 0.001 *562.2832 = 0.5623 kg mol/ hr.
H2O outlet = 0 kg mol/ hr.
H2 outlet = 0.995 *10550.8393 = 10498.08511kg mol/ hr ≈ 10500 kg mol/hr.
Composition at PSA Outlet

CO 1.3343 0.0127 28 37.3604
H2 10500 99.982 2 21000
CO2 0.01826 0.0002 44 0.80344
CH4 0.5623 0.005 16 8.9968
TOTAL 10501.9148 100 21047.16064
Table-5 outlet composition of PSA
The above data are plotted in pie chart given below
CO2 CO CH4
0% 0% 0%
H2
100%
fig-7 outlet composition of PSA

Overall material balance flow sheet for H2 production
Reformer tube
Shift reactor
Co2 Absorption unit
PSA unit
Fig-8 Material balance flow sheet of hydrogen production

Streams Component Mol. % kg mol / hr

CH4 85.21 2811.416
C2H6 0.0794 261.972
C3H8 0.0189 62.3586
i-C4H10 0.004 13.1976
n-C4H10 0.0039 12.8676
A i-C5H12 0.0013 4.2892
n-C5H12 0.0008 2.6395
n-C6H14 0.0002 0.6599
CO2 0.0269 88.7538
N2 0.0125 41.2424
2.707
CH4 2.707 562.2832
H2O 39.28 8159.1507
H2 42.44 8813.1498
B CO 14.94 3103.0169
CO2 0.43 88.7538
N2 0.2 41.2424
CH4 2.7115 562.2832
H2O 30.9668 6421.4543
H2 50.8804 10550.8393
C CO 6.4345 1334.297
CO2 8.8078 1826.443
N2 0.1989 41.2424
CH4 2.9706 562.2832
H2O 33.925 6421.4543
H2 55.7408 10550.8393
D CO 7.0492 1334.297
CO2 0.0965 18.2644
N2 0.2179 41.2424
H2 99.987 10500
E CO
CO2
0.0127
0.0002
1.3343
0.01826
Table-6 Material balance of hydrogen production

Chapter 4
Energy balance
4.1 Energy balance at individual equipment
4.1.1 Energy balance at steam reformer
Refinery off-gas Composition at Reformer Inlet

Component Flow rate kg/hr Cp at 450k (kJ/kg.k)
CH4 44982.656 2.7369
C2H6 7859.16 2.339
C3H8 2743.7784 2.34765
i-C4H10 765.4608 2.3592
n-C4H10 746.3208 2.3571
i-C5H12 308.8224 2.3343
n-C5H12 205.881 2.33
n-C6H14 58.08 2.3438
CO2 3905.1672 0.978
N2 1154.7872 1.049
Table-7 Inlet gas properties of reformer
= MCP∆T
= {(44982.656 * 2.7369) + (7859.16 * 2.339) + (2743.7784 * 2.34765) + (765.4608 * 2.3592) +
(746.6208 * 2.3571) + (308.8224 * 2.3343) + (205.881 * 2.33) + (58.08 * 2.3438) +
(3905.1672 * 0.9780) +(1154.7872 * 1.049)}*(450-298)
= 24 * 106 kJ/kg.k
Outlet from Reformer

Component Flow rate kg / hr Cp at 700 k (kJ/kg.k)
CH4 8996.5312 3.602
H2O 146864.5884 2.08
CO 86884.4732 1.113
H2 17626.2996 14.6
CO2 3905.1672 1.126
N2 1154.7872 1.098
Table-8 outlet gas properties of reformer

CHAPTER-4 ENERGY BALANCE
Qout= MCP∆T
= {(8996.5312 * 3.602) + (146864.5884 * 2.08) + (86884.4732 * 1.113) +
(17626.2996 * 14.6) + (3905.1672 * 1.126) + (1154.7872 * 1.098)} *
(700 -298)
= 280.43 * 106 kJ/hr
∆Q= Qout-Qin
= 256.43*106 kJ/hr
4.1.2 Energy balance at steam generator

Q=MCP∆T =>M=Q/CP∆T
Where T1 =373 k
T2 = 298 k
CP =38.73 kJ/Kmol.k
= (256.43*106 ) / (38.73*75)
= 88279.5421 kgmol/hr
Export stream= (88279.5421 -11262.1607)
= 77017.3814 kmol/hr
4.1.3 Energy balance at shift converter
Inlet of shift reactor

Component Flow rate kg / hr Cp at 623 k (kJ/kg.k)
CH4 8996.5312 12.546
H2O 146864.5884 8.677
CO 86884.4732 7.276
H2 17626.2996 7.197
CO2 3905.1672 11.311
N2 1154.7872 7.008
Table-9 Inlet gas properties of shift converter
Qin=MCP∆T
= {(8996.5312 * 12.546) + (146864.5884 * 8.677) + (86884.4732 * 7.276)

+ (17626.2996 * 7.197) + (3905.1672 * 11.311) + (1154.7872 * 7.008)} *
(623 -298)
6
= 714.515*10 kJ/hr

