Sunteți pe pagina 1din 159

A PLANT DESIGN PROJECT ON

PURIFICATION OF SYNTHESIS GAS (208MMSCFD): REMOVAL OF ACID


GASES BY MDEA SOLUTION
Session 2009-2013

Supervised By:
Prof. Dr. Arshad Chughtai
Submitted By:
Waqas Iqbal CE09-10M08

Abdul Salam CE09-10M21

Haroon Saeed CE09-10M34

Ahmad Riaz Khan PG09-10M05

Institute Of Chemical Engineering and Technology


University ofthe Punjab,
Lahore.
Approval Certificate

It is certified that this report is submitted by the following students.

Waqas Iqbal CE09-10M08

Abdul Salam CE09-10M21

Haroon Saeed CE09-10M34

Ahmad Riaz Khan PG09-10M05

SUPERVISOR:
Prof. Dr. Arshad Chughtai .........................................
Institute of Chemical Engineering and Technology, Signature
University of the Punjab, Lahore.

External Examiner: ………………………………………..


Signature

II
Supervisor
Prof.Dr. Arshad Chughtai
Innovators:

Waqas Iqbal Abdul Salam Haroon Saeed Ahmad Riaz Khan


waqasiqbal.ce engr.abdulsalam09 haroon1988icet ark.khan.78
@gmail.com @gmail.com @gmail.com @gmail.com

Message:
“Throughout our university life we learned a lot of things not just about study but also
about life from our fellows and our teachers. We have made lifelong friendship,
memories and lived a dream life. Our teachers played hugely important role in
grooming our personality, they not only taught us engineering but more importantly
they tried best to make us a good human being and a responsible citizen. Words are not
enough to thanks them and we promise we will carry on this identity of I.C.E.T to new
level where ever we will go in future INSHAALLAH”

III
Acknowledgement
All praises to Almighty ALLAH who gave us light in darkness and gave us ability and
strength to complete our research project and all respects are for His Prophet
Muhammad (PBUH, on whom be ALLAH’S blessings and salutations)

We take immense pleasure in thanking our worthy teachers for their valuable help
regarding our research project. We all owe special thanks to our project supervisor
Prof. Dr. Arshad Chughtai, who helped us throughout our research work and during
the compilation of this Design project. His motivation, guidance and kind words
always encouraged us to work with commitment. Whenever we found ourselves in any
sort of trouble, we always found him available to cater the issue. This sort of
generosity and favor is highly commendable.

We are grateful to our parents for their special prayers that helped us achieve this
tedious task in the compilation of this design project.

IV
ABSTRACT
Synthesis gas produced from wood feed stock usually contains gaseous impurities
such as carbon dioxide and hydrogen sulphide which are acids in aqueous solution
thus highly corrosive to the processing equipment and poisonous to Catalyst,
impurities laden-gas is also highly toxic and malodorous and is referred to as “sour
gas”.

The purpose of project is to design “Amine Treating Unit” (ATU). There are many
processes for the recovery of acid gas from Synthesis gas but we selected Absorption
Process by using Amine solvents (MDEA), because the design of the process is
economically most favorable. The economics of the plant also make balance with the
efficiency and is most suitable to the oil and gas reserves of Pakistan.

The process selected for this purpose is the Absorption Process by using Amine
solvents (MDEA) and the unit is designed to treat 208MMSCFD of Synthesis gas. This
Design Project includes introduction and processing of various methods employed for
the Acid gas recovery from Synthesis gas.

ChemCAD, Aspen HYSYS, MS Excel, and MS Visio are the softwares that has been
used for the calculations and designing of the project.

The details of this Project contains material and energy balances across the Amine
treating unit (ATU), individual equipments design, instrumentation and control, cost
estimation, and Operational Problems of Amine treating unit (ATU).

In summary, the focus on the future improvements in the Absorption process by using
Amine Solvents makes this project distinctive and particularly relevant for educating
present or perspective engineers. We worked very hard to complete this project. Our
aim is to stimulate young future engineers. We also strived to develop the design of the
Amine Treating unit (ATU) that will capture engineer’s attention and is easy for the
engineers to use and adapt.

V
Table of Contents
1. INTRODUCTION
1.1 Synthesis Gas 1
1.2 Synthesis Gas: A Historical Overview 1
1.2.1 Historical Terminology Related to Different types of Synthesis gas 2
1.2.2 From Feedstock to Synthesis Gas: A brief over view 3
1.3 Need of Purification of Synthesis Gas 3
1.4 Application of Synthesis Gas 6
1.5 Principal Gas Phase Impurities 9
1.6 Gas purification 10
1.6.1 Absorption 11
1.6.2 Adsorption 21
1.6.3 Membrane Permeation 22
1.6.4 Chemical conversion 24
1.6.5 Condensation 24

2. PROCESS SELECTION
2.1 Process Selection 25
2.2 Process Description 28
2.3 Equipments used in The Process 29
2.4 Process Flow Diagram for Amine Sweetening Process 33

3. MATERIAL BALANCE
3.1 Introduction 34
3.2 Synthesis Gas Composition 35
3.3 Inlet Gas Separator 36
3.4 Mass Balance on Absorber 41
3.5 Mass balance on Stripper 44
3.6 Balance across over-head separator 46

VI
3.7 Balance across the overhead reflux drum 47
3.8 Overall material balance 47

4. ENERGY BALANCE
4.1 Introduction 48
4.2 Conservation of Energy 48
4.3 Forms of Energy 49
4.4 Inlet Separator 50
4.5 Absorber 59
4.6 Lean Solvent Exchanger 69
4.7 Lean/Rich amine exchanger 70
4.8 Over head Stripper Condenser 71
4.9 Stripper 74
4.10 Energy Balance across Hydraulic Turbine 79

5. EQUIPMENT DESIGN
5.1 Inlet Separator 81
5.2 Plate Heat Exchanger 85
5.3 Absorber Design 96
5.4 Stripper Design 109
5.5 MDEA Surge Drum 119

6. INSTRUMENTATION & PROCESS CONTROL


6.1 Amine Plant Control 120
6.2 Process Instrumentation Diagram for Amine plant 121

7. COST ESTIMATION
7.1 Plant Cost Estimation 122
7.2 Capital Investment 122
7.2.1 Direct costs 122

VII
7.2.2 Indirect costs 123
7.3 Types of Cost Estimation 123
7.4 Methods of Estimating Capital Investment 123
7.5 Percentage of Delivered Equipment Cost 123
7.6 Direct Cost 126
7.7 In-Direct cost 127

8. HAZOP STTUDY
8.1 HAZOP study 128
8.1.1 Objectives of HAZOP study 129
8.1.2 HAZOP Team 129
8.1.3 Strength of HAZOP 129
8.1.4 Weakness of HAZOP 129
8.1.5 Responsibility of HAZOP Team Members 130
8.1.6 Guide Words 130
8.2 HAZOP Study of storage Tank for MDEA 131

9. OPERATIONAL PROBELMS
9.1 Problems occurring during operation 134
9.2 Foaming 134
9.3 Corrosion 135

9.4 Chemical Losses 137


9.5 Losses due to Volatility 137
9.6 Entrainment 137

10. BIBLOGRAPHY 138

VIII
Chapter 1 Introduction
Chapter 1 Introduction

1.1 Synthesis Gas:


The word “Synthesis gas” now a day primarily refer to the mixture of Carbon monoxide and
hydrogen gas in different proportion containing small amount of carbon dioxide and other
traces. There are other names as well for this mixture of carbon dioxide and hydrogen
depending upon their origin and uses. For example:

On the basis of Application


1. CO and H2 mixture is also called as “Methanol Synthesis Gas” Because of their use in
production of Methanol CH3OH.
2. “Oxo Gas “ Is another name for CO and H2 mixture due to Hydroformylation

On the basis of origin


1. CO and H2 mixture Obtained from coal and steam can be called as “water gas “
2. Gas(CO+H2) produce from steam cracking of methane CH4 is called as “Crack gas “
Various raw Material which can be use for generation of Synthesis gas are :

 Hard Coal
 Brown Coal
 Natural Gas
 Mineral Oil Fractions
 Petroleum Gas
 Biomass
 Heavy Oil

Light oil fractions and Natural gas is most suitable for production of synthesis gas since they
contain high fraction of H2.

Revival of coal gasification is in progress by now in some part of world due to increasing oil
crisis and shortage

Synthesis gas can also be made from plastics using chemical recycling process which are use
to convert plastics to gaseous raw material (synthesis gas ) and liquid

1.2 Synthesis Gas: A Historical Overview:


The synthesis gas production history date back to long time ago in 1800s. In times date back to
1800s town gas was produce by gasification of coal, prior to the extensive availability of natural
gas and electricity. The town gas was then used for various purposes like residential cooking,

1
Chapter 1 Introduction

for lightening street lights and for industrial heating. With time the increasing demand for
chemicals and energy developed interest in field of synthesis gas technology. The main reason
for this was:

1. Due to high flexibility, synthesis gas can be used in variety of process like fuel
production, power generation, chemical manufacturing.
2. Synthesis gas provide better opening to use renewable fuels and low cost fuel as it
can be produce from multiple kind of solid fuel.

Below we will look into some historical development in the field of Synthesis gas:

1804: Coal Gas use for lighting was first patented

1813: Westminster Bridge which is in London was first light up with use of town gas on the

eve of New Year with help of wooden pipe for delivery of gas.

1816: Town gas was use for first time to Light up streets light in Baltimore Maryland, US

1800s: Town gas was use to replaces lanterns and candle in factories which lead to

possibility of night shift and evolution of industrial age.

1.2.1 Historical Terminology Related to Different types of Synthesis gas:


Water Gas: It is type of syn gas which is produce by reaction of steam with hot coke which
results in gaseous mixture containing Hydrogen and Carbon Monoxide in equal volume.

Producer gas: Reaction of coke with humid air produce syngas which contain nitrogen
diluent in significant amount, such gas is called producer gas

Town gas: It is a type of synthesis gas which is produced from coal. In 1800s it was basically
used for lighting. To create yellow flame for purpose of lighting, heavy hydrocarbons were
added.

Blast Furnace Gas: It is the product gas which is obtained from blast furnace where iron
oxide reduces using coke to produce iron. This process produces gas which contains
nitrogen in large amount.

2
Chapter 1 Introduction

1.2.2 From Feedstock to Synthesis Gas: A brief over view:


Synthesis Gas is normally yield from process of gasification in which the feed stock containing
carbon is process in the presence of high temperature and pressure depending on the
composition of feed stock normally temperature range is from 800 to 1500 degree Celsius . The
heat required for the process can be obtained from external heat source or by the process of
partial oxidation in which a portion of feed stock is reacted with oxygen to release the heat
required.

The next stage in production of synthesis gas is the called as reaction phase. In this phase the
feed stock react with oxygen, water vapors and carbon dioxide in case of oxygen rich material
the reaction is initiated by thermal decomposition.

The next stage in processing of synthesis gas is the purification stage. The gas produce in
previous steps is raw synthesis gas which is not very clean to be use in further process. In
purification process impurities like carbon dioxide, tar, ash, sulfur compound, methane, water
vapors is removed. After completion of purification process the ratio of carbon monoxide and
hydrogen is also adjusted depending on the product for which production this synthesis gas will
be use further. This synthesis gas is now ready for further use

When synthesis gas is brought in contact with different catalyst which mostly contain
compound of metal like copper, iron, Manganese, cobalt then new complex molecules are
formed. Now a days scientist working on finding new ways of creating already discovered
molecular combination by experimenting synthesis gas with different catalysts This is how
environmental friendly fuel can be made now a days.

1.3 Need of Purification of Synthesis Gas:


The synthesis gas obtained as result of gasification is cleaned or purify from sulfur bearing acid
gases like Carbonyl sulphide and Hydrogen disulphide to make them according to
environmental emission regulation or to save the downstream catalyst from poisoning or both.
According to The environmental regulation the sulfur contents in product syn gas should be less
than 30 parts per million by volume (ppmv) in order to meet the stack gas emission target of 4
parts per million by volume of sulfur dioxide. The synthesis should be purify to meet emission
standard set by global regulatory authority and also to meet the desires standard for
downstream use or applications.

When synthesis gas is used for combustion process or applications then it should be purify to
meet the required standard of atmospheric emission by keeping emission like SOx and NOx in
control. To determine the amount of purity of synthesis gas required for combustion process
we take help of material balances involve in combustion and assuming in what way synthesis

3
Chapter 1 Introduction

gas will be oxidized in the furnace or combustor(for calculation and estimation is considered
appropriate to assume impurities like NH3 and H2S are all converted into NOx and SO2 stack
emission ). The process where flue gases are scrubbed with the help of selective catalytic
reduction the sulfur removal from synthesis gas is also required to keep NOx under control.

In case of particulate the level of tolerance is negligible because downstream applications


cannot let particulate or fine ash to accumulate over extended operations that’s why the gas
purification methods currently use reduce particulate level to below all environmental
standard.

In the chemical or fuel production process the purity of synthesis gas is determined by catalyst
requirements. In some cases even small amount of impurities can damage or poison whole
catalyst so purification requirements in case of catalyst are quite strict and stringent. For
example Van Der Burgt and Higman (2003 ) showed that catalyst which is used in Fischer-
Tropsch(FT) for production of liquid fuel requires that the syn gas use as raw material should
contained combined HF+HCl+HBr less than 10 ppb. Now a day such techniques are use which
purify gas to such level that it can be used in FT process. So before using syngas as raw material
it is necessary to purify it to meet downstream applications. Below we will see in table the
purification level of synthesis gas required for different downstream applications

4
Chapter 1 Introduction

TABLE 1.1 Synthesis Gas Purification Requirements1


Impurity Turbines Chemical Fuel Cell Environmental
Production
Particulate Typical: <1ppmv in fuel, wide Process requirements often
range possible((Stringer, 1989; exceed environmental;
Wenglarzet al., 1986; Bossart et typical stack range (see
al.,1990; GE Power Systems, 1999) notes)PM10 < 0.015 lb/10
BTU (Ratafia-Brown et al.,
2002)

Total Sulphur Environmental or maybe set by Turbine stack SO2 range


6
SCR catalyst (~10 ppmv H2S fuel 0.03–0.2 lb/10 BTU
gas )(DeBiasi, 2005) (Ratafia-Brown et al., 2002)

Total Nitrogen Environmental Stack NOx limit, typical


Compound range 2 ppm–25 ppm.

Traces Impurities Set by material corrosion limits; See


See notes
notes for
Halides typical range 0.4–0.6 ppm molten
for molten
(Takematsu and Maude, 1991). Catalyst carbonate and
carbonate
and solid oxide fuel
Alkali (Na,K) Vendor specs, typical range 0.02–1 and solid
process
ppmw fuel (GE Power Systems, oxide fuel
1999).
specific
cell below
Metal (Hg,Cd,Se, V etc. ) Environmental and vendor specs. Recent IGCC permits: Hg
6
stacks emission~0.5 lb/10
BTU (WePower SCPC and
IGCC Information, 2003).