Outlet of shift reactor

Component Flow rate kg/hr Cp at 700 k (kJ/kg.k)
CH4 8996.5312 11.88
H2O 15586.1774 8.951
CO 37360.316 7.451
H2 21101.6786 7.035
CO2 80363.5052 11.489
N2 1154.7872 7.351
Table-10 outlet gas properties of shift converter
Qout=MCP∆T
= {(8896.5312 *11.88) + (15586.1774*8.951) + (37360.316 * 7.451) +
(21101.6786*7.035) + (80363.5052*11.489) + (1154.7872*7.351)}* (700-298)
6
= 1149.48*10 kJ/hr
∆Q= Qout-Qin
6
= (1149.48 - 714.515)*10 kJ/hr
6
= 434.965*10 kJ/hr
5.1.4 Energy balance at CO2 Absorber
Inlet of CO2 absorber

CH4 8996.5312 9.736
H2O 15586.1774 9.185
CO 37360.316 7.013
H2 21101.6786 6.974
CO2 80363.5052 9.871
N2 1154.7872 6.991
Table-11 Inlet gas properties of CO2 Absorber

Qin=MCP∆T
= {(8996.5312*9.736) + (15586.1774*9.185) + (37360.316*7.013) +
(21101.6786*6.974)+ (80363.5052*9.871) + (1154.7872*6.991)}* (366-298)
6
= 98 * 10 kJ/hr
Outlet of CO2 Absorber

CH4 8996.5312 8.552
H2O 15586.1774 8.026
CO 37360.316 6.965
H2 21101.6786 6.895
CO2 803.6336 8.89
N2 1154.7872 6.961
Table-12 outlet gas properties of CO2 Absorber
Qout= MCP∆T
= {(8996.5312*8.552) + (155861774*8.026) + (37360.316*6.965) +
(21101.6786*6.895)+ (803.6336*8.89)+(1154.7872*6.961)}*(466-298)
6
= 104.65*10 kJ/hr
∆Q= Qout-Qin
6
= (104.65 - 98)*10
6
= 6.65 * 10 kJ/hr
4.1.5 Energy balance at PSA
Intlet of PSA
CH4 8996.5312 9.736
H2O 15586.1774 8.185
CO 37360.316 6.015
H2 21101.6786 6.972
CO2 803.6336 9.723
N2 1154.7872 6.921
Table-13 Inlet gas properties of PSA

Qin= MCP∆T
= {(8996.5312*9.736) + (15586.1774*8.185) + (37360.316*6.015) +
(21101.6786*6.972) + (803.636*9.723)+ (1154.7872*6.921)}*(373-298)
6
= 50.48*10 kJ/hr
Outtlet of PSA
CO 37.3604 7.12
H2 21000 6.993
CO2 0.80344 10.662
Table-14 outlet gas properties
Qout=MCP∆T
= {(37.3604*7.12) + (21000*6.993) + (0.80344 * 10.662)}*(500-298)
6
= 29.72 * 10 kJ/hr
6
ΔQ = -20.76*10 kJ/hr
Now ∆M= Min-Mout

= 38227.464 kg/hr
∆T= 500 - 373
= 127 k
Cp= ΔQ/MΔT
6)
= (20.76 *10 /(38227.464*127)
= 4.27 kJ/kg.k
4.1.6 Off-gas temperature calculation
∆M= 8996.5312 + 15586.1774 + 1154.7872
= 25737.4958 kg/hr
Q= MCP∆T
∆T= Q/MCP
6
= (20*10 )/ (25737.4958*4.27)
= 181.98 k
T-298=181.98 k
T= 479.985 k (Off-gas temperature)

Chapter 5
Equipment design
5.1 CO2Absorption column design
Fig-9 CO2 Absorption column

CHAPTER-5 EQUIPMENT DESIGN
Basis: 99% of CO2 is absorbed
The feed gas rate= 20736.5592 kmol/hr
G1= 20736.5592 kmol/hr

Feed concentration, y1= 0.088 mole
Y1= y1/ (1-y1)
= (0.088)/ (1- 0.088)
= 0.096 mole
Feed gas rate on solute free basis (Gs) = G1* (1-y1)
= 20736.5592*(1-0.088)
= 18911.74 kmol/hr
CO2 gas entering = G1*y1
= (20736.5592)*(0.088)
= 1824.817 kmol/hr
Therefore CO2 absorbed= 1824.817*0.99
= 1806.569 kmol/hr
CO2 leaving = 18.247 kmol/hr
Concentration of Y2= 18.24/GS
= 18.24/18911.74
= 0.00096 mole
Concentration of y2= Y2/ (1+Y2)
= 0.00096/(1+0.00096)
= 0.00095 mole
Equation of equilibrium line Y= 1.32X……………………. (6.1)
X1= Y1 /1.32
= 0.096/1.32
= 0.073
Now the material balance equation is GS (Y1-Y2) = LS(X1-X2)
18911.74*(0.096-0.00096) =LS (0.073- 0)
LS=24621.53 kmol/hr
Actual liquid rate is 1.25 times the original, LS= 1.25*24621.53
= 30776.91 kmol/hr

The liquid at the bottom of the tower (L1) = LS+ CO2 absorbed
= 30776.91 + 1806.569
= 32583.48kmol/hr
5.1.1 Calculation of tray or column diameter
3
Data given:- ρG= 2.82 kg/m
3
= 0.175 lb/ft
3
ρL= 1038 kg/m
3
= 64.67 lb/ft
Now flow parameter (FLV) = (L1/G1)* (ρG/ ρL)0.5

0.5
= (32583.48/20736.5592)*(0.175/64.67)
= 1.57* 0.052
= 0.082 unit
Now calculate CSB= 0.23 from graph between FLV and tray spacing 18
0.5 0.2
inch Superficial velocity Usfl= CSB*[( ρL- ρG)/ρG] *(σ/20) ft/sec
= 0.23*1.004*19.19
= 4.5 ft/sec
Taking the operating velocity as 70% of the flooding velocity
US= 4.5* 0.70
= 3.15 ft/sec
Volumetric flow rate of gas = 164563/ 2.82
3
= 58355.674m /hr
3
= 2060811.178 ft /hr
Active tray area (Aa)= volumetric flow rate of gas/ operating velocity
= 2060811.178/(3.15*3600)
2
= 181.73ft
Tower cross section (AT)= Aa/(1-fd)
= 181.73/(1-0.2)
2
= 227.1625ft
0.5
Tower diameter ( DC) = (227.1625*4/3.14)
= 17 ft
= 5.2 m

5.1.2 Calculation of column height

Data given:-
GS= 1665.711kmol/hr y1= 0.088
LS= 2828.75 kmol/hr y2= 0.0008
Kxa= 1.25 kmol/m3.s.∆x x 2= 0
Kya= 0.075 kmol/m3.s.∆y
Now the vapour-liquid equilibrium data are found from the equation given below
y= 1.32x/(1+0.32x)………………………..(6.2)
X 0 0.01 0.03 0.05 0.07
y= 0 0.013 0.039 0.064 0.090
1.32x/(1+0.32x)
Table-15 vapour- liquid equilibrium data
Now plotting the equilibrium data on x-y plane and the operating line also plotted on the same
graph for determining the number of theoretical plate required
Fig-10 Operating line and Equilibrium line graph

From graph the number of ideal tray found is equal to 23
Number of real tray =
= 23/ 0.65
= 35
Now the slop –Kxa/Kya= -1.25/0.075
= - 16. 67
Now P1(x,y) = (0.0805, 0.107)
From graph P1 (xi, yi) = (0.0905, 0.103)
Slop -Kxa/Kya = - (Kxa/Kya)*(1-y) im/ (1-x)im
( ) ( )
Now (1 –y)im = ( )
( )
( ) ( )
(1 –y)im = ( )
( )
= 0.894
( ) ( )
(1 –x)im = ( )
( )
( ) ( )
(1 –x)im = ( )
( )
= 0.914
-Kxa/Kya = - (Kxa/Kya)*(1-y) im/ (1-x) im
= -16.67*(0.894/0.914)
= -16.30
From graph P2(x,y) = (0.035, 0.050)
P2 (xi, yi) = (0.0375, 0.048)
( ) ( )
(1 –y)im = ( )
( )
= 0.950

( ) ( )
(1 –x)im = ( )
( )
= 0.963
-Kxa/Kya = -16.67*(0.950/0.963)
= -16.44
From graph P3(x,y) = (0.0275,0.040)
P3(xi,yi)= (0.03, 0.038)
( ) ( )
(1 –y)im = ( )
( )
= 0.960
( ) ( )
(1 –x)im = ( )
( )
= 0.971
-Kxa/Kya= -16.67*(0.960/0.971)
= -16.48
( )
NtG =∫ dy
( ) ( )
∫ ( ) dy
= Area under the graph
Y 0.107 0.050 0.040
yi 0.103 0.048 0.038
f(y) 250 500 500
Table-16 Data of y and f(y)

600
500
400
300
f(y)
Series1
200
100
0
0 0.04 0.05 0.107
y
Fig-11 the graph between y and f(y)
Now the graph is plotted between y and f(y)

The number of gas phase transfer unit(NtG) = area under the
curve = 32
Number of gas phase transfer unit from grap (NtG) =32
Height of gas phase transfer unit (HtG) = G/Kya
G=G1/AT
2
G1= 20736.5592/32 kmol/h.m
2
= 648.017 kmol/h.m
G2= Gs/(1-y2)*1/AT
= 18911.74/(0.9992*32)
2
= 591.465kmol/h.m
G= (G1+G2) /2
= (648.017 + 591.46) /2
2
= 619.7385 kmol/h.m
HtG= 619.7385/(270*2.285)
= 1.004
Height (h)= HtG*NtG
= 1.004*32
= 32 m