Produce in-situ;
Carbonyl
controlled to avoid turbine
material deposits

Carbon dioxide Environmental No standard to date

Fuel Cells: For molten carbonate fuel cells (MCFCs), earlier studies and requirements are
summarized by Thambimuthu (1993). For solid oxide fuel cells (SOFCs), recent studies have
established the required purity for multiple trace species; see papers by Gemmen and Trembly
(2006) and Trembly et al. (2007a, 2007b, 2007c).2

PM10: The particulate material lesser than 10 microns

5
Chapter 1 Introduction

1.4 Application of Synthesis Gas:


1. Power Generation:

Synthesis gas is a combustible material and can be used in various combustion processes as
fuel. It can also be used to produce steam which in turn can be used to produce electricity from
steam cycle using prime mover, gas engines, turbine as well as fuel cell.

In the big scale project that used coal gasification for the operation of gas turbine to produce
electricity using combined cycle technology, it is possible to operate that gas turbines on syngas
with combined cycle. This will provide opportunity to implement the idea of large scale
electricity production using syngas (biomass) without actually employing much effort on small
scale technologies of biomass gasification. Eventually by using this idea we can convert coal
fired power plant into biomass plant (bio syngas) for short term, it will help us to produce large
amount of green (environmental friendly) electricity. Implementation of this short term
possibility is more beneficial to produce large amount of clean, environmental friendly
electricity than relying just on those small scale green electricity production facilities. In this
way national governments and environmental authorities stringent emission limits can also be
met. This idea is already implemented in many facilities around the world For example, 253
Mega Watt coal fired entrained flow (IGCC) plant in Netherlands (Buggenum) is about 18 % by
weight biomass (bio syngas ) co fired.

1. Automobile Fuels:
It is widely expected that in future syngas will be used to produce large amount of Ultra clean
Transportation duel from process like GTL. Methanol/ DME and Fischer-Tropsch Diesel are the
prominent example of this idea.

 Methanol:
Methanol can be produce by using syngas. It can be produce by catalytic reaction of hydrogen
and carbon monoxide and some amount of carbon Dioxide. These reactions proceed with the
contraction of volume and both are exothermic in nature. This presence of small amount of
Carbon Dioxide keep the reaction in optimum zone in other words it enhance the reaction, As
these reaction are exothermic and proceed with reduction in volume so higher pressure and
lower temperature are favorable condition for reaction to occur.

It Important to keep an eye on side reaction of this process as those side reaction are also
highly exothermic and lead to the formation of many by product like that of methane DME
(Dimenthyl ether ) and higher alcohols. Now a days all over the world Methanol on Industrial

6
Chapter 1 Introduction

scale is produce by conversion of Syn Gas in the presence of desire catalyst. The process of
production of methanol is divided into three types on the basis of pressure used:

1. Lower pressure process using conditions of 50-100 bar


2. Medium pressure process employing 100-250 bar
3. Higher pressure process using 250-300 bar

Synthesis of Methanol from synthesis Gas involve following main reactions:

CO + 2H2 CH3OH

CO2 + 3H2 CH3OH + H2O


Both high and low pressure processes mainly differ on the basis of reactor design, operating
conditions and catalyst employed. Low pressure process are largely used in world now a
days due to their several advantages which includes better flexibility in the selection of
plant size, lower investment, better operational reliability , production cost.

 Fischer- Tropsch Synthesis:


In this process two moles H2 react with one mole CO to produce mostly straight chain
hydrocarbon (paraffin CxH2x) and primary alcohols with small quantity of unsaturated
hydrocarbon and branched hydrocarbon. The side reaction of FT Process includes coke
deposition, carbid formation, methanation, oxidation of catalyst.

Optimum operating condition for Fischer-Tropsch Synthesis include pressure in range of 25-60
bar and temperature should be in range of 200-350oC. Almost 20% of chemical energy is
dissipated in form of heat due to exothermic nature of this reaction. Following chemical
reaction take place:

CO + 2H2 H2O + -(CH2)-


Various types of synthetic fuel can be produce from synthesis gas by using Fischer-Tropsch
process. These product include light olefins, synthetic crude (light synthetic crude oil ), heavy
waxy hydrocarbons. Then further treatment of synthetic crude can produce high quality lube
oils, diesel fuel, naptha, aromatic liquid product. Fischer-Tropsch process can be operated on
various operating conditions to produce various types of product for example Fischer-Tropsch
synthesis process is carried out at high temperature of 330-350oC for direct production of light
olefins and gasoline similarly FT process is carried out at low temperature of 220-250oC for
production of diesel fuel and waxes.

7
Chapter 1 Introduction

2. Chemical Synthesis:
 Ammonia :
Large amount of ammonia (85% ) produce world wide is used in the synthesis of fertilizers
while the remaining amount of ammonia is use in other useful application. Every nitrogen
atom which is used in industry in various application is obtained somehow (indirectly or
directly) from ammonia or nitric acid (derivative of ammonia). NH3 is used in the synthesis of
plastics, explosives, fibers for used in polyamides, polyurethane, polyacronitril, fertilizers,
animal feed. Ammonia production process required two main thing firstly nitrogen
concentration should be high and secondly the amount of CO and CO 2 should be limited to less
than 20 ppmV.3 So before using synthesis gas amount of CO and CO2 should be controlled by
using various CO and CO2 removal process. Ammonia production is carried out at temperature
of 350-550oC and at a pressure of 100-250 bar in the presence of suitable catalyst. :

N2 + 3H2 2NH3

 Hydroformylation of olefins :
This process is also called as Roelen reaction or oxo-synthesis process for the manufacturing
of aldehydes on commercial scale. It is a catalytic reaction in which reaction take place
between synthesis gas (containing hydrogen and carbon monoxide) and olefins to form
aldehydes. These aldehydes contains additional carbon atom. The reactions occur as shown
below. In this reaction CO and H2 is added catalytically into olefins which result in aldehydes.

H2 + CO + R-CH=CH2 R-CH(CH3)-CHO + R-CH2-CH2-CHO

Alcohols and aldehydes are produce on industrial scale through Hydroformylation reaction.
The most significant products of oxo synthesis are C3-C19. Out of these butanal is one of the
most important product. Most used olefin is propene. The Products of oxo-synthesis is further
converted into aldol-condensation products, carboxylic acid, alcohols, primary amine.

 Hydrogen in refineries:
In refineries main source of hydrogen is synthesis gas. Synthesis gas is obtained from heavy oil
through gasification and mainly from natural gas through steam reforming. This hydrogen is
used in refinery for purpose of hydro-treating and in other hydro-processing process.
Hydrogenation of olefins and removal of impurities (nitrogen and desulphurization) is
accomplished by using hydro treating. There are many hydro-treating units in refinery for
hydro treatment of several product fractions which includes heating oil, gasoline, kerosene,

8
Chapter 1 Introduction

diesel etc and also for pretreatment of feedstock which is used in catalytic cracking process.
On the other hand transportation fuels can by produce from the products obtained as a result
of hydro processing operation. Hydro processing operation basically involves the production of
lighter products from heavy oil fractions. The feed stock requirement for hydro cracking is 4 :
sum of CO2 And CO should be less than or equal to 10-15ppmV, H2 should be more than or
equal to 98% by volume, O2 should be less than or equal to 100 ppmV, inert gas should be less
than 2% by volume.

1.5 Principal Gas Phase Impurities:


The principal gas phase impurities that must be removed by gas purification processes are listed
in Table.

Acid Gas:
It is a gas containing acidic components such as CO2, H2S,COS (carbonyl sulphide), CS2(carbon
sulphide) RSH that can form acidic solutions when mixed with water.

Composition:
Mainly contains of CO2 and H2S gases. Both gases can cause corrosion. These gases are obtained
after a sweetening process applied to a sour gas.

9
Chapter 1 Introduction

1.6 Gas purification:


It involves the removal of vapor-phase impurities from gas streams. The processes which have
been developed to accomplish gas purification vary from simple once-through wash operations
to complex multiple-step recycle systems.
The primary operation of gas purification processes generally falls into one of the following five
categories:

Chemical
Absorption in to a
liquid
Physical
Adsorption on a
solid

Gas Purification
Permeation through
a membrane

Chemical conversion
to another
compound

Condensation

10
Chapter 1 Introduction

1.6.1 Absorption:
It refers to the transfer of a component of a gas phase to a liquid phase in which it is soluble.
Stripping is exactly the reverse-the transfer of a component from a liquid phase in which it is
dissolved to a gas phase. Absorption is undoubtedly the single most important operation of
gas purification processes.
 Chemical Absorption
It is a type of separation process in which absorbent solution (solvent) reacts chemically with
acid gases presence in natural gas to produce compounds. E.g. Gas Sweetening process
• The compounds can be dissociated by heating or operating at low pressure of stripping.
• Used solvent is regenerated and re-use again

I. Amine solutions
Amines are of three types.

 Primary Amines:
Amines which have two hydrogen atoms directly attached to a nitrogen atom, such as
monoethanolamine(MEA) and 2-(2-aminoethoxy) ethanol (DGA), are called primary
amines and are generally the most alkaline.

 Secondary Amines:
Diethanolamine(DEA) and Diisopropanolamine(DPA) have one hydrogen atom directly
attached to the nitrogen atom andarecalled secondary amines.
Primary and secondary amines are known for their non-selectivity, and can remove
comparatively more CO2than H2S from the feed syngas stream.

 Tertiary Amines:
Triethanolamine (TEA) and Methyldiethanolamine (MDEA) represent completely substituted
ammonia molecules with no hydrogen atoms attached to the nitrogen, and are called tertiary
amines.

In comparison, a tertiary amine process such as MDEA and physical solvent systems of Selexol
and Rectisol can selectively remove first H2S then CO2
from a feed gas stream, and thus in principal, has a higher degree of control with meeting the
needed clean syngas specification. Also, MDEA has a lower circulation rate and regeneration
energy requirement than primary and secondary amine processes of MEA and DEA
respectively.

11
Chapter 1 Introduction

Table 1.2 Approximate Guidelines for Amine Process5

NOTES:
1. These data alone should not be used for specific design purposes. Many design factors must be considered for actual plant
design.
2. Dependent upon acid gas partial pressures and solution concentrations.
3. Dependent upon acid gas partial pressures and corrosiveness of solution. Might be only 60% or less of value shown for
corrosive systems.
4. Varies with stripper overhead reflux ratio. Low residual acid gas contents require more stripper trays and/or higher reflux
ratios yielding larger
reboiler duties.
5. Varies with stripper overhead reflux ratios, rich solution feed temperature to stripper and reboiler temperature.
6. Maximum point heat flux can reach 20,000–25,000 Btu/hr-ft2at highest flame temperature at the inlet of a direct fired fire
tube. The most satisfactorydesign of firetube heating elements employs a zone by zone calculation based on thermal efficiency
desired and limiting the maximum tube wall temperature as required by the solution to prevent thermal degradation. The
average heat flux, Q/A, is a result of these calculations.
7. Reclaimers are not used in DEA and MDEA systems.
8. Reboiler temperatures are dependent on solution conc. flare/vent line back pressure and/or residual CO2content required. It
is good practice to operatethe reboiler at as low a temperature as possible.
9. According to Total.
10. B.L. Crynes and R.N. Maddox, Oil Gas J., p. 65-67, Dec. 15 (1969). The heats of reaction vary with acid gas loading and
solution concentration. Thevalues shown are average

12
Chapter 1 Introduction

Applications of Amine Solutions


a) MEA

Advantages:
 used in solution of 15-18 wt%, to avoid corrosion.
 Low solvent cost.
 Good thermal Stability.
 reacts strongly with CO2 and H2S.
 High solution capacity at moderate concentrations typically acid gas. Pickup 0.33–0.40,
mols/mol amine,
 contaminated solution can be easily reclaimed.
 recommended for treatment of natural gas with low acid gas content (<10%)
 enables compliance with strict acid gas specifications.

Disadvantages:
 Operation energy consuming.
 Required very careful operation of unit.
 High corrosion potential than any other alkanolamines.
 Non selective removal in a mix acid gas system.
 High vapor pressure causes high vaporization losses in low-pressure operation.
 easily degraded.

 by oxidation
 by reaction of COS and CS
 by overheating the solution

13
Chapter 1 Introduction

b) DEA

Advantages:
• used in 15-20 wt% solution but upgraded from 25-40 wt% solution
• reduced in solution circulation flow rate and energy consumption
• Greater resistance to degradation than MEA
• Low in vapor pressure make DEA losses are reduced
• Effective in simultaneously remove CO2 and H2S
• Preferable to replace MEA for treatment of natural gas with low acid gas
content

Disadvantages:
 Operation energy consuming.
 Required very careful operation of unit.
 The reclaiming of contaminated solutions is more complex since vacuum distillation may
be required6

14
Chapter 1 Introduction

c) MDEA

Advantages:
 used in 35 –50 wt% solution.
 Selective removal of H2S
 it can be partially regenerated ina simple flash
 for extraction of H2S and leaving some CO2in treated gas
 For production of CO2 with little H2S to enhance oil recovery fluid.
 H2S enrichment of acid gas before treatment in Claus unit.
 not behave in the same way as MEA and DEA
 rate of reaction for MDEA-H2S extremely fast
 rate of reaction for MDEA-CO2involves formation of carbonic acid and slow
 Lower corrosion rates.
 Lower heat of reaction results in lower regeneration energy.
 It is more economical with respect to rates of solvent circulation and requirements for
energy7
Disadvantages:
 Contact time is too short for absorption of all CO2.
 For enhancing CO2 absorption some promoters should have to be added.
 Cannot be reclaimed by conventional reclaiming techniques.

15
Chapter 1 Introduction

Reaction of H2S & CO2 with Amine8


Beside the type of amine (primary, secondary. tertiary), a common mechanism applies for the
reaction of H2S.

Reaction 2 is instantaneous; the rate of diffusion of H2S from vapor to liquid phase controls the
rate of absorption of H2S.

For CO2, rate of absorption proceeds by two parallel chemical reaction schemes.

16
Chapter 1 Introduction

 Hydration of CO2 to carbonic acid which is then neutralized by amine to give


bicarbonate salt. The absorption of CO2 is limited by usually carbonic acid mechanism.

 The second mechanism consists of direct reaction of the amine and CO2 to form a
zwitterionic intermediate which reacts with a second mole of amine to form the amine
carbamate.Only primary and secondary amines such as MEA, DEA, and DGA can react
via the carbamate mechanism. With these classes of amines, carbamate formation is
rapid and the bulk of the CO2 is absorbed in this way.In the carbamate mechanism, two
moles of amine are consumed for each mole of CO2absorbed. Thus, primary and
secondary amines have a maximum practical CO2 loading of 0.5mole/mole.

17
Chapter 1 Introduction

II. Potassium Carbonate Solutions


 specific feature is absorption takes place at high temperature(110-120C)
 frequent use of term is ‘hot carbonate’
 same operating principle as amine process
 absorber and regenerator at similar temperatures
 has different flow scheme where heat recovery is concerned
 performance of conventional process with respect to sales
 gas specifications greatly improves by used of additives
 known commercial processes are:
– Catacarb
– Benfield
– Giammarco-Vetrocoke

18
Chapter 1 Introduction

 PHYSICAL ABSORPTION:
In this process an organic solvent is used to remove the acid gases from syngas. The process is
carried out at low temperatures and high pressures. In physical absorption the loading capacity
of the solvent is mathematically described by Henry’s law which states that the absorption is
directly proportional to the partial pressure of the acid gas component in the syngas. Hence the
more the volume of the syngas to be processed, the more is the solvent rate required for the
desired absorption. This is shown in the fig below. During solvent regeneration reboiling is used
along with flashing and stripping which raises the temperature and reduces the solubility of
absorbed aid gases.