[12]
Mechanical design
5.1.3 Shell design
Data given:-
Diameter of the column =5.2 m
Height of the column= 32 m
2
Outside pressure is 1atm= 0.1 MN/m
Design pressure Pd= 0.1*1.05
2
= 0.105 MN/m
Shell is I.S 2825-1969
2
Allowable stress f= 98.1 MN/m
Welding joint efficiency j= 0.85
5 2
Modulus of elasticity E= 1*10 MN/m
Now DO/L= 5.2/32
= 0.1613
By using DO/L ratio we can found K and M value from table given in book
Now K=0.224, M=2.54
M
P= K*E*(t/Do)
5 2.54
0.105= 0.224*10 *(t/5.2)
t= 0.051 m
= 51 mm
Checking plastic deformation:-
1
P= 2f*(t/Do)*
1  [1.5U (1  0.2Do / l) /100 * (t / Do)]
Where out of roundness (U) = 1.5% for new vessel
1
P= 2*98.1*(0.051/6.4)*
1  [1.5 *1.5(1  0.2 * 0.2) /100 * (0.051/ 5.2)]
2
= 0.417 MN/m
0.415>0.105
The shell thickness is correct

5.1.4 Head design

Assume Torispherical head
Fig-12 Torispherical head
Head thickness th= PDoC/2fJ

Where C→ stress concentration factor
“C” calculates from hE/DO and t/DO data table given in book
2
hE= [least of hO, Do /4Ro, (Doro/2)]
Do=Di+ 2ts
= 5.2+ 2*0.051
= 5.3 m
Assume Ri=RO=DO= 6.502 m
ho = Ro√( ) ( )
= 6.502√( ) ( )
= 0.823m
2
Do /4RO= (28.09)/ (4*6.502)
= 1.08 m

1/2 0.5
(Doro/2) = (5.3*0.390/2)
= 1.017 m
hE=ho=0.823 m
hE/Do=0.823/5.3
= 0.155
t/Do= PC/2fJ
= 0.105*C/ (2*98.1*0.85)
-3
t/Do = 0.6*10 C
Now C can found from t/Doand hE/Do table given in
book t/Do= 0.002
C= 4.1
th= 0.002*Do
= 0.002*5.3
= 0.0106 m
= 10.6 mm
5.1.5 Support design
Assume the support is skirt support
Fig-13 Cylindrical Skirt support

(i) Stress on skirt support due to dead weight of vessel
∑
fdb =
Now ∑
But ts=
-3 6 -3
0.8*10 /(2*96*10 *0.90)+ 3*10
= 0.003 m
= 3mm
4
= 3.14*6.4*0.003*32*7.7*10 N
= 148549.632 N
Wa= 18% of WS
= 26738.93 N
∑ N
∑ 175.2 KN
Wins=
-3 -3 3
= 3.14*(6.4+2*75*10 )*75*10 *32*5.64*10
= 278394.912 N
Wtray= 1000*( D2)*26

2
= 1000*0.785*5.3 *23
= 507164.95 N
Wloader = 365*(32+4)
= 13140 N
W1= Di * ρ L*L
2
-3 2
= (3.14/4)* (5.2 - 2*75*10 ) 1000*32
= 981250 N

∑
= 1955.238 KN
Now to calculate period of vibration
-5 3/2 1/2
=6.36*10 (H/D) *(W/ts)
-5 3/2 1/2
= 6.35*10 (32/5.2) (1754.2/0.003)
= 0.223 < 0.5
K2= 1
-5 3/2 1/2
=6.36*10 (H/D) *(W/ts)
-5 3/2 1/2
= 6.35*10 (32/5.2) (2284.067/0.003)
= 0.7 > 0.5
K2= 2
K1=0.7(cylindrical)
K= K1*K2
=0.7*2
= 1.4
∑
Now fdb(min)=
= / m2
∑
fdb(max) =
= KN/m2
(i) Stress due to wind load

(ii) KP1h1
-3
= 1.4*0.8*21*6.4*10
0.150 MN
(iii) K P2h2
-3
1.4*0.8*11*6.4*10 = 0.07884 MN

Total banding moment
( )
= 0.150*(21/2)+ 0.07884*32/2
= 2.836 MN
2
= MN/m
(iii) Stress due to seismic load

T= 0.167 to 0.615
CS (max) = 0.02/T
= 0.02/0.615
= 0.032
CS (min) = 0.02/T
= 0.02/0.617
= 0.119
Now fsb(min) =
=21/tsk KN/m2
fsb(max) =
= 62.85/tsk KN/m2

Resultant tensile stress (ft)R= (fwbor fsb)greater- fdb
2
= 0.077/tsk MN/m
Resultant compressive stress (fC)R= (fwbor fsb)greater+ fdb
2
= 0.208/ tsk KN/m
Now (ft)R≤ftJ
0.077/tsk= 96*0.90
tsk= 0.0009 m
= 0.9 mm
Similarly (fC)R= 0.125*E *(tsk/D)
0.208/tsk= 0.125*2*105*tsk/5.2
-3
tsk= 6.42*10 m
= 6.42 mm
Bolting plate requirement:
∑ ( )
(fc)max =
A = Dm1
Dm= Do+1
Z= D21
Take 1 = 100mm =0.1m

Dm= 5.2 +0.1
= 5.3
2
Z= (3.14*5.3 *0.1)/4
2
= 2.206m
A= 3.14*5.3*0.1
2
= 1.7 m

CHAPTER-5 EQUPMINT DESIGN
∑ =1955.238 KN
Msb = CWH
Msb = *0.032*1955.238*32
= 1334.8 KN
= 1.3348 MN
-3
( ) = (1955.238*10 /1.7) + (2.836/2.206)
2
= 2.435 MN/m
( ) ‹ 9.5 MN/m2
 all the data are correct and it is suitable for design
( )
tBP = 1*√
=0.1*√ = 0.027 m
tBP = 27 mm
tBP > 20mm ,than gussets plate be used to reinforce the plate
tBP = √
Breath of bearing plate (b) = 100 mm
Number of bearing plate (N) =

= 3.14*5.3/0.1
=167 gusset plate

Here l/b=1
2
M (max) = My = -0.119fcl
2
= -0.119*2.435*(0.1)
= 0.0029 MJ

CHAPTER-5 EQUPMINT DESIGN
tBP = √
tBP = √
= 0.013 m
= 13 mm
Dimension of bearing plate = l*b*tBP
= 0.1*0.1*0.013
-4 3
= 1.3*10 m
Stability factor (j) = Wmin*R/Mwb
= 175*45/2836
= 2.77 >1.5
But there is no anchor bolt design because, stability factor (j) > 1.5
Component Number Dimension
Bearing plate 167 0.1*0.1*0.027
Gusset plate 167 0.1*0.1*0.013
Anchor bolt 0 0
Table-17 component required for design
PARAMETER DESCRIPTION
Tower MOC SS304
Tower ID 5.2 m
Tower OD 5.3 m
Shell thickness 0.051 m
Head thickness 0.0106
Height of tower(Without support) 32 m

Type of Head Torispherical head
Tower Support Skirt support
Skirt MOC SS304

Skirt Height 4m
Skirt thickness 0.0009 m

Type Pall ring
MOC Metal (ss)
Table-18 Specification for CO2 Absorber Column

Chapter 6
Process control
6. Measurement and control devices:
Control is considered an important part of chemical engineering processes by controlling the
variables within the desired limits , this is for achieving desired production level or for ensuring
the safety of operation and operators. This is done by reading variables values and comparing
them to the desired values then process variables are adjusted which affects the variables to be
controlled until the desired values are obtained.
6.1. Purpose of using measurement and control devices:

{1} operating the plant within safety limits as follows:
[a] Keeping variables {pressure , temperature , flow ... etc. } within safety limits.
[b] Exposing danger areas and indicating any danger sign and automatic shut down when danger
appears.
[c] Indicating the danger of operating process used. That is when {if} there is danger in the
operation used, the devices will indicate it to us.
{2} accomplishing the required production rate.
{3} keeping the type of product {make up of product is part of required Specifications}.
{4} operating at minimum cost {without affecting any of the three previous purposes}.
6. 2. How to make a plan for measurement and control devices:

{1} we determine, in the control circuits, the variables to be controlled in the operating process:
[a] Level control devices .
[b] Pressure control devices.
[c] Flow control devices.
[d] Temperature control devices.
{2} we determine the practical variables to be controlled to make the product as required
specifications.
{3} determine the extra circuits required for safe operation.
{4} determine extra devices to monitor the operation of the plant by operators .
{5} determine places of taking samples for laboratory.
{6} determine the need for recording devices and places of reading, whether it is internal or in
control room .
{7} determine warning devices for shut down in danger cases.
 To achieve required performance and effectiveness from all devices, the following
common variables:
 Level control.
 Pressure control.
 Flow control.
 Temperature control.
 Ratio control.
CHAPTER-6 PROCESS CONTROL
6. 3. Models of measurement and control systems.
{1} level control {Lc}:

In each device there is a separator between two levels and we want to keep the separating line at
a specific level, we can do this by automatic control of the flow from the device by placing a
valve in the pump flushing line.
However, in tanks and reservoirs, the maximum liquid level of tank capacity is kept
{maintained} by automaticcontrol; the following diagram shows how the controlling device is
placed at the device exit. When the level exceed the required limit, a message is sent to the
control device which is divided into two parts . The first part compares the measured value with
required value and is called {the comparer}. The second part [called control} sends a message to
the control valve with the value of comparison, that is the difference between measured and
desired values the value is then opened or closed according to this value .
{2} pressure control {PC}:

The pressure control process is necessary for most operations of treating and receiving steam and
gas. the controlling method depends on the type of operation and device used , for example
controlling pressure in reactors , heat exchangers and absorption columns by direct relief in the
open air where gas is expelled out providing that the gas is not poisonous or expensive.
{3} flow control {FC}:

Usually flow control is used in pumps and storing vessels or any other device, a tank is used for
draining extra flow this control is also used for compressors and pumps that operate at constant
speed and a constant volume flows from them, in this case a bypass control is used.
{4} Ratio control {RC}:

This is used when we want to keep a constant ratio between two flows as in the figure , we find
that in the controlling device in the current {A} in the distillation column sends a message to the
controlling device , and the current control {B} sends a message to the control device , this way
the ratio is controlled . in the event a change in the flow of either current, the control device
sends a message to control management {A,B} to the adjust the flow to the required ratio of {A ,
B} currents .
{5} temperature control { TC}

The temperature is controlled by changing the hot or cold flow medium.

CHAPTER-6 PROCESS CONTROL
{Keys to control codes used}

CODE EXPLANATION
FC : FLOW CONTRALLER
FR : FLO W RECORDER
FRC : FLOW RECORDER CONTROLLER
FI : FLOW INDICATR
PA : PRESSURE ALARM
PI : PRESSURE INDICATOR
PIC : PRESSURE INDICATOR CONTROLLER
PRC : PRESSURE RECORDER CONTRALLER
PSV : PRESSURE SAFETY VALVE
TI : TEMPERATURE INDICATOR
TA : TEMPERATURE ALARM
TIC : TEMPERATURE INDICATOR CONTROLLER
LA : LEVEL ALARM
LIC : LEVEL INDICATOR CONTRALLER
LRC : LEVEL RECORDER CONTRALLER

Chapter7
Safety prevention loss
7.1. Safety and prevention loss :
Safety and reducing injures are important considerations in designing and operating chemical
plants.
The main danger, in chemical plants, comes from the effective of chemical compounds which
result from, or used in, reaction since these compounds affect the human body. Some are
poisonous and fatal. The operators are the most subjected to these injures. Some of these
materials are harmless while others have extremely dangerous effects.
Generally speaking , chemical elements can be dangerous , since the strong liquefied factors like
acids , bases and oxidized elements can destroy all micro living tissues in the human body, eyes
noses , and throats are especially sensitive to spray , dust and many steams and gases .
The proper planning of a plant will have great effect on minimizing the spread of fires.
Dangerous operations should be earned out in a separate building with walls against fire and
explosion.
7. 2. Aims of industrial security:

They incorporate the following factors:
{1} prevention {protection}.
{2}putting fire out.
{3} protection against contamination.
 These objects will be explained as follows:
{1} prevention {protection}:

The human is protected against dangers, from manufacturing process, by protective equipment
including the following:
 FIRSTLY : HEAD PROTECTION :
Against falling solid objects by using helmets.

 Protective helmet specifications :
(1) To be light weight so that the weight does not affect the head.
(2) To be poor conductor of heat.
(3) Its material is not affected by water to facilitate cleaning.

CHAPTER-7 Safety and prevention les
(4) To be nonelectric conductor.
(5) To have ventilation.
(6) To withstand the shock of a {20 kilo} body falling from {30meters height} without breaking.
• SECONDLY : EYES PROTECTION :
Some of dangers facing eyes, in plants, generally:

(1) Files and flying shrapnel from scraping, lathing ...etc.
(2) Industrial smoke and fumes.
(3) Oxidized and hot materials.
(4) Poor lighting at places of work.
(5) Bright rays resulting from electrical welding.
(6) Fumes and dust suspended in the air.
 Eye protective devices:
(1) Helmet attached protectors.

(2) All types of glasses including those for welding.
(3) Clear barriers normally fixed on machinery.
(4) Protectors or electrical welding hats.
 THIRDLY: PROTECTION EARS AGAINST NOISE:
There are various ear protectors {sound mufflers}

{1} Ear plugs:
There are many types, most suitable is that made of {portain} which takes the shape of the space
where it is located within few seconds.
{2}Ear cover:
Normally made of plastic and made up of two layers. It contains a sound absorbing material that
prevents sound from reaching the drum.
{3} Helmets:
They cover head and ears together. They are made of two 'layers separated by sound absorbing
material or vacuum.

CHAPTER-8 Safety and prevention less
 FOURTHLY :PROTECTING RESPIRATORY SYSTEM:
It is achieved by special devices and equipment that protect it against fumes and poisonous
gases, most important are:
(1) Elastic mask:
Made of elastic fluid and placed firmly on the nose. It is equipped with one or two plastic boxes
containing filter, made of cotton 5 to filter out dust.
(2) Cotton mask:
It is a filter in itself. Made of cotton to be placed on mouth and nose .it is used several times a
day or two days depending on work atmosphere.
(3) Trapping gas devices:
This type is used to trap inhaled poisonous gases by passing them over chemical matter that
reacts with and keep it.
 FIFTHLY : PROTECTING HANDS :
Gloves are used frequently in contacting hot objects or that conducting electricity. They do not
protect against cuts or amputation; but reduces injury.
 Main types are:
(1) Those used in cleaning.