Loading Capacity of Solvent Vs Partial Pressure9

Characteristics:
 Acid gases dissolve in the solution under pressure and temperature
 Favoured by high acid gas partial pressure concentrations (contributed by both pressure
of CO2 and/or H2S) and low temperature
 Use solvent is an operating parameter that will dictate the degree of efficiency of
absorption
 Solvent is regenerated by low pressure expansion of solution rich in dissolved acid gases
 Involves no chemical reaction between acid gases and the solvent

19
Chapter 1 Introduction

Principle Physical Solvents:10

Properties of solvents:
For industrial used, properties of solvents should have:
• high solubility with respect to acid gases
• low viscosity at operating temperature to facilitate solvent circulation
• resistivity to corrosion of carbon steel
• high thermal stability, i.e. not degraded under operating conditions (T, P, reaction)
• low vapor pressure at operating conditions to minimize solvent loss
• reasonable price

20
Chapter 1 Introduction

1.6.2 Adsorption:
It is the selective concentration of one or more components of a gas at the surface of a micro
porous solid. The mixture of adsorbed components is called the adsorbate, and the micro
porous solid is the adsorbent. The attractive forces holding the adsorbate on the adsorbent are
weaker than those of chemical bonds, and the adsorbate can generally be released (desorbed)
by raising the temperature or reducing the partial pressure of the component in the gas phase
in a manner analogous to the stripping of an absorbed component from solution. When an
adsorbed component reacts chemically with the solid, the operation is called chemisorption
and desorption is generally not possible.

Although adsorption can be practiced with many solid compositions, the great majority ofgas-
purification and dehydration adsorbents are based on some
form of silica, alumina (including bauxite), carbon, or certain silicates, the so-called molecular
sieves. The silica and alumina-base adsorbents are primarily
used for dehydration, while activated carbon has the specific ability of adsorbing organic vapors
and is very important for this purpose. The molecular sieves have very unusual properties with
regard to both dehydration and the selective adsorption of other compounds.

21
Chapter 1 Introduction

Physical Properties Of Desiccant Materials:11

1.6.3 Membrane Permeation:


It is a relatively new technology in the field of gas purification. Permeation is
• a technique that used in separating He and H2from other gases
• develop extensively for natural gas treatment
• based on difference in permeation rate that characterizes the speed of diffusion of various
constituents through membrane
• separation takes place through very fine hollow fibers of micro porous membrane.
• ‘fast gases’ like H2, He He and less content of CO2 and H2S are diffused through membrane
• ‘slow gases’ cannot pass through membrane, only constitute residual gas

22
Chapter 1 Introduction

Permeation rates of Gases12:

Advantages:
 Operational simplicity. The one-stage systems have no moving parts. For the two-stage
systems, the addition of the recycle adds some complexity.
 Reduced space requirements
 Ideal for remote locations
 Can be used to debottleneck existing solvent-based plant. In such cases, the membrane
is used for bulk acid gas removal, and the existing solvent-based system is used for the
final cleanup.
 contains little or no H2S.
 in treating NG very rich in CO2(over 20%)
 use lower CO2content to around 2%

Disadvantage:
 cannot be widely used until improve in permeability and selectivity of membrane and
resistance to deterioration.
 Because membranes use pressure as the driving force of the process, there may be a
considerable energy requirement for gas compression.

23
Chapter 1 Introduction

1.6.4 Chemical conversion:


It is the principal operation in a wide variety of processes, including catalytic and non-catalytic
gas phase reactions and the reaction of gas phase components with solids. The reaction of
gaseous Species with liquids and with solid particles suspended in liquids is considered to be a
special case of absorption and is discussed under that subject.

1.6.5 Condensation:
As a means of gas purification is of interest primarily for the removal of volatile organic
compounds(VOCs) from exhaust gases. This process consists of simply cooling the gas stream to
a temperature at which the Organic compound has a suitably low vapor pressure and collecting
the condensate.

24
Chapter 2 Process Selection
Chapter 2 Process Selection

2.1 PROCESS SELECTION:

Method used for gas treatment has various effects on the overall gas processing process and
facility. It usually affects the methods which are selected for various other processes like acid
gas removal, liquids fractionation, sulfur recovery, liquid product treatment and liquid recovery.
Following point’s designer must keep in mind while selecting any process for treatment of
gas13:

1. Designer must know the acid gas specifications.


2. The composition of hydrocarbon in gas should be considered.
3. The quantity (concentration ) and types of impurities which are present in the sour gas
must be consider
4. Concentration should be paid to the pressure and temperature of sour gas entering the
system and the required pressure and temperature of sweet gas which should be
obtained after treatment.
5. Residue gas specification should be noted
6. Volume of sour gas which should be treated
7. Selectivity needed for removal of acid gas
8. The environmental authorities regulations and limits regarding air pollution( emission
limits )
9. Operating and capital cost.
10. Specifications of liquid product
11. Selected process royalty cost.

Selection of the process can be done quite easily by examining the chart below shown14:

In our process the the partial pressure of acid gas of the feed (syngas ) is 71.355 psia while
the partial pressure of acid gas in the product is 7.178 psia. By comparing these values on
the chart above shown we get the following result

25
Chapter 2 Process Selection

Our process lies in the region where physical or amine system is feasible. We have to make now
selection between the amine or physical system.

The physical absorption process has draw back compare to other process that it is economically
less feasible when partial pressure of acid gas is low because capacity of physical solvent is
function of partial pressure.

According to Stupin, partial pressure of acid gas above 200 psia is suitable for physical
absorption whereas low partial pressure of acid gas is suit able for alkaline solution absorption.

Schaaf and Tennyson (1977) indicated that chemical solvents are use at partial pressure
between (60-100psia)and above this pressure range physical solvent is used15

From the discussion above made, chemical absorption would be our choice. In chemical
absorption we have different types of amines. We have selected a tertiary amine (Methyl di
ethyl Amine) due to the following distinctions over primary and secondary amines 16.

 MDEA serves saving of energy from reduced reboiler duties (reflux ratio 0.5 to 1.0) and
lower overhead condenser duties. Highly selective towards H2S when compared with
CO2, resulting in lower circulation rates and recycling higher quality of acid gas to
sulphur recovery unit.
 MDEA can be used in greater concentration thus a greater capacity to react with acid
gas

26
Chapter 2 Process Selection

 Usually the concentration 30-50% and 0.4-0.5 moles acid gas pick up per mole of MDEA
has increased the capacity of existing unit and allowed the equipment to be to be
considerably smaller for newer units. High pick up rate and high concentration reflects
lower solvent circulation rates for equivalent capacities

 MDEA has less heat of reaction with CO2 and H2S as compared with DEA and MEA

 The ranking of corrosivity of amines are as follows

MEA >> DEA >> MDEA

27
Chapter 2 Process Selection

2.2 Process Description:

The synthesis gas first enters the knock out drum followed by absorber in which most of the
absorption takes place. The solvent which is used for extraction of acid gas enters from top of the
absorber.

After the absorption of acid gases in absorber the solvent leaves the absorber from the bottom
and this solvent is called as Rich solvent (contain absorbed acid gases). This rich solvent then
passes through heat exchanger after which its temperature raises. In heat exchanger this rich
solvent exchanges heat with lean solvent coming from the stripper.

This rich solvent then enters in stripper where acid gases and some amount of water vapors are
removed from it and this mixture of water vapor and acid gases passes through the condenser and
then enters separator where water vapors are separated from acid gases. The water which left the
separator from bottom is the pump back to top of stripper column

The solvent which leaves from bottom of stripper is now called as lean solvent as acid gases are
removed from it. This solvent then passes through the heat exchanger where heat exchange takes
place between lean and rich solvent. Then this solvent enters the absorber from its top at
temperature and pressure of 110oF and 432psia respectively.

The typical synthesis gas production required for methanol production17:

The treated gas having H2S content of about 2ppmv is then sent to the ZnO bed to meet the
desired concentration of H2s of 10-5mol % to synthesize methanol

28
Chapter 2 Process Selection

2.3 EQUIPMENTS USED IN THIS PROCESS:

I. Inlet Separator:

The characteristic, objective and alternative equipment of inlet separator are mentioned below :

Objectives:
The main objective of inlet separator is to prevent liquid contaminants from entering in amine
system. These liquid contaminates are mostly hydrogen condensate, water or mist.

Characteristic:
Inlet separator is basically employ demister pad which remove liquid contaminates from carrying
over to amine system. It is a demister containing vertical drum.

Alternatives Equipment:
The equipment which can be used as replacement of inlet separator is Cartridge filter separator

II. Absorber:
The characteristic, objective of Absorber are mentioned below:

Objective:
The main application of absorber is to remove acid gas from the feed.

Characteristic:

 There are about to 2 or 3 packing bed or about 20 trays in fractionation column.


 To check the level at bottom of column there are three level gasses at bottom.
 One other thing which is necessary is this that there should be pressure differential
measuring instruments in column to keep close eye on pressure differential. The slow
pressure differential shows that there is some kind of fouling on bed or tray and the sharp
difference in pressure indicates that there is foaming.
 To avoid condensation of hydrocarbon the inlet temperature of lean solution should be
about 5 degree C higher than temperature of feed gas. On the other end if the
temperature of lean solution is much higher then there will be decrease in the amount of
acid gas picked by it and will result in higher loss of water as well

29
Chapter 2 Process Selection

III. Amine Flash Drum:


The characteristic, objective of Amine flash drum are mentioned below:

Objective:
The primary objective of Amine flash drum is to remove entrained liquid hydrocarbon and
dissolved gas prior to sending them to amine/amine heat exchanger& stripper for recovery of
amine solution.

Characteristics:

 It basically a three phase horizontal drum.


 To obtain good degassing the amine flash drum must be operated at low pressure
 The retention time of liquid in the amine flash drum is about 10 to 20 minutes.

Alternative Equipment:

Hydraulic turbine can be used in place of flash drum. Through the use of hydraulic turbine we can
produce power to drive circulation pumps.

IV. Amine/ Amine Heat Exchanger:


The characteristic, objective and alternative equipment of amine/amine heat exchanger are
mentioned below:

Objective:
The function of amine/amine heat exchanger is to heat the rich solution ( acid gas containing
solution ) before sending it to stripper ( regenerator). This reduces the heating load on stripper to
some extent.

Characteristics:

 It is shell and tube exchanger having lean solution on shell side whereas rich solution is in
tube side.
 To minimize the chances of erosion or corrosion as a result of mix flow, vaporization
should be as minimum as possible in exchanger.
 Maximum 1m/s velocity should be allowed.
 If more than one exchanger is to be used then exchangers will be installed one above the
other vertically. Rich solution will then enter the bottom exchanger from its lower part
and any released gas will flow out by moving upward alone amine solution.
 The inlet temperature of lean solution is about 110-130 degree C
 The outlet temperature of rich solution is about 90-110 degree C

30
Chapter 2 Process Selection

Alternative:
The alternative equipment for this purpose is plate frame exchanger . This exchanger offer high
heat transfer rates and larger surface area but are more prone to fouling.

V. Regenerator:
The characteristic, objective of Regenerators are mentioned below:

Objective:
The function of regenerator is to remove acid gases from rich solution by stripping so that rich
amine solution is regenerated.

Characteristics:

 There are about to 2 or 3 packing bed or about 20 trays in fractionation column.


 One other thing which is necessary is this that there should be pressure differential
measuring instruments in column to keep close eye on pressure differential. The slow
pressure differential shows that there is some kind of fouling on bed or tray and the sharp
difference in pressure indicates that there is foaming.
 To prevent loss of amine due to physical entrainment at the tower of regenerator there is
demister pad is installed.

VI. Reboiler:
The objectives, characteristics of Reboiler are shown below:

Objectives:
The main purpose of Reboiler is to add heat to the acid gases containing rich solution to generate
energy for moving the chemical reaction in backward direction which will result in stripping of acid
gases from rich solution and reboiler also produce steam required to remove acid gases. The
overhead reflux ratio governed the efficiency of stripping.

Characteristics:

 The reboiler mostly use is kettle type. The recommended tube pitch is square.
 The outlet temperature of the regenerated solution depends on amine strength and
operating pressure.
 The heating medium rate controls the duty of reboiler.
 The prevent amine degradation the temperature of less than 145 degree C is
recommended for tube skin.

31
Chapter 2 Process Selection

 To enhance the good natural circulation, space should be left below the bundle. This space
will also provide place for sludge deposition.
 To avoid overheating and localized drying the layer of liquid should be high enough that it
totally covers the tube bundle.
 Vapor volume should be high enough to prevent solution entrainments.

VII. Reflux Drum:


The objectives, characteristics of Reflux drum are shown below:

Objective:
The purpose of refuel drum is to recover the condensed water in condenser as stripper reflux and
also to remove any condensed hydrocarbon.

Characteristics:

 It is a demister pad containing horizontal or vertical drum.


 The temperature in the reflux drum should be as low as possible to prevent or
minimize concentration of water entrainment and amine to downstream facilities.
 The facilities of oil skimming should be provided.

VIII. Surge Tank:


The objectives, characteristics of surge tank are shown below:

Objectives:

Surge tank has spare capacity equal to that of amine solution hold up for maintenance unloading
or emergency

Characteristics:

 This is a cone roof or fixed roof Atmospheric storage tank.


 To prevent degradation of amine with oxygen blanketing is done with treated gas or
nitrogen.
 The operating temperature in surge tank should be higher than the freezing point of
solution.

32
Chapter 2 Process Selection

2.4 Process Flow Diagram for Amine Sweetening Process:

33
Chapter 3 Material Balance
Chapter 3 Material Balance

3.1 Introduction:
A mass balance (also called material balance) is an application of law of conservation of mass to
the analysis of physical systems. By accounting for material entering and leaving the system,
mass flows c a n b e identified which might have been unknown or difficult to measure without
this technique. The exact conservation law used in the analysis of system depends on the
context of problem but all revolve around mass conservation. That is that matter cannot
disappear or be created spontaneously.

The general form quoted for a mass balance is the mass that enters a system must, by
conservation of mass, either leave the system or accumulate within the system.

Mathematically the mass balance for a system within the system without chemical reaction is
as follows.

Input = Output + Accumulation


Strictly speaking the above equation holds also good for systems with chemical reactions if the
terms in the equation are taken to refer to total mass i-e the sum of chemical species of the
system. In the absence of chemical reactions the amount of any chemical species flowing in and
out will be same; This gives rise to an equation for each species in the system. However if this is
not the case then the mass balance equation must be amended t0 allow for the generation or
depletion (consumption) of each chemical species. Some use one term in this equation to
account for chemical reactions, which will be negative for depletion and positive for generation.
However, the conventional form of this equation is written to account for both a positive
generation term (i.e. product of reaction) and a negative consumption term (the reactants used
to produce the products). Although overall one term will account foi the total balance on the
system, if this balance equation is to be applied to an individual species and then the entire
process, both terms are necessary. This modified equation can be used not only for reactive
systems, but for population balances such as occur n particle mechanics problems. The
equation is given below; Note that it simplifies to the arlier equation in the case that the
generation term is zero.

Input + Generation = Output + Accumulation + Consumption


In the absence of a nuclear reaction the number of atoms flowing in and out are the same, even
in the presence of a chemical reaction. To perform a balance the boundaries of the system
must be well defined Mass balances can be taken over physical systems at multiple scales. Mass
balances can be simplified with the assumption of steady state, where the accumulation term is
zero 1>5.

34
Chapter 3 Material Balance

Here an assumption is taken that there is no chemical reaction is taking place and our system is
steady state process. Hence

Mass in = Mass out

3.2 Synthesis Gas Composition:18

Design Basis: 208mmscfd =22167

Component Mole % Molar Flow


lbmole/hr
H2 0.3198 7089
CO2 0.1658 3675.648
CO 0.1462 3242.0364
H2O 0.3541023 7849.63
CH4 0.01316 291.4674
C2H4 8.35E-5 1.86654
C2H6 1.65E-5 0.373308
C6H6 2.54E-5 0.563
C10H8 7.05E-7 0.01563
NH3 7.696E-5 1.706
H2S 0.000336 7.46616
N2 0.000379 8.32764

35
Chapter 3 Material Balance

3.3 Inlet Gas Separator:

Vapor (V)

300

Feed (F)

205

Condensate Liquid (L)

301

Our inlet gas separator has a temperature of 110 °F, so those components which have critical
temperature less than 110 °F will remain in gas phase. Otherwise they will be in liquid phase.

Gaseous Phase Components Liquid Phase Components


H2 H2O
Co2 NH3
CO C6H6
CH4 C10H8
C2H4
C2H6
H2S
N2

36
Chapter 3 Material Balance

Hydrogen Sulfide has not critical temperature less than 110 °F but it has a very high vapor
pressure so that at this temperature of inlet gas separator, H2S will be present in gas phase.

According to Roult,s Law,

Ya = Mole fraction of component in vapor

Xa= Mole fraction of component in liquid

Pva= vapor pressure of component

P= Total pressure (in PSI)

Antoine Equation,

( )

Where A,B and C are constants

T = Temperature in kelvin K

P*= Saturated vapor pressure in mmHg

Inlet gas separator temperature = 110°F =316.33K

Component A B C ln(P*) (P*)psi (P*)mmHg


H2O 18.3036 3816.44 -46.13 4.179 1.263 65.30
NH3 16.9481 2132.50 -32.98 9.42 238.52 4536.9
C6H6 15.9008 2788.51 -52.36 5.33 4.02 206.44
C10H8 16.1426 3992.01 -71.29 -0.06 .0182 0.94

37
Chapter 3 Material Balance

Vapor pressure determination using Antoine Eq. is given as follows.

P = 429.5psi

Using Roult,s Law,

1. For Water:
YH2O = XH2O = 2.9406 x 10-3 XH2O (1)
2. For Ammonia:
YNH3 = XNH3 = 0.555 XNH3 (2)
3. For Benzene:
YC6H6 = XC6H6 = 9.35 x 10-3 XC6H6 (3)
4. For Naphthalene:
YC10H8 = XC10H8 = 4.23 x 10-5 XC10H8 (4)

 Overall material Balance on Inlet gas Separator

Using Component Balance

I. For H2:
7089.5 = XH2L + YH2V
As it is only present in Vapor phase, so XH2L = 0
7089.5 = YH2V
YH2 = (5)
II. For CO2:
3674.73 = YCO2 V
YCO2 = (6)
III. For CO:
3241.36 = YCO V
YCO = (7)
IV. For CH4:
291.69 = YCH4 V
YCH4 = (8)
V. For C2H4:
1.86 = YC2H4 V

38
Chapter 3 Material Balance

YC2H4 = (9)
VI. For C2H6:
0.367 = YC2H6 V
YC2H6 = (10)
VII. For H2S:
7.44= YH2S V
YH2S = (11)
Viii. For N2:
8.39 = YN2 V
YN2 = (12)
IX. For H2O:
7849.39 = XH2O L + YH2O V
From Eq.1
7849.39 = YH2O/2.9406 x 10-3 L + YH2O V
7849.39 = YH2O { L (340.136) + V }
YH2O = ( )
(13)
X. For NH3:
1.706 = XNH3 L + YNH3 V
From Eq.2
1.706 = YNH3/0.555 L + YNH3 V
1.706 = YNH3 {1.80 L +V}
YNH3 = * (14)
+
XI. For C6H6:
2.44 = XC6H6 L + YC6H6 V
From Eq.3
2.44 = YC6H6/9.35 x 10-3 L + YC6H6 V
2.44 = YC6H6 {106.95 L + V}
YC6H6 = (15)
* +
XII. For C10H8:
0.0156 = X C10H8 L + YC10H8 V
From eq.4
0.0156 = YC10H8/4.23 x 10-5 L + YC10H8 V
0.0156 = YC10H8 {23640.6L + V}
YC10H8 = * +
(16)

39
Chapter 3 Material Balance

Now , we know that ∑

Adding all the mole fractions (adding eq. 5 to eq.16)

1= + + + + + + + + ( )
+

+* +*
* + + +

Multiplying by V on both sides

V=V[ + ( )
+* +* +* ]
+ + +

We know that
L = 22167 – V
Putting this value in above Equation and solving by computer program
V = 14358
L = 22167 – 14358
L = 7809
By putting the value of V in Eq. (5 to 16) , we get
Composition of stream 300:
YH2 0.494
YC02 0.256
YCO 0.2258
YCH4 0.0203
YC2H4 0.00013
YC2H6 0.000026
YH2S 0.00052
YN2 0.00058
YH2O 0.00294
YC6H6 2.87 x 10-6
YNH3 6.0 x 10-5
YC10H8 8.5 x 10-11

40
Chapter 3 Material Balance

3.4 Mass Balance on Absorber:

302 H2S 4ppm


CO2 2 mole%

311
Amine recirculation rate

300

V = 14358

303

E
For stream 300:
Component Mole % Molar Flow
H2 0.494 7092.852
CO2 0.256 3675.648
CO 0.2258 3242.0364
H2O 0.00294 42.21252
CH4 0.0203 291.4674
C2H4 0.00013 1.86654
C2H6 0.000026 0.373308
C6H6 0.00000287 0.04120746
C10H8 8.5E-11 1.22043E-06
NH3 0.00006 0.86148
H2S 0.00052 7.46616
N2 0.00058 8.32764

41
Chapter 3 Material Balance

Amine Circulation rate:


For MDEA,
( )
GPM =

Where Gas Flow = 135mmscfd

H2S = mole % of H2S to be removed = 0.0518%

CO2 = mole % of CO2 to be removed = 23.6%

M.wt = molecular weight of amine = 119.16

ML = acid gas loading i-e = 0.40

Wt = amine solution weight percent re-circulated = 50%

So,
( )
GPM =

GPM = 3919

Solution density at standard state = 8.68

Then ,

3919 x 8.68 x = 2041015.2

Using recommended 15% safety factor, lean amine flow rate = 2041015.2 x 1.15

= 2347167.48

We know , re-circulated MDEA contains . We assume that H2S is completely


stripped off, so only CO2 is present in re-circulated amine.

Amine present in solution = 0.50 x 2347167.48

= 1173583.74

42
Chapter 3 Material Balance

= 9848.80

So,

Acid gas present (CO2) = 49.24

= 2166.689

Water present in solution = 0.50 x 2347167.48

= 1173583.74

Moles of water =

= 65200

Lean amine re-circulation rate (including acid gas) = 65200 + 9848.589 + 49.24

= 75098

We can write,

D = 10680.037 + 0.02D + 4 x 10-6

D = 10680.037 + 0.0200D

D = 10898

In D stream,

CO2 = 10898 x 0.02

CO2 = 217.96 = 9590.24

H2S = 10898 x 4 x 10-6

H2S = 0.0218 = 0.7412

In E stream,

CO2 = 161728.5 + 2166.689 – 9590.24

43
Chapter 3 Material Balance

CO2 = 154304.95 = 3507.28

H2S = 253.844 – 0.7412

H2S = 253.1028 = 7.44

H2O = 759.834 + 1173583.74 – 759.834

H2O = 1173583.74 = 65200

MDEA = 9848.589 308

3.5 Mass balance on Stripper:

306

312

305 309

307
Inlet stream 305: Out Stream 307:

MDEA = 1173583.74 MDEA = 1173583.74

Water = 1173583.74 Water = 1173583.74

44
Chapter 3 Material Balance

H2S = 254.218 CO2 = 2166.68

CO2 = 154308

CO2 in C stream would be as = 154308 – 2166.68

= 152141.32

H2S in C stream would be as = 254.218 – 0

= 254.218

Usually 0.8% water is lost in c stream

So, = 0.8% x 1173583.74 = 9388.66

Make up water is added usually to replenish this loss

So, make up water = 9388.66

C stream would be as:

CO2 = 152141.32

H2S = 254.218

H2O = 9388.66

Total flow rate of C stream = sum of all = 161784.198

45
Chapter 3 Material Balance

3.6 Balance across over-head separator:


308

313

312

309

Inlet stream 313: Outlet stream 308:

CO2 =? CO2 = 152141.31

H2S =? H2S = 254.218

H2O =? H2O = 9388.66

Reflux stream 309 = D=? Stream C = makeup water

Our reflux drum has a temperature of 130 °F , so those components which have a critical
temperature less than 130 °F will remain in gaseous phase otherwise they would remain in
liquid phase.

Gaseous phase components Liquid phase components

CO2 H2O

H2S

So feed stream contain same CO2 and H2S as in the vapor phase.i-e

CO2 = 152141.32 and H2S = 254.214

46
Chapter 3 Material Balance

It is reported that reflux ratios between to mole of water per mole of acid gas are generally
used to make the process work properly.19

Moles of acid gas above reflux drum = 3548 + 7.447

= 3465.477

Taking reflux ratio as =

Reflux 309 stream (D) would be = 1.26 x 3465.477

= 4366.501

= 78597 of water

3.7 Balance across the overhead reflux drum:


Water:

AH2O + 9388.66 = 9388.66 + 78597

AH2O = 78597

Stream A will now become

CO2 = 152141.31

H2S = 254.218

H2O = 78597

Total flow = 230992.33

3.8 Overall material balance:


Feed + makeup water = sweet gas + condensate + acid gas

413207 + 9388.66 = 120291.5 + 140568 + 161784.198

422595.66 = 422643.7

47
Chapter 4 Energy Balance
Chapter 4 Energy Balance

4.1 Introduction:
As with mass, energy can be considered to be separately conserved in all but nuclear process.
The conservation of energy, however differ from that of mass in that energy can be generated
(or consumed) in a chemical process. Material can change form, new molecular species can be
formed by chemical process, but total mass flow into a process unit must be equal to flow out
at the steady state. The same is not true of energy. The total enthalpy of outlet streams will not
equal to that of inlet streams if energy is generated or consumed in the process; such as that
due to heat of reaction. Energy can exist in several forms: heat, Mechanical energy, electrical
energy, and these are the total energy that is conserved. In process design, energy balance are
made to determine the energy requirements of the process: heating, cooling and power
required. In plant operation, energy balance (energy audit) on the plant will show the pattern
of the energy usage, suggest areas for conservation and savings.

4.2 Conservation of Energy:


As for material, a general equation can be written for the conservation of energy:

Energy out = energy in + generation – consumption – accumulation

It is the statement of first law of thermodynamics. An energy balance can be written for any
process step. Chemical reaction will evolve energy (exothermic) or consume energy
(endothermic). For steady state processes, the accumulation of both mass and energy will be
zero. Energy can exist in many forms and this, to some extent, makes an energy balance more
complex than material balance.

In our project we are using the steady state energy balance i.e

Amount of heat in = Amount of heat out

As we are using the relation given below for the calculation of heat

Q= m Cp ∆T

Where

Q = Amount of heat

M = mass

Cp = specific heat

∆T = Given Temperature – reference temperature

48
Chapter 4 Energy Balance

4.3 Forms of Energy:


i. Potential energy:

Energy due to position;

Potential energy = gz

Where z = height above some arbitrary datum, m

G = gravitational acceleration (9.8 m/s2)

ii. Kinetin energy:

Energy due to motion;

Kinetin energy = u2/2

Where u = velocity, m/s

iii. Internal energy:

The energy associated with molecular motion. The temperature T of the material is a measure
of its internal energy U;

U = f(T)

iv. Work:

Work is done when a force acts through a distance;

W = FD

Where F = force

D = Distance

v. Heat:

Energy is transferred either as heat or work. A system does not contain “ Heat” but the transfer
of heat or work to a system changes its internal energy. Heat taken in by a system from its
surrounding is conventionally taken as positive and that given out as negative.

vi. Electrical energy:

Electrical and mechanical forms of energy are included in the work term in an energy balance.
Electrical energy will only be significant in an energy balance on electrochemical processes.

49
Chapter 4 Energy Balance

4.4 Inlet Separator:

300

205
Syn gas

301

 General Energy Balance Equation:-

Q- Ẇs =ΔH+ΔEx+ΔEp (1)

Assumption:-

Negligible effect of ΔEp and ΔEx so we take

ΔEx=0 ; ΔEp=0

No moving parts , Hence

Ẇs=0

Equation (1) reduces to

Q = ΔH (2)

Energy balance on different streams link with Inlet Separator:


Reference temperature is 77F

For Stream No 205 :


Components:

50
Chapter 4 Energy Balance

I. Hydrogen:
Formula used is Q = oCpΔT

o(Molar flow rate )=7093.44 , Cp= 6.9

Q= o x Cp x ΔT
Q= 7093.44 x6.9x33

Q=1615176.288

II. Carbon Dioxide CO2:


Formula used is Q = oCpΔT

o(Molar flow rate )=3657.555 , Cp=9.12

Q= o x Cp x ΔT
Q=3657.555x9.12 x33

Q=1100777.753

III. Carbon Monoxide CO:


Formula used is Q = oCpΔT

o(Molar flow rate )=3236.382 , Cp= 6.97

Q= o x Cp x ΔT
Q=3236.382 x 6.97 x 33

Q=744400.2238

IV. Water H2O


Formula used is Q = oCpΔT

o(Molar flow rate )=7862.6349 , Cp=17.98

Q= o x Cp x ΔT
Q= 7862.6349 x 17.98 x33

Q=46611`5215.792

51
Chapter 4 Energy Balance

V. Methane CH4:
Formula used is Q = oCpΔT

o(Molar flow rate )=288.171 , Cp=8.7

Q= o x Cp x ΔT
Q= 288.171 x 8.7 x 33

Q= 82733.8941

VI. Ethylene C2H4:


Formula used is Q = oCpΔT

o(Molar flow rate )=1.8575 , Cp= 10.7

Q= o x Cp x ΔT
Q= 1.8575 x 10.7 x 33

Q=655.91665

VII. Ethane C2H6:


Formula used is Q = oCpΔT

o(Molar flow rate )= 0.36 , Cp= 13.09

Q= o x Cp x ΔT
Q= 0.3657 x 13.09 x 33

Q= 157.9954

VIII. Benzene C6H6:


Formula used is Q = oCpΔT

o(Molar flow rate )= 0.563 , Cp= 21.13

Q= o x Cp x ΔT
Q= 0.563 x 21.13 x 33

Q= 392.60

52
Chapter 4 Energy Balance

IX. Tar C10H8:


Formula used is Q = oCpΔT

o(Molar flow rate )= 0.0156 , Cp=33.88

Q= o x Cp x ΔT
Q= 0.01562 x 33.88 x 33

Q= 17.47

X. Ammonia NH3:
Formula used is Q = oCpΔT

o(Molar flow rate )= 1.76 , Cp= 8.63

Q= o x Cp x ΔT
Q= 1.76 x 8.63 x 33

Q= 502.5100184

XI. Hydrogen Sulphide H2S:


Formula used is Q = oCpΔT

o(Molar flow rate )=7.448112 , Cp=8.63

Q= o x Cp x ΔT
Q= 7.448112 x 8.63 x 33

Q= 2022.832738

XII. Nitrogen:
Formula used is Q = oCpΔT

o(Molar flow rate )=8.401293 , Cp= 6.97

Q= o x Cp x ΔT
Q= 8.401x 6.97 x 33

Q=1932.381403

53
Chapter 4 Energy Balance

Total heat (Q) of this stream is = 8213985.662

For Stream No 301:


Components:
I. Water H2O
Formula used is Q = oCpΔT

o(Molar flow rate )=7808.2191 , Cp=17.98

Q= o x Cp x ΔT
Q= 7808.2191 x 17.98 x33

Q=4632928.721

II. Benzene C6H6:


Formula used is Q = oCpΔT

o(Molar flow rate )= 0.05356974 , Cp= 21.13

Q= o x Cp x ΔT
Q= 0.05356974 x 21.13 x 33

Q= 37.353644

III. Tar C10H8:


Formula used is Q = oCpΔT

o(Molar flow rate )= 0.0156 , Cp=33.88

Q= o x Cp x ΔT
Q= 0.01562 x 33.88 x 33

Q= 17.47

IV. Ammonia NH3:


Formula used is Q = oCpΔT

o(Molar flow rate )= 0.843372 , Cp= 8.63

54
Chapter 4 Energy Balance

Q= o x Cp x ΔT
Q= 0.843372 x 8.63 x 33

Q=240.1839119

Total Heat for Stream 301 is 4633223.702

For Stream 300:


Components:
I. Hydrogen:
Formula used is Q = oCpΔT

o(Molar flow rate )=7092.852 , Cp= 6.9

Q= o x Cp x ΔT
Q= 7092.852 x6.9x33

Q=1615042.4

II. Carbon Dioxide CO2:


Formula used is Q = oCpΔT

o(Molar flow rate )=3675.648 , Cp=9.12

Q= o x Cp x ΔT
Q=3675.648 x 9.12 x33

Q=1106223.022

III. Carbon Monoxide CO:


Formula used is Q = oCpΔT

o(Molar flow rate )=3242.0364 , Cp= 6.97

Q= o x Cp x ΔT
Q=3242.0364 x 6.97 x 33

Q=745700.7924

55
Chapter 4 Energy Balance

IV. Water H2O


Formula used is Q = oCpΔT

o(Molar flow rate )=42.21252 , Cp=17.98

Q= o x Cp x ΔT
Q= 42.21252 x 17.98 x33

Q=25046.37662

V. Methane CH4:
Formula used is Q = oCpΔT

o(Molar flow rate )=291.4674 , Cp=8.7

Q= o x Cp x ΔT
Q= 291.4674 x 8.7 x 33

Q= 83680.29054

VI. Ethylene C2H4:


Formula used is Q = oCpΔT

o(Molar flow rate )=1.86654 , Cp= 10.7

Q= o x Cp x ΔT
Q= 1.86654 x 10.7 x 33

Q=659.075274

VII. Ethane C2H6:


Formula used is Q = oCpΔT

o(Molar flow rate )= 0.373308 , Cp= 13.09

Q= o x Cp x ΔT
Q= 0.373308 x 13.09 x 33

Q= 161.2578568

56
Chapter 4 Energy Balance

VIII. Benzene C6H6:


Formula used is Q = oCpΔT

o(Molar flow rate )= 0.041 , Cp= 21.13

Q= o x Cp x ΔT
Q= 0.041 x 21.13 x 33

Q= 28.73354978

IX. Tar C10H8:


Formula used is Q = oCpΔT

o(Molar flow rate )= 1.22043E-06 , Cp=33.88

Q= o x Cp x ΔT
Q= 1.22043E-06x 33.88 x 33

Q= 17.47

X. Ammonia NH3:
Formula used is Q = oCpΔT

o(Molar flow rate )= 0.86148 , Cp= 8.63

Q= o x Cp x ΔT
Q= 0.86148 x 8.63 x 33

Q= 245.34

XI. Hydrogen Sulphide H2S:


Formula used is Q = oCpΔT

o(Molar flow rate )=7.46616 , Cp=8.23

Q= o x Cp x ΔT
Q= 7.46616 x 8.63 x 33

Q= 2027.734394

57
Chapter 4 Energy Balance

XII. Nitrogen:
Formula used is Q = oCpΔT

o(Molar flow rate )=8.32764 , Cp= 6.97

Q= o x Cp x ΔT
Q= 8.32 x 6.97 x 33

Q=1915.440476

Total Q for stream 300 is 3580730.466

So Over all on Inlet Separator Heat IN= Heat out

3580730.466 =(4633244.686+8213985.662)

58
Chapter 4 Energy Balance

4.5 Absorber:

302

311

300

303

 General Energy Balance Equation:-

Q- Ẇs =ΔH+ΔEx+ΔEp (1)

Assumption:-

1. Negligible effect of ΔEp and ΔEx so we take

ΔEx=0 ; ΔEp=0

2. No moving parts , Hence


Ẇs=0

Equation (1) reduces to

Q = ΔH (2)

59
Chapter 4 Energy Balance

Energy Balance on different streams related to Absorber


Reference Temperature = 77F

For Stream 300 :


Components:
I. Hydrogen:
Formula used is Q = oCpΔT

o(Molar flow rate )=7092.852 , Cp= 6.9

Q= o x Cp x ΔT
Q= 7092.852 x6.9x33

Q=1615042.4

II. Carbon Dioxide CO2:


Formula used is Q = oCpΔT

o(Molar flow rate )=3675.648 , Cp=9.12

Q= o x Cp x ΔT
Q=3675.648 x 9.12 x33

Q=1106223.022

III. Carbon Monoxide CO:


Formula used is Q = oCpΔT

o(Molar flow rate )=3242.0364 , Cp= 6.97

Q= o x Cp x ΔT
Q=3242.0364 x 6.97 x 33

Q=745700.7924

60
Chapter 4 Energy Balance

IV. Water H2O


Formula used is Q = oCpΔT

o(Molar flow rate )=42.21252 , Cp=17.98

Q= o x Cp x ΔT
Q= 42.21252 x 17.98 x33

Q=25046.37662

V. Methane CH4:
Formula used is Q = oCpΔT

o(Molar flow rate )=291.4674 , Cp=8.7

Q= o x Cp x ΔT
Q= 291.4674 x 8.7 x 33

Q= 83680.29054

VI. Ethylene C2H4:


Formula used is Q = oCpΔT

o(Molar flow rate )=1.86654 , Cp= 10.7

Q= o x Cp x ΔT
Q= 1.86654 x 10.7 x 33

Q=659.075274

VII. Ethane C2H6:


Formula used is Q = oCpΔT

o(Molar flow rate )= 0.373308 , Cp= 13.09

Q= o x Cp x ΔT
Q= 0.373308 x 13.09 x 33

Q= 161.2578568

61
Chapter 4 Energy Balance

VIII. Benzene C6H6:


Formula used is Q = oCpΔT

o(Molar flow rate )= 0.041 , Cp= 21.13

Q= o x Cp x ΔT
Q= 0.041 x 21.13 x 33

Q= 28.73354978

IX. Tar C10H8:


Formula used is Q = oCpΔT

o(Molar flow rate )= 1.22043E-06 , Cp=33.88

Q= o x Cp x ΔT
Q= 1.22043E-06x 33.88 x 33

Q= 0.00136449

X. Ammonia NH3:
Formula used is Q = oCpΔT

o(Molar flow rate )= 0.86148 , Cp= 8.63

Q= o x Cp x ΔT
Q= 0.86148 x 8.63 x 33

Q= 245.34

XI. Hydrogen Sulphide H2S:


Formula used is Q = oCpΔT

o(Molar flow rate )=7.46616 , Cp=8.23

Q= o x Cp x ΔT
Q= 7.46616 x 8.63 x 33

Q= 2027.734394

62
Chapter 4 Energy Balance

XII. Nitrogen:
Formula used is Q = oCpΔT

o(Molar flow rate )=8.32764 , Cp= 6.97

Q= o x Cp x ΔT
Q= 8.32 x 6.97 x 33

Q=1915.440476

Total Q for stream 300 is 3580730.466

For Stream 302 :


Components:
I. Hydrogen:
Formula used is Q = oCpΔT

o(Molar flow rate )=7092.852 , Cp= 6.9

Q= o x Cp x ΔT
Q= 7092.852 x6.9x33

Q=1615042.4

II. Carbon Dioxide CO2:


Formula used is Q = oCpΔT

o(Molar flow rate )=217.96 , Cp=9.12

Q= o x Cp x ΔT
Q=217.96 x 9.12 x33

Q=655597.2416

III. Carbon Monoxide CO:


Formula used is Q = oCpΔT

o(Molar flow rate )=3242.0364 , Cp= 6.97

63
Chapter 4 Energy Balance

Q= o x Cp x ΔT
Q=3242.0364 x 6.97 x 33

Q=745700.7924

IV. Water H2O


Formula used is Q = oCpΔT

o(Molar flow rate )=42.21252 , Cp=17.98

Q= o x Cp x ΔT
Q= 42.21252 x 17.98 x33

Q=25046.37662

V. Methane CH4:
Formula used is Q = oCpΔT

o(Molar flow rate )=291.4674 , Cp=8.7

Q= o x Cp x ΔT
Q= 291.4674 x 8.7 x 33

Q= 83680.29054

VI. Ethylene C2H4:


Formula used is Q = oCpΔT

o(Molar flow rate )=1.86654 , Cp= 10.7

Q= o x Cp x ΔT
Q= 1.86654 x 10.7 x 33

Q=659.075274

VII. Ethane C2H6:


Formula used is Q = oCpΔT

o(Molar flow rate )= 0.373308 , Cp= 13.09

Q= o x Cp x ΔT

64
Chapter 4 Energy Balance

Q= 0.373308 x 13.09 x 33

Q= 161.2578568

VIII. Benzene C6H6:


Formula used is Q = oCpΔT

o(Molar flow rate )= 0.041 , Cp= 21.13

Q= o x Cp x ΔT
Q= 0.041 x 21.13 x 33

Q= 28.73354978

IX. Tar C10H8:


Formula used is Q = oCpΔT

o(Molar flow rate )= 1.22043E-06 , Cp=33.88

Q= o x Cp x ΔT
Q= 1.22043E-06x 33.88 x 33

Q= 0.00136449

X. Ammonia NH3:
Formula used is Q = oCpΔT

o(Molar flow rate )= 0.86148 , Cp= 8.63

Q= o x Cp x ΔT
Q= 0.86148 x 8.63 x 33

Q= 245.34

XI. Hydrogen Sulphide H2S:


Formula used is Q = oCpΔT

o(Molar flow rate )=0.0218 , Cp=8.23

Q= o x Cp x ΔT

65
Chapter 4 Energy Balance

Q= 0.0218 x 8.63 x 33

Q= 5.920662

XII. Nitrogen:
Formula used is Q = oCpΔT

o(Molar flow rate )=8.32764 , Cp= 6.97

Q= o x Cp x ΔT
Q= 8.32 x 6.97 x 33

Q=1915.440476

Total Q for stream 302 is 2538082.872

For Stream 303 :


Components:

I. Carbon Dioxide CO2:


Formula used is Q = oCpΔT

o(Molar flow rate )=3507 , Cp=9.38

Q= o x Cp x ΔT
Q=3507 x 9.38 x75

Q=2467174.5

II. Water H2O


Formula used is Q = oCpΔT

o(Molar flow rate )=65200 , Cp=18.02

Q= o x Cp x ΔT
Q= 65602 x 18.02 x75

Q=88117800

66
Chapter 4 Energy Balance

III. Hydrogen Sulphide H2S:


Formula used is Q = oCpΔT

o(Molar flow rate )=7.477232968 , Cp=8.3

Q= o x Cp x ΔT
Q= 7.477232968x 8.3 x 75

Q= 4654.577523

IV. MDEA:
Formula used is Q = oCpΔT

o (Molar flow rate )=9849 lbmol/hr , Cp= 69.04

Q= o x Cp x ΔT
Q= 9849 x 69.04 x 75

Q= 50998122

Total Q for stream 307 is 141587751.1

For Stream No 311:


Components:
I. Carbon Dioxide CO2:
Formula used is Q = oCpΔT

o(Molar flow rate )=49.24 , Cp=9.12

Q= o x Cp x ΔT
Q=49.24 x9.12 x33

Q=`14819.2704

II. Water H2O


Formula used is Q = oCpΔT

o(Molar flow rate )=65200 , Cp=18.02

67
Chapter 4 Energy Balance

Q= o x Cp x ΔT
Q= 65602 x 18.02 x33

Q=38771832

III. MDEA:
Formula used is Q = oCpΔT

o(Molar flow rate )= 9849 , Cp= 65.33

Q= o x Cp x ΔT
Q= 9849 x 65.33 x 33

Q= 21233360.61

Total Heat for Stream 306 is 60020011.88

For Absorber Heat of reaction = Heat out – Heat in= Stream(300 +306 )-
Stream (302-307)= -80525091.6

68
Chapter 4 Energy Balance

4.6 Lean Solvent Exchanger:

311 310

E-1

For stream 310:


Temperature = 177F
Difference in temperature is =ΔT= 100F
QMDEA= oCpΔT= 9849 x 71.25 x 100 =70174125

Qwater= oCpΔT =65200 x 18.07 x 100 = 117816400

QCarbon Dioxide= oCpΔT = 49.24 x 9.53 x 100 = 46925.72

Heat In = 70174125+117816400 +46925.72

Heat in = 188037450.7

For stream 311:


Temperature = 110 F
Difference in temperature = ΔT= 33F
QMDEA= oCpΔT=9849 x 64 x 33= 20801088

Qwater = oCpΔT= 665200x 17.5 x 33 = 37653000

Qcarbon Dioxide = oCpΔT= 4924 x 912 x 23 = 14819.27

Heat Out = 20801088+37653000 +14619.27

Heat Out= 5846890

 QDuty = Heat in - Heat Out


= 129568543.4 BTU/hr OR 129.568

69
Chapter 4 Energy Balance

4.7 Lean/Rich amine exchanger:

General Energy Balance Equation:-

Q- Ẇs =ΔH+ΔEx+ΔEp (1)

Assumption:-

1. Negligible effect of ΔEp and ΔEx so we take

ΔEx=0 ; ΔEp=0

2. No moving parts , Hence


Ẇs=0

Equation (1) reduces to

Q = ΔH (2)

Difference in temperature is =ΔT= 99 F


QMDEA= oCpΔT= 9849 x 73.28 x 99 =71448756

Qwater= oCpΔT =65200 x 18.13 x 99 = 117025524

QCarbon Dioxide= oCpΔT = 49.24 x 9.65 x 99= 47041

Heat out = 71448756+117025524 +47041

Heat out = 188521321

70
Chapter 4 Energy Balance

Difference in temperature is =ΔT= 181F


QMDEA= oCpΔT= 9849 x 73.28 x181=130628533

Qwater= oCpΔT =65200 x 18.13 x 181 = 213955756

QCarbon Dioxide= oCpΔT = 49.24 x 9.65 x 181 =160602.17

Heat In = 130628533+213955756+160602.17

Heat in = 344744891

 QDuty = Heat in - Heat Out


= 156223570 BTU/hr OR 156.22

4.8 Over head Stripper Condenser:

306 313

Energy balance on streams Linked with Stripper Condenser


 For Stream 306

I. Carbon dioxide CO2


Formula used is Q = oCpΔT

o(Molar flow rate )= 3457.757 , Cp= 9.67

Q= o x Cp x ΔT
Q= 3457.757 x 9.67 x 126

Q= 4213000.284

II. Hydrogen Sulphide H2S


Formula used is Q = oCpΔT

71
Chapter 4 Energy Balance

o(Molar flow rate )= 7.477 , Cp= 8.4

Q= o x Cp x ΔT
Q= 7.477 x 8.4 x 126

Q=7913.6568

III. Water H2O


Formula used is Q = oCpΔT

o(Molar flow rate )= 4366.5 , Cp= 18.14

Q= o x Cp x ΔT
Q= 4366.5 x 18.14 x 126

Q= 9980247.06

Total Heat (Q) for stream IN = 14201161

For stream 313:


I. Carbon dioxide CO2
Formula used is Q = oCpΔT

o(Molar flow rate )= 3457.757 , Cp= 9.25

Q= o x Cp x ΔT
Q= 3457.757 x 9.25 x 53

Q= 1695165

II. Water H2O


Formula used is Q = oCpΔT

o(Molar flow rate )= 4366.5 , Cp= 17.99

Q= o x Cp x ΔT
Q= 4366.5 x 17.99 x 53

Q=3273.281

72
Chapter 4 Energy Balance

III. Hydrogen Sulphide H2S


Formula used is Q = oCpΔT

o(Molar flow rate )= 7.477 , Cp= 8.26

Q= o x Cp x ΔT
Q= 7.477 x 8.26 x 53

Q= 4163327

Total Heat (Q) for stream OUT = 5861765

Heat IN – Heat OUT = -8339395.6

73
Chapter 4 Energy Balance

4.9 Stripper:

306

309

305

307

Energy balance on different streams linked with stripper

 General Energy Balance Equation:-

Q- Ẇs =ΔH+ΔEx+ΔEp (1)

Assumption:-

1. Negligible effect of ΔEp and ΔEx so we take

ΔEx=0 ; ΔEp=0

2. No moving parts , Hence


Ẇs=0

Equation (1) reduces to

Q = ΔH (2)

74
Chapter 4 Energy Balance

Reference Temperature = 77F

 For Stream 305


Components:
I. MDEA
Formula used is Q = oCpΔT

o(Molar flow rate )= 1173584 , Cp= 0.615

Q= o x Cp x ΔT
Q= 1173584 x 0.615 x 123

Q= 88775742

II. Water H2O


Formula used is Q = oCpΔT

o(Molar flow rate )= 1173584 , Cp= 1.007

Q= o x Cp x ΔT
Q= 1173584 x 1.007 x 123

Q= 145361256

III. Hydrogen Sulphide H2S


Formula used is Q = oCpΔT

o(Molar flow rate )= 254.218 , Cp= 0.219

Q= o x Cp x ΔT
Q= 254.218 x 0.219 x 123

Q= 6847.8703

IV. Carbon Dioxide CO2


Formula used is Q = oCpΔT

o(Molar flow rate )= 154308 , Cp= 0.246

75
Chapter 4 Energy Balance

Q= o x Cp x ΔT
Q= 154308 x 0.246 x 123

Q= 238812897

Total Heat (Q) for stream A = 23812897

For Stream 307:


I. MDEA
Formula used is Q = oCpΔT

o(Molar flow rate )= 1173584 , Cp= 0.658

Q= o x Cp x ΔT
Q= 1173584 x 0.658 x 181

Q= 139771476

II. Water H2O


Formula used is Q = oCpΔT

o(Molar flow rate )= 1173584 , Cp= 1.018

Q= o x Cp x ΔT
Q= 1173584 x 1.018 x 181

Q= 216242193

III. Carbon Dioxide CO2


Formula used is Q = oCpΔT

o (Molar flow rate) = 2166.68 , Cp= 0.226

Q= o x Cp x ΔT
Q= 2166.68 x 0.226 x 181

Q=356102299

Total Heat (Q) for stream B = 356102299

76
Chapter 4 Energy Balance

For stream 306:


Components
I. Carbon dioxide CO2
Formula used is Q = oCpΔT

o(Molar flow rate )= 152141.3 , Cp= 0.22

Q= o x Cp x ΔT
Q= 152141.3 x 0.22 x 126

Q= 4217357.4

II. Water H2O


Formula used is Q = oCpΔT

o(Molar flow rate )= 78597 , Cp= 1.007

Q= o x Cp x ΔT
Q= 78597 x 1.007 x 126

Q=9972544.6

III. Hydrogen Sulphide H2S


Formula used is Q = oCpΔT

o(Molar flow rate )= 254.218 , Cp= 0.246

Q= o x Cp x ΔT
Q= 254.218 x 0.246 x 126

Q= 7879.7411

Total Heat (Q) for stream D = 14197782

For (309) Reflux Stream:

77
Chapter 4 Energy Balance

Components
I. Water H2O
Formula used is Q = oCpΔT

o(Molar flow rate )= 78597 , Cp= 0.999

Q= o x Cp x ΔT
Q=78597 x 0.999 x 53

Q= 4161475

Heat of Reaction =-80525091.6


Reboiler heat Hb
= (Total Q for stream B + Total Q for stream D)-(Total Q for stream A+ Heat of
reaction+ Total Q for reflux stream)

=207850800

78
Chapter 4 Energy Balance

4.10 Energy Balance across Hydraulic Turbine:


303

152 F
445 Psia Ẇs

304

30 Psia
T= ?

 General Energy Balance Equation:-

Q- Ẇs =ΔH+ΔEx+ΔEp (1)

Assumption:-

3. System is perfectly insulated (no heat loss ) i.e Q=0


4. Negligible effect of ΔEp and ΔEx so we take

ΔEx=0 ; ΔEp=0

Equation (1) reduces to

- Ẇs = ΔH (2)

5. Assuming that the volume remain constant ( i.e process streams are liquid )
 Calculation of the shaft work:-
W= v.dp + P.dv dv = 0 according to condition (3)
So
W= v(P2 – P1) (3)

Density of rich MDEA = 30.896

79
Chapter 4 Energy Balance

Average Molecular weight of rich MDEA = 31.86

Molar flow rate (inlet & outlet) = o= 78563.47

Volume of inlet and outlet stream


V= 78563.471 lbmol/hr x 31.86 lbm/lbmol x ft3/30.896 lbm
V= 81014.76521 ft3/hr (4)
Putting Eq (4) in Eq (3)
W= V (P2 – P1)
=81014.765 ft3/hr x (445 -30)psia x (1m3/(3.28)3ft3) x (101325 pa/14.7psia)

= 6567347847

 Converting to horse power:-


=656734784 J/hr x 1BTU/1055J x 1 hp/2544.433
Ẇs =2446.50 hp

 Assuming 50% (Adiabatic Efficiency ):-


Ẇs = 1223.25 hp
Putting this in equation (2)
- Ẇs = ΔH
-1223.25= oCp(T2-T1)
Let Cp be constant

o= 78563.471

Average Cp= 25.67

Now putting these values


= -1223.25hp x 760 watts/1hp x ((1J/s)/1 watts) x (1 BTU/1055J) x (1lbmol
F/2567BTU) x (hr/ 78563.467 lbmol) x (3600s / 1hr )
-1.573 = T2-T1
-1.573 + T1=T2
-1.573 + 152 = T2
150.42 F= T2

80
Chapter 5 Equipment Design
Chapter 5 Equipment Design

5.1 Inlet Separator:


Design of Separator:
Here we will read about following topics:

 Basic Function of separators.


 Different types of separators.
 Criteria for selecting separator.
 Method for designing separator.

Basic Principle:
The main purpose of separator is to separator liquid from vapor and vice versa. This separation
is accomplished by providing velocity low enough so that vapor get separated from liquid.
Gravity plays vital role in this separation along with density difference.

Different types of separators:


Basically there are three different types of liquid vapor separator:

 Horizontal vapor liquid separator.


 Vertical vapor liquid separator.
 Knock-out drums.
a) Horizontal vapor liquid separator:
This type of separator is used when liquid contents are sufficiently high and when L/D (length to
diameter ratio) is great than 5.

b) Vertical vapor-liquid separator:


This type of separator is used when liquid contents are low and when L/D (length to diameter
ratio) is great than 3 and less than 5.

c) Knock-out drums:
This type of separator is used when very low liquid content are present in inlet stream. Due to
this reason Knock out drum is mostly installed on compressor inlet stream to stop liquid from
going in the compressor and damaging it.

81
Chapter 5 Equipment Design

Criteria for selecting separator:


Knock out drum is mostly installed on compressor inlet stream to stop liquid from going in the
compressor and damaging it. So this cannot be included in selection criteria.

As far as vertical and horizontal separator are concerned both have same designing procedure
and have same design calculations but they only differ in one parameter that is value L/D ratio.
If L/D ratio is greater than 5 than Horizontal is use if it is between 5 and 3 than vertical is used .

Method for designing separator:

Vapor volumetric rate = 1.58

Liquid volumetric rate =0.01784

Density of vapor= 1.353 = 21.67

Density of liquid = 62.2 = 996.348

1. Calculation of settling velocity of liquid droplets:

20 ( )

= Liquid density,

= vapour density,

= settling velocity,

( )

2. Calculation of maximum superficial vapor velocity given by following


equation:

= Maximum velocity

82
Chapter 5 Equipment Design

= Liquid density,

= vapour density,

√ = 1.97 or 0.602

3. Calculation of minimum vessel diameter:

= minimum vessel diameter

= settling velocity, if demister pad is used

= gas or volumetric flow

= 2.06 m

4. Calculation of liquid depth:

Holding time for natural gas- condensate separator = 2-6 mints21

Taking holding time = 6 mints

= 1.928 m

83
Chapter 5 Equipment Design

5. Calculation of vessel length:

22

L =2.0D + Ld + Thickness of demister pad

L = 2.0 x 2.06 + 1.928m + 0.3048 m =6.34845045 m

Checking ratio:

If , then resize the tank 23

84
Chapter 5 Equipment Design

5.2 Plate Heat Exchanger:


Basically a plate heat exchanger is used to achieve the desired flow pattern by using corrugated
plates in addition to gasket and corner ports. In plate exchanger fluid pattern is such that fluid
goes through alternate channels. Plates are provided with connection for fluid and are held in a
frame. Plate heat exchanger in which gasket is used as sealing element are also know gasketed
exchanger.

The plate spacing in plate exchanger is normally in the range of 1.3 to 6.4 mm. There are certain
factors which determine the size and numbers of plates, these factors are pressure drop, fluid
physical properties, temperature program and flow rates. The main function of plate
corrugation is to give enough strength to plate to overcome differential pressure and also
introduce fluid turbulence. All plates are then composed in frame by using pressure
arrangement.

85
Chapter 5 Equipment Design

Useful data on PHE24

Unit Plates
2
Size 1540-2500m Thickness 0.5-1.2 mm
Number of plates Up to 700 Size 0.03-2.2 m
Port size Up to 39cm Spacing 1.5-5.0 mm
Corrugation depth 3-5 mm

Standard Performance Limits:25

 Maximum operating pressure 25 bar


 With special construction 30 bar
 Maximum temperature 160oC
 With special gaskets 200oC
 Maximum flow rate 3600m3/h
 Heat transfer coefficient 3500-7500 W/m2 oC
 Heat transfer area 0.1 – 2200m2
 Maximum connection size 450mm
 Temperature approach as low as 1 oC
 Heat recovery as high as 93 %
 Heat transfer coefficient 3000-7000 W/m2 oC
 NTU 0.3-4.0
 Pressure drop 30 kpa per NTU

Advantages of Plate heat exchanger


1. High heat transfer and high turbulence:
Different plate patterns and corrugation in plate heat exchanger induces high heat
transfer and high turbulence. For example the use of embossed plate pattern results in
high turbulence when fluid velocities are low on other hand plate having herringbone
pattern are arrange in such a way that their corrugation are in alternative direction ,
this causes swirling motion of fluid which ultimately results into high heat transfer
coefficient.
2. Reduced fouling:
Due to the presence of uniform flow pattern, high turbulence, smooth plate surface
and absence of stagnant area the fouling in plate heat exchanger is much less and
frequent cleaning can be avoided.

86
Chapter 5 Equipment Design

3. True Counter Flow:


In PHE greater temperature difference can be achieved by making fluid to move in
opposite direction.
4. Close temperature approach:
In PHE due to presence of true counter flow, efficient heat transfer and better flow
characteristics it is possible to achieve temperature approach as low as 1-2 oF
5. Multiple duties:
PHE has advantage that two or more than fluids can be heated or cooled in the same
unit by using intermediate divider section between heat transfer plates.
6. Easy maintenance:
It is easy to clean and inspect PHE because of configuration of PHE. PHE can be easily
opened by removing the bolts and then sliding away the end frame. In similar way
gasket of PHE can be replaced easily.
7. Lightweight:
PHE employs less surface area and has less liquid volume space. These features make
PHE lighter that other types of exchangers.
8. High Viscosity application:
PHE can handle high viscosity fluid because In PHE turbulence can be induce at low
velocities
9. Saves Servicing time and space:
It takes half time to open PHE for rebuilding, maintenance and inspection than shell
and tube exchanger. Also PHE requires about one half to one fifth area compare shell
and tube exchanger using for same application.
10. Less operational problems and lower cost:
In PHE erosion- corrosion, noise, flow induced vibration are not present which are
usually present in shell and tube exchange due to impingement attack. These
exchanger have low manufacturing cost and high thermal efficiency due to which they
are more economical as compare to exchangers of other type having same heat duty .

87
Chapter 5 Equipment Design

Construction features of PHE26:

Feature Advantages Benefits


PHE concept Efficient heat transfer, low Reduced capital cost, smaller
weight foundation
Modular construction Flexibility Easy to modify for altered
duties
Fixed frame and movable Easily accessible heat Reduced shutdown time
press plates transfer area
Metallic contact between Minimized vibration Longer life time greater
plates reliability
Bearing boxes on tightening Reduced friction Easy opening and closing,
bolts reduced maintenance
One- step plate pressing High dimensional tolerances Improved performance
Glue-free gaskets Simplified regasketing while Reduced shut-down time,
still in frame reduced maintenance cost
Two-components oven- Superior bonding Greater reliability
cured epoxy on glued
gaskets

Construction of Plate Heat exchanger:


 Plate
The plates use in PHE are available in wide variety of embossed and corrugated
patterns. The main reason of using corrugation to produce high turbulence which
ultimately results in high heat transfer than the heat transfer achieve in shell and tube
exchanger of same duties. The advantages of using embossed pattern is this that these
pattern provide more strength to plates and also enhance the effective surface area.
The most frequently used corrugation are wash board or intermating troughs and the
herringbone or chevron patterns.
Plate Material:
Carbon steel is used rarely due to poor corrosion resistance.
27
Commonly used PHE Materials:

88
Chapter 5 Equipment Design

Stainless steel AISI 304 Incoloy 825


Stainless steel AISI 316 Monel 400
Avesta SMO 254 Hastelloy B
Titanium, titanium-0.2% Hastelloy C-276
(Palladium stabilized ) Aluminum brass 76/22/2
Tantalum Cupronickel (70/30)
Inconel 600 Cupronickel (90/100)
Inconel 625 Diabon F 100

 Gasket selection:
The main points which should be consider while selecting any gasket are shape, good
sealing ability, temperature and chemical resistance. Different gaskets and their
28
respective operating temperature are shown in below:
 Styrene butadiene rubber (80 oC)
 Nitrile rubber ( 140 oC)
 Ethylene propylene rubber (150 oC)
 Resin- cured butyl rubber (140 oC)
 Fluorocarbon rubbers (180 oC)
 Fluoroelastomer (100 oC)
 Compressed asbestos fiber (260 oC)
 Silicon elastomers ( low temperature application )
 Tie bolts:
The tie bolts use in PHE are mostly made from 0.5%Mo-1%Cr low alloy steel. Different
types of tightening devices (pneumatic, hydraulic or electric) can by use for packing
large units.

89
Chapter 5 Equipment Design

Comparison between Shell & tube heat exchanger and Plate heat exchanger:29

Features Traditional PHE STHE


Multiple duty Possible Impossible
Piping connection From one direction(on frame From several directions
plate)
Heat transfer ratio 3-5 1
Operating weight ratio 1 3-10
Hold-up volume Low High
Space ratio 1 2-5
Welds None Welded
Sensitivity to vibrations Not sensitive Sensitive
Gaskets On every plate On each flanged joint
Detection of leakage Easy to detect on the exterior Difficult to detect
Access for inspection On each side of plate Limited
Time required for opening 15 min with pneumatic 60-90 min
tightener
Repair Easy to replace plate and/or Requires tube plugging (
gasket decreased capacity)
Modification Easy by adding and removing Impossible
plates
Fouling 10-25% that of STHE -----------

Plate heat exchanger design calculation


1. Heat Transfer Area:
Physical properties of hot fluid (Lean Amine)

= 938.4618

=0.0003018 Pa-sec

K=0.3443

Cp=110684

90
Chapter 5 Equipment Design

Physical properties of cold fluid (Rich Amine)

= 921.3411

=0.0005557 Pa-sec

K=0.3350

Cp=101919

The heat duty of Lean/Rich Exchanger as calculated before is

=156.231 or 45784.3 kW

( ) ( )
ΔTlm= ( ) = 38.6
( )

NTU is based on maximum temperature difference.


( )
NTU= = 1.16

30
FT factor calculated from graph for 1:1 pass is =0.975

As in this exchanger both stream are light organic liquid so the value of overall coefficient (U)
31
taken from table is 2200

Q=UAΔT

A( total heat transfer area )= = = 548.763 m2

Assumptions (some typical dimensions) 32

Effective plate area = 2.2 m2


Effective length = 1.5 m
Width = 0.5 m
Plate spacing = 5mm
Channel cross-sectional area= (5x10-3) x 0.5 = 2.5x10-3 m2
Hydraulic mean diameter= 2x (5x10-3) = 0.01 m
Plate thickness = 0.75mm

91
Chapter 5 Equipment Design

Number of plates = =

Plates per pass = = 125

2. Hp calculation for Lean Amine


( )
Channel velocity= x x

= x( )
x =1.02

Re(Reynolds’s No)=

= = 31789

Pr (Prandtl No) =

= = 97

Nu (Nuesselt No) = 0.26 x (Re)0.65 x (Pr)0.4

= 0.26 x (31789)0.65 x (97)0.4 = 1368

Hp = Nu x

= 1368 = 471128 Wm-2 oC

3. Hp calculation for Rich Amine


( )
Channel velocity= x x

= x( )
x =1.03

Re(Reynolds’s No)=

= = 17240

Pr (Prandtl No) =

92
Chapter 5 Equipment Design

= = 169

Nu (Nuesselt No) = 0.26 x (Re)0.65 x (Pr)0.4

= 0.26 x (17240)0.65 x (169)0.4 = 1147

Hp = Nu x

= 1147 = 38453 Wm-2 oC

4. Overall Coefficient:
33
Fouling factor for rich and lean amine (light organic) is = 10000 Wm-2 oC-1

We Take plate thickness as 0.75 mm and we use titanium material which has thermal
conductivity of 21 Wm-1 oC-1

= + + + +
( ) ( )

= + + + +

= 2.829x10-4

U= 3524 Wm-2 oC-1

The value of overall coefficient is much above the supposed value so the calculated number of
plate per pass is satisfactory

5. Pressure Drop
 For Lean amine
Jf = 0.60 x (Re)-0.3
= 0.60 x (31789)-0.3
= 0.0267

Path length = plate length x number of passes = 1.5 x 1 = 1.5 m

 Plate pressure drop

ΔPp=8 x Jf x x density x

93
Chapter 5 Equipment Design

ΔPp= 8 x 0.0267 x x 938 x

= 15655

 Port pressure drop


We take port dia as 39 cm =0.39 m

Then area of the port is = 0.119 m2


( )

Velocity through port=

=2.67

ΔPpt= 1.3 x

= 4351

Total Pressure drop = 15655 +4351 = 20000

=0.2 bar

 For rich amine


Jf = 0.60 x (Re)-0.3
= 0.60 x (17240)-0.3
= 0.032

Path length = plate length x number of passes = 1.5 x 1 = 1.5 m

 Plate pressure drop

ΔPp=8 x Jf x x density x

ΔPp= 8 x 0.032 x x 921x

= 18848

94
Chapter 5 Equipment Design

 Port pressure drop


We take port dia as 39 cm =0.39 m

Then area of the port is = 0.119 m2


( )

Velocity through port=

=2.72

ΔPpt= 1.3 x

= 4437

Total Pressure drop = 18848 +4437 = 23285

=0.23 bar

The pressure drop is well between the limits so the design of exchanger and number
of plates is good. So plate heat exchanger can be considered for this duty

95
Chapter 5 Equipment Design

5.3 Absorber Design:


Absorber
The removal of one or more selected components from a mixture of gas by absorption into a
suitable solvent.

Choice between Plate & Packed column:


Vapor liquid mass transfer operation may be carried either in plate or packed column. These
two types of operation are quite different. The relative merits of plate over packed column are
as follows:

1. Plate column are designed to handle wide range of liquid flow rates without flooding.
2. If a system contains solid contents; it will be handled in plate column, because solid will
accumulate in the voids, coating the packing materials and making it ineffective.
3. Dispersion difficulties are handled in plate column when flow rate of liquid are low as
compared to gases.
4. For large column heights, weight of the packed column is more than plate column.
5. If periodic cleaning is require, man holes will be provided for cleaning. In packed columns
packing must be removed before cleaning.
6. For non-foaming systems the plate column is preferred.
7. Design information for the plate column is more readily available and more reliable than
that for packed column.
8. Inter stage cooling can be provided to remove heat of reaction or solution in plate column.
9. When temperature change is involved, packing may be damaged.

Choice of Plate Type34:


There are three main types of plate, sieve plate, bubble cap and value plate. We have selected
sieve plate because:

1. They are lighter in weight and less expensive. It is easier and cheaper to install.
2. Pressure drop is low as compared to valve and bubble cap plates.
3. Peak efficiency is generally high.
4. Maintenance cost is reduced due to the ease of cleaning.
5. In case of capacity rating, sieve plate has high rank as compared to valve and bubble plates.

Sieve plate:
Sieve plate is simplest type of cross-flow plate. Vapor passes up through perforations in the
plate; and the liquid is retained on the plate by vapour flow. The perforations are usually small

96
Chapter 5 Equipment Design

holes, but larger holes and slots are used. The arrangement, number and size of the holes are
design parameters.

Because of their efficiency, wide operating range, ease of maintenance and cost factors, sieve
and valve trays have replaced the once highly thought of bubble cap trays in many applications.

Factors affecting the absorption Column :


Vapor Flow Conditions:
1. Foaming
2. Entrainment
3. Weeping/dumping
4. Flooding

Foaming:
Foaming refers to the expansion of liquid due to passage of vapor or gas. Although it provides
high interfacial liquid-vapor contact, excessive foaming often leads to liquid buildup on trays. In
some cases, foaming may be so bad that the foam mixes with liquid on the tray above.

Whether foaming will occur depends primarily on physical properties of the liquid mixtures, but
is sometimes due to tray designs and condition. Whatever the cause, separation efficiency is
always reduced.

Entrainment:
Entrainment refers to the liquid carried by vapor up to the tray above and is again caused by
high vapor flow rates. It is detrimental because tray efficiency is reduced: lower volatile
material is carried to a plate holding liquid of higher volatility. It could also contaminate high
purity distillate. Excessive entrainment can lead flooding.

Weeping/Dumping:
This phenomenon is caused by low vapor flow. The pressure exerted by the vapor is insufficient
to hold up the liquid on the tray. Therefore, liquid starts to leak through perforations. Excessive
weeping will lead to dumping. That is the liquid on all trays will crash (dump) through to the
base of the column (via a domino effect) and the column will have to be re-started. Weeping is
indicated by a sharp pressure drop in the column and reduced separation efficiency.

97
Chapter 5 Equipment Design

Flooding:
Flooding is brought about by excessive vapor flow, causing liquid to be entrained in the vapor
up the column. The increased pressure from excessive vapor also backs up the liquid in the
down comer, causing an increase in liquid holdup on the plate above. Depending on the degree
of flooding, the maximum capacity of the column may be severely reduced. Flooding is
detecting by sharp increases in column differential pressure and significant decrease in
separation efficiency.

State of trays & Packing:


Remember that the actual number of trays required for a particular separation duty is
determined by the efficiency of the plate. Thus, any factors that cause a decrease in tray
efficiency will also change the performance of the column. Tray efficiencies are effected by
fouling, wear and tear and corrosion and the rates at which these occur depends upon the
properties of the liquids being processed. Thus appropriate materials should be specified for
tray construction.

Column Diameter:
Vapor flow velocity is dependent on column diameter. Weeping determines the minimum
vapor flow required while flooding determines the maximum vapor flow allowed, hence column
capacity. Thus, if the column diameter is not sized properly, the column will not perform well

Standard Design steps:


1) Calculation of theoretical number of stages.
2) Calculation of actual number of stages.
3) Calculation of diameter of column.
4) Calculation of weeping point.
5) Calculation of pressure drop.
6) Downcomer design.
7) Entrainment calculations.
8) Calculation of height of column.

98
Chapter 5 Equipment Design

ABSORBER DESIGN
Flow rate = 10898 Ibmole/hr
Pressure = 422 psia
Temperature = 110 F
Flow rate = 14358 Ibmole/hr 302 CO2 = 217.96 Ibmole/hr
Pressure = 429.5 psia H2S = 0.0218 Ibmole/hr
Temperature = 110 F H2 = 7092.85 Ibmole/hr
3
Density = 21.47 kg/m CO = 3242.036 Ibmole/hr
Avg. wt = 18.9985 Ib/Ibmole CH4 = 291.467 Ibmole/hr
CO2 = 3675.648 Ibmole/hr C2H4 = 1.866 Ibmole/hr
H2S = 7.46616 Ibmole/hr C2H6 = 0.373308 Ibmole/hr
H2 = 7092.85 Ibmole/hr C6H6 = 0.0412 Ibmole/hr
CO = 3242.036 Ib mole/hr C10H8 = 1.22 x 10-6 Ibmole/hr
CH4 = 291.467 Ibmole/hr NH3 = 0.8615 Ibmole/hr
C2H4 = 1.866 Ibmole/hr N2 = 8.3276 Ibmole/hr
300
C2H6 = 0.373308 Ibmole/hr H2O = 42.2125 Ibmole/hr
C6H6 = 0.0412 Ibmole/hr
C10H8 = 1.22 x 10-6 Ibmole/hr
NH3 = 0.8615 Ibmole/hr Flow rate = 75098 Ibmole/hr
N2 = 8.3276 Ibmole/hr Density = 1001.48 kg/m3
H2O = 42.2125 Ibmole/hr 311 Avg. wt = 31.2969 Ib/Ibmole
Pressure = 432 psia
Temperature = 110 F
CO2 = 49.24 Ibmole/hr

303 MDEA = 9848.8 Ibmole/hr


H2O = 65200 Ibmole/hr

Flow rate = 78563.309 Ibmole/hr


Pressure = 445 psia
Temperature = 152 F
CO2 = 3507.28 Ibmole/hr
H2S = 7.44 Ibmole/hr
H2O = 65200 Ibmole/hr
MDEA = 9848.589 Ibmole/hr

99
Chapter 5 Equipment Design

1. Calculation of theoretical number of stages:35


The main component which we want to be absorbed in MDEA is H2S.so, we take it as a
reference.

H2S:

In = 3.73

Out = .0109

Moles of H2S absorbed = 3.719

Eai =

= 0.997 or 99.7%

Minimum ⁄ for H2S.

( ) min = Ki Eai

L◦ = lean oil entering absorber.

Vn+1 = rich gas entering absorber.

Value of K depends on T & P.

So, average tower conditions for ki:

T = 110 °F

P= = 433psia.

36
Ki = 1.6

So, ( )min = 1.6 x 0.997

= 1.5952.

Operating ( )○ = 1.25 (1.5952)

= 1.994.

100
Chapter 5 Equipment Design

Operating absorption factor

Aio = ( )○ .

= 1.246.

Theoretical stages at operating conditions.

Eai = AioN+1 – Aio / AioN+1 – 1

0.997 = (1.246)N+1 – 1.246 / (1.246)N+1 – 1

(N+1) log 1.246 = log ( )

(N+ 1)(0.0995) = 1.919

N = 19.09.

It means 19 theoretical trays are needed.

2. Calculation of Actual Number of stages:


We take 70% efficiency.

So,

Actual number of stages = = 27 stages.

3. Calculation of Diameter of Column:37


Flooding velocity is given by

Uf = K1

Where,

Uf = Flooding vapor velocity in m/s , base on net column cross-sectional area.

K1 = Constant obtained from figure 11.27 vol.6 Coulson & Richardson .

FLV =

101
Chapter 5 Equipment Design

Where,

Lw =Liquid mass Flow rate ,

Vw = Vapour mass Flow rate ,

In this Case,

Lw = 148.045

Vw = 17.18

Pv = 21.47 [ ]

PL = 1001.48

FLV =

= 1.26

We use Plate Spacing 700mm.


38
K1 = .034

Then, UF = 0.034

= 0.23

We take actual velocity as 85% of flooding velocity

So, Uv = 0.85 x 0.23

= 0.20

Maximum volumetric vapor flow rate =

=0 .80

Net area required = An =

= 4 m2

102
Chapter 5 Equipment Design

We take downcomer area as 12% of total area

Column cross sectional area = Ac =

= 4.55 m2

Down comer area = Ad = 4.55 -4 = .55m2

Active area , bubbling area = Aa= Ac – 2 Ad

= 4.55 – 2(0.55)

= 3.45 m2

Total hole area as 10% of active area , so

Hole area = AH = 0.10 x 3.45 = 0.345 m2

Column diameter = Dc =

= 2.40 m.

4. Calculation of Weeping Point:


For the calculation of weeping point, hole diameter must be selected so that at lowest
operation rate, the vapor flow velocity is still above weeping point.

Maximum liquid flowrate = 148.045

Minimum liquid rate , at 70% turn down = 0.70 x 148.045

= 103.631

x 100 = x 100 = 12%

39
= 0.77

lw = 0.77 x 2.40 = 1.85m

we know

103
Chapter 5 Equipment Design

how = 750 * + 2/3

Lw = weir length, m

how = height over weir , mm liquid

Lw = liquid flow rate

Minimum how = 750 [ ] 2/3

= 109mm.

We take , hw = 50mm

hw + how = 109 + 50 = 159mm.


40
K2 = 31.2
( )
Uh(min) = [ ( )
]

Uh = minimum vapor velocity through holes, m/s

Dh = hole diameter, mm
( )
Uh = ( )
]

Uh = 0.77m/s

Actual minimum vapor velocity =

= 1.62 m/s.

So, minimum operating rate will be well above weeping point.

5. Calculation of Pressure drop:


= 9.81 x 10-3 ht PL

= total pressure drop , Pa (N/m2)

104
Chapter 5 Equipment Design

ht = total pressure drop , mm liquid

Total pressure drop is giver by

ht = hd + (hw + how) + hr

ht = total plate pressure drop

hd = dry plate pressure drop

hr = residual head

hw = height of weir

how = weir crest, mm liquid

hd = 51 [ ]2

Co = Orifice coefficient

Uh = Vapor velocity through holes , m/s

Uh = = 2.32 m/s.

We take carbon steel plate, so

plate thickness = 5mm

hole diameter = 5mm

so,

41
Co = 0.84

hd = 51 [ ]2 [ ]

= 8.34 mm

hr =

= 12.48mm

105
Chapter 5 Equipment Design

ht = 12.48 + 8.34 + 50 + 109

= 179mm liquid

= 9.81 x 10-3 x 179 x 1001.48

= 1757 Pa

= 0.26 Psia (per plate)

6. Down comer Design:


The downcomer area and the plate spacing must be such that the level of the liquid and froth in
the downcomer is well below the top of outlet weir on the plate above. If the liquid rises above
the outlet weir the column will flood.

hb = (hw + how) + ht + hdc

Where,

hb = downcomer backup, measured from plate surface, mm

hdc= head loss in downcomer, mm

hdc = 166 [ ]2

where,

hdc = head loss in downcomer, mm

Lwd = liquid flowrate in downcomer, kg/s

Am = Either downcomer area or clearance area under the downcomer Aop which is smaller.

Aop = hop Lw

Where, hop = height of bottom edge of apron above plate

Lw = length of weir

hop = hw – 10

= 50 – 10 = 40mm

So, Aop= 0.040 x 1.85m

106
Chapter 5 Equipment Design

= 0.074m

hdc = 166 [ ]2

= 6.62mm

So, backup in downcomer = hb= (50 +109) +6.62 + 179

= 34..62mm = 0.33462m

Then , backup in downcomer < ½ (plate spacing + weir height)

0.33462 < ½(0.700 + 0.50)

0.33462 < 0.375

So, plate efficiency is acceptable.

7. Entrainment Calculation:
For checking entrainment , we calculate

Uv =

Uv = = 0.2 m/s

% flooding =

= = 86%

We already know FLV

FLV = 1.26
42

It is well below 0.1, so there is no chance of entrainment and process is satisfactory.

8. Calculation of Height of Column:


No. of plates = 27

Tray spacing = 0.700m

107
Chapter 5 Equipment Design

Tray thickness = 0.005m

Total thickness of trays = 0.135m

Top clearance = 1m

Bottom clearance = 1m

Total height = 20m

108
Chapter 5 Equipment Design

5.4 Stripper Design:


Stripper:
“It is a counter current multi-stage separation column, with liquid feed at top and vapor feed at
the bottom stage”.

Stripping Phenomenon:
Stripping is a mass transfer operation that involves the transfer of a solute (as H2S & CO2 in our
case) from the liquid phase to the gas phase.

Stripping Agents:

 Air
 Stream
 Inert gas
 Hydrocarbon gases
 Reboiled vapors (as in our case)

Types of Stripper:
i. Refluxed Stripper:
It is employed if simple stripping is not sufficient to achieve the desired separation and
contacting trays are needed above the feed tray.

ii. Reboiled Stripper:


If the bottom product from a stripper is thermally stable, it may be Reboiled at the bottom of
the column.

iii. Open steam/Air stripper:


Direct steam may also be used. Sometimes air or inert gases may also be used
(Combination of above can be made based on system’s requirement)
 Principle of separation: difference in volatilities
 Created or added phase: vapor
 Separating agent: stripping vapor

109
Chapter 5 Equipment Design

Flow rate = 78563.309 Ibmole/hr


Pressure = 25 psia 308
3
Density = 935.24 kg/m
Avg. wt = 31.7742 Ib/Ibmoe
Temperature = 200 F
CO2 = 3507.28 Ibmole/hr
H2S = 7.48 Ibmole/hr
H2O = 65200 Ibmole/hr
MDEA = 9848.589 Ibmole/hr

Flow rate = 3986.8 Ibmole/hr


Pressure = 21.4 psia
305 Density = 1.96 kg/m3
Avg. wt = 40.59 Ib/Ibmoe
Temperature = 203 F
CO2 = 3457.76 Ibmole/hr
H2S = 7.48 Ibmole/hr
307
H2O = 521.6 Ibmole/hr
Flow rate = 75098 Ibmole/hr
Pressure = 30 psia
Temperature = 258 F
CO2 = 49.24 Ibmole/hr
MDEA = 9848.8 Ibmole/hr
H2O = 65200 Ibmole/hr

110
Chapter 5 Equipment Design

Standard Design Steps:


Calculation of

1) Theoretical number of stages.


2) Actual number of stages.
3) Diameter of column.
4) Weeping point.
5) Pressure drop.
6) Downcomer design.
7) Entrainment calculations.
8) Height of column

1. Calculation of theoretical number of stages:43


The main component which we want to be stripped from MDEA is H2S. So, we take it as a
reference.

Let us suppose that 100% of H2S is not stripped and very minute quantities remains in the lean
MDEA coming back from Stripper.

Fraction of H2S stripped = Esi = 0.998

Minimum V/L for H2S = ( )min =

Value of K depends on T & P.

So, average tower conditions for value of ki:

T = 230 °F

P = 26psia.
36
Ki = 35

So, ( )min = =

= 0.0285

Operating ( )○ = 1.25 (0.0285)

= 0.0356.

111
Chapter 5 Equipment Design

Operating stripping factor

Si = ( )○ . Ki = 0.0356 x 35

= 1.246.

Theoretical stages at operating conditions.

ESi = SiN+1 – Si / SiN+1 – 1

0.998 = (1.246)N+1 – 1.246 / (1.246)N+1 – 1

(N+1) log 1.246 = log ( )

(N+ 1)(0.0955) = 2.0969

N = 20.78

It means 21 theoretical trays are needed.

2. Calculation of Actual Number of stages:


We take 70% efficiency.

So,

Actual number of stages =

= 30 stages.

3. Calculation of diameter of column:37


Flooding velocity is given by

Uf = K1

Where,

Uf = Flooding vapor velocity in m/s , base on net column cross-sectional area.

K1 = Constant obtained from figure 11.27 vol.6 Coulson & Richardson .

FLV =

112
Chapter 5 Equipment Design

Where,

Lw =Liquid mass Flow rate ,

Vw = Vapour mass Flow rate ,

In this case,

In this Case,

Lw = 315

Vw = 20.38

Pv = 1.96 [ ]

PL = 935.24

FLV =

= 0.71

We use Plate Spacing 800mm.


38
K1 = .054

Then, UF = 0.054

= 1.18

We take actual velocity as 85% of flooding velocity

So, Uv = 0.85 x 1.18

= 1.00

Maximum volumetric vapor flow rate =

=10.4

Net area required = An =

113
Chapter 5 Equipment Design

= 10.4 m2

We take downcomer area as 12% of total area

Column cross sectional area = Ac =

= 11.82 m2

Down comer area = Ad = 11.82 – 10.4 = 1.42m2

Active area , bubbling area = Aa= Ac – 2 Ad

= 11.82 – 2(1.42)

= 8.98 m2

Total hole area as 10% of active area , so

Hole area = AH = 0.10 x 8.98 = 0.898 m2

Column diameter = Dc =

= 3.88 m.

4. Calculation of Weeping Point:


For the calculation of weeping point, hole diameter must be selected so that at lowest
operation rate, the vapor flow velocity is still above weeping point.

Maximum liquid flowrate = 315

Minimum liquid rate , at 70% turn down = 0.70 x 315

= 220.5

x 100 = x 100 = 12%

39
= 0.77

lw = 0.77 x 3.88 = 2.99m

we know

114
Chapter 5 Equipment Design

how = 750 * + 2/3

Lw = weir length, m

how = height over weir , mm liquid

Lw = liquid flow rate

Minimum how = 750 [ ] 2/3

= 138mm.

We take , hw = 50mm

hw + how = 138 + 50 = 188mm.


40
K2 = 31.2
( )
Uh(min) = [ ( )
]

Uh = minimum vapor velocity through holes, m/s

Dh = hole diameter, mm
( )
Uh = ( )
]

Uh = 6.17m/s

Actual minimum vapor velocity =

= 8.11 m/s.

So, minimum operating rate will be well above weeping point.

5. Calculation of Pressure drop:


= 9.81 x 10-3 ht PL

= total pressure drop , Pa (N/m2)

115
Chapter 5 Equipment Design

ht = total pressure drop , mm liquid

Total pressure drop is giver by

ht = hd + (hw + how) + hr

ht = total plate pressure drop

hd = dry plate pressure drop

hr = residual head

hw = height of weir

how = weir crest, mm liquid

hd = 51 [ ]2

Co = Orifice coefficient

Uh = Vapor velocity through holes , m/s

Uh = = 11.6 m/s.

We take carbon steel plate, so

plate thickness = 5mm

hole diameter = 5mm

so,

41
Co = 0.84

hd = 51 [ ]2 [ ]

= 20 mm

hr =

= 13mm

116
Chapter 5 Equipment Design

ht = 188 + 13 + 20

= 221mm liquid

= 9.81 x 10-3 x 221 x 935.24

= 2027.6 Pa

= 0.29 Psia (per plate)

6. Downcomer Design:
The downcomer area and the plate spacing must be such that the level of the liquid and froth in
the downcomer is well below the top of outlet weir on the plate above. If the liquid rises above
the outlet weir the column will flood.

hb = (hw + how) + ht + hdc

Where,

hb = downcomer backup, measured from plate surface, mm

hdc= head loss in downcomer, mm

hdc = 166 [ ]2

where,

hdc = head loss in downcomer, mm

Lwd = liquid flowrate in downcomer, kg/s

Am = Either downcomer area or clearance area under the downcomer Aop which is smaller.

Aop = hop Lw

Where, hop = height of bottom edge of apron above plate

Lw = length of weir

hop = hw – 10

= 50 – 10 = 40mm

So, Aop= 0.040 x 2.99m

117
Chapter 5 Equipment Design

= 0.120m

hdc = 166 [ ]2

= 13.07mm

So, backup in downcomer = hb= (50 +138) +13.07 + 221

= 422.07mm = 0.422m

Then , backup in downcomer < ½ (plate spacing + weir height)

0.422 < ½(0.800 + 0.50)

0.422 < ½ 0.425

So, plate efficiency is acceptable.

7. Entrainment Calculation:
For checking entrainment , we calculate

Uv =

Uv = = 1 m/s

% flooding =

= = 85%

We already know FLV

FLV = 0.71
42

It is well below 0.1, so there is no chance of entrainment and process is satisfactory.

8. Calculation of Height of Column:


No. of plates = 30

Tray spacing = 0.800m

118
Chapter 5 Equipment Design

Tray thickness = 0.005m

Total thickness of trays = 0.15m

Top clearance = 1m

Bottom clearance = 1m

Total height = 25m

5.5 MDEA Surge Drum:


Flow rate of MDEA = 2349334.04 Ib/hr
Density of MDEA at 160oF = 64.6 Ib/ft3

Basis 24 hours
Vol. of MDEA for 24 hr = 2349334.04 x 24/64.6 = 872817.6 ft3
Total vol. of vessel = vol. of MDEA + 10% allowance
= 872817.6 x 1.10 = 960099.36 ft3
Let us suppose that 0.3% of MDEA solution is slipped in the surge tank
=960099.36 *0.03=2858.29 ft3=81m3

V = d2h/4
[1]
Let, h/d = 3 or h = 3d
V = 3 d /4
3

From here, d = 3.25m so, h=9.75 m

Design Specifications
Time of operation = 24hr
Dia. Of vessel = 3.25m
Height of Vessel = 9.75m
Recommended material of instruction is carbon steel

119
Chapter 6 Instrumentation & Process Control
Chapter 6 Instrumentation & Process Control

6.1 Amine Plant Control


Optimal amine control will reduce corrosion, energy consumption, improved treated gas
quality, reduce hydrocarbon load to sulphur recovery unit and improve H2S/CO2 ratio to
Sulphur recovery unit.

In Amine contactor bottom section most of the heat of reaction44 is released. If there is high
amine loading then it will lead towards corrosion. In the following control scheme we have used
the temperature near the middle of the amine absorber to reset the control the amine flow. By
controlling the amine flow rate the chances of corrosion due to temporary overloading of rich
amine solution is reduced. Level is controlled in the absorber by using Proportional controller.
Sweet gas pressure is maintained by using Proportional Integral Controller.

In Regenerator section we have used flow ratio control45 to set the reboiler heat medium mass
flow at a fixed value in relation to the rich amine and second control method on regenerator
uses the temperature between the top tray and overhead condenser to reset the reboiler heat
medium flow.

In lean/rich MDEA Exchanger, the rich MDEA is more important because it after the exchanger
it leads to Regenerator column. Any change in its dynamic can alter the dynamics of the whole
column. Hence the lean MDEA stream is manipulated to keep the temperature of rich MDEA
constant.

Further in Lean MDEA cooler, the lean MDEA stream is the key stream because it then flows to
absorber and hence failure to meet the required temperature will affect the absorber
performance. Hence