(2) Those used in welding.
(3) Those used in chemical industries.
(4) Plastic {nylon} gloves that are used once. They are common in hospitals and laboratories.
{2} putting fire out:

 Main causes of fire are:
(1) Oxygen.
(2) Fuel.
(3) Heat.
 Material s for distinguishing fire:
(1) Water:
The basic aim of using water is cooling, for it absorbing heat from burning object, thereby
lowering temperature below flash point and as a result the fire is distinguished.
(2) Carbon dioxide:
It is an inert gas heavier than air. It reduces the amount of oxygen surrounding the fire so that
oxygen quantity is less than that required for burning.

CHAPTER-7 Safety and prevention les
(3) Foam:
It is known in plants as industrial foam because it results mechanical aeration of foam and water
solution.
(4) Dry chemical materials:
Most important is that containing more than {90%} sodium bicarbonates which are grinded to
small particles.
(5) Evaporating liquids:
They are hybrid hydrocarbons {producing salts} they prevent combustion and isolate the area
from oxygen they do not conduct electricity and therefore can be used to put fire containing
electrical equipment.
{3} protection against pollution:
• Pollutants can be divided into three types:
(a) Solid.
(b) Liquid.
(c) Gaseous.
Solid matter pollutes earth and liquid matter pollutes water, where gaseous ones pollute air.
8. 3. Methods of treating and disposing of industrial debris:

Industrial debris has many dangerous if it has exceeded the agreed and allowed limits. It has
harmful effects on environment, in general and man in particularly. For that reason; laws and
controls were put in place to limit pollution by industrial debris.
Since treating industrial debris increases production cost, we will explain some methods for
treating debris.
{1} Getting rid of it at source:
This happens in emergencies as a result of operating plants above their designed production
capacity which causes tanks and production units to over flow. The treatment is by having plants
operate around its capacity.
{2} Retrieving product that seeps with debris:
Retrieving as much as possible of the product from debris this is used when the product is
expensive.
{3} controlling the rate of drainage:
The rate is slowed in the ambient temperature where it is diluted but concentration remains
within allowed limits.
{4} Reversing the direction of debris drainage:
This is done chemically in special units; one disadvantage is that it is costly.

CHAPTER-8 Safety and prevention less
7. 4. Dangers associated with material used in manufacturing and methods of
protection against them:
{1} Hydrogen:
Very light, colouless , spreads fast in atmosphere no health hazard , but affects breathing in
closed spaces , danger arising is a combustion accompanied by strong crack .
Should be placed in unclosed places , to be placed in cold well ventilated places near.
firefighting equipment.
{2} Nitrogen:
Chemically inert, colouless and heavier than hydrogen, it does not ignite; but has effect on the
breathing process in closed spaces.
To be kept away from hydrogen and oxygen and to be in open places.
{3} Carbon Dioxide ( CO2 ):

Carbon Dioxide gas is not toxic but high concentration might cause asphyxiation due to lack of
oxygen. The maximum permissible concentration is 0.5 % by vol. A carbon dioxide
concentration of above 10 % by vol. might be fatal after a few minutes of exposure.
Since carbon dioxide is heavier than air, it will always accumulate in the lowest places, canals,
basement, and other places underground without adequate ventilation may be entered with
permission of shift supervisor.
{4} Carbon Monoxide ( CO ):

Pure carbon monoxide is odor and colorless, hence, not noticeable and therefore particularly
dangerous.
An exposure of half an hour to one hour to a 0.18 – 0.26 % by vol. concentration will be fatal.
Carbon monoxide has a stunning effect and is lethal. Mixed with air it is explosive.
First aid measures are:
Carry the victim outside, have him breathe deeply, start artificial respiration, if possible with
oxygen masks, in case of respiratory difficulty or paralysis, Call A Doctor.

Conclusion
A plant for producing 500 tons/day of H2 gas using refinery off gas is the scope of the present
work. In this regard complete material balance, energy balance, design of an equipment (CO2
Absorber), has been done, cost is nearly not that much due of using refinery off gas as a feed we
can use hydrogen for many process to product another component or as a fuel .

References
1 "Hydrogen". Van Nostrand's Encyclopedia of Chemistry. Wylie-Interscience.
2005. pp. 797–799. ISBN 0-471-61525-0.
2. Today’s Refinery, January 1995 issue.
3. 2001-Fuels usable for fuel reforming.
4. 2004-George W. Crabtree, Mildred S. Dresselhaus, and Michelle V.
Buchanan,The Hydrogen Economy.
5. www.wikipedia.org
6. The optimal design of pressure swing adsorption systems by Olive j smith,
Arthur w. westerterp j. chemical engineering science. Vol. 46 No. 12,pp. 2967-2976,1991.
7. L. Schlapbach, A. Zuttel: “Hydrogen-storage materials for mobile applications”, Nature,
414 (15 Nov. 2001), p. 353-357.
8. Oh, P. P.; Ray, A. K.; Rangaiah, G. P. Triple-Objective Optimization of an.
Industrial Hydrogen Plant. J. Chem. Eng. Jpn. 2001, 34 (11), 1341.
9. Hyman, M. H. Simulate Methane Reformer Reactions. Hydrocarbon Process. 1968, 47,131.
10. Chemical process principles- material and energy balance by
O.A.Hougen, K.M. Watson, R.A.Ragatz.
11. Mass transfer operation by Dr.B.K Dutta.
12. Equipment Design by B.C.Bhattacharya.
13. Chemical Reaction Engineering by Octave Levenspiel.
th
.14. Robert, H. Perry & Cecil, H. Chilton, “Chemical Engineers’ Handbook”, 5
Edition, McGraw-Hill Company-1973.
15.Handbook of piping design by G.K.Sahu, first edition, New age international
pub, 1997, p31-37.


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State of Libya

MINISTRY OF HIGHER EDUCATION AND SCINTIFIC RESEARCH

BRIGHT STAR UNIVERSITY - EL-BREGA

Faculty of technical engineering

Production of hydrogen from refinery

Project N.O. : CHE 2016 002 A 019

1. Adeal Ali Salem Aswiri 13172

‫جبِؼخ إٌجُ اٌسبطغ – اٌجز‪٠‬مخ‬

‫كلية الهندسة التقنية‬

‫إٔزبج اٌ‪١ٙ‬ذر‪ٚ‬ج‪ ِٓ ٓ١‬اٌغبساد اٌغ‪١‬ز ِصٕؼخ ِٓ اٌّصفبح‬

‫رلُ اٌّشز‪ٚ‬ع ‪CHE 2016 002 A 019:‬‬

‫‪13122‬‬ ‫‪ .1‬ػبدي ػٍ‪ ٟ‬سبٌُ اٌص‪٠ٛ‬ز‪ٜ‬‬

1stExaminer( The supervisor 2ndExaminer (The co-supervisor)

CHAPTER 1: 1.1 Introduction 1-2

CHAPTER 2: Process Description

CHAPTER 3: Material Balance

CHAPTER 7: Safety and prevention loss

Figure. No. Title Page No.

1 Temperature vs. exit carbon monoxide 6

Table No. Title Page No.

1 Refinery off-gas composition 3

Flv -flow parameter

Keywords: Hydrogen production, Steam methane reforming process, Exergy analysis;

PRODUCTION OF HYDROGEN 1 CHEMICAL ENGINEERING DEPARTMENT

1.2 PHYSICAL PROPERTIES OF HYDROGEN:

1.3 USES OF HYDROGEN

 It is used to prepare low temperature in liquid state.

PRODUCTION OF HYDROGEN 2 CHEMICAL ENGINEERING DEPARTMENT

1.4 refinery off-gas stream

1.4.1 Refinery off-gas composition

Component Mol. % Mol. Wt.

Table-1 refinery off-gas composition

PRODUCTION OF HYDROGEN 3 CHEMICAL ENGINEERING DEPARTMENT

1.5.1 Industrial reforming

CH4+ H2O ⇌CO + 3 H2……………………………… (2.1)

PRODUCTION OF HYDROGEN 4 CHEMICAL ENGINEERING DEPARTMENT

1.6. shift reactor

CO + H2O→ H2 + CO2……………………….. (2.3)

PRODUCTION OF HYDROGEN 5 CHEMICAL ENGINEERING DEPARTMENT

1.7. pressure swing adsorber

loading L2 of adsorbent at adsorption pressure P1 and temperature T2 and reduced pressure

PRODUCTION OF HYDROGEN 6 CHEMICAL ENGINEERING DEPARTMENT

Regeneration phase consist of several steps;

 Expansion to adsorption pressure, where the adsorbed components start to desorb

CH4 + H2O + heat →CO + 3H2……………….. (2.4)

PRODUCTION OF HYDROGEN 7 CHEMICAL ENGINEERING DEPARTMENT

1.9.2. Coal Gasification

1.9.3. Partial Oxidation of Hydrocarbons

CH4 + 1/2O2 →CO + 2H2 + heat………….. (2.6)

1.9.4. Biomass Gasification

In biomass conversion processes, a hydrogen-containing gas is normally produced in a manner

PRODUCTION OF HYDROGEN 8 CHEMICAL ENGINEERING DEPARTMENT

PRODUCTION OF HYDROGEN 9 CHEMICAL ENGINEERING DEPARTMENT

Photo-biological production of hydrogen is based on two steps: photosynthesis (2.12) and

Hydrogen Production: 4H+ + 4e– →2H2 …………………… (2.13)

PRODUCTION OF HYDROGEN 10 CHEMICAL ENGINEERING DEPARTMENT

PRODUCTION OF HYDROGEN 11 CHEMICAL ENGINEERING DEPARTMENT

= (30.8521 + 50.0794 + 70.0189 + 90.004 + 90.0039 + 110.0013 + 11*0.0008 +

Steam=3 1.1378 3299.3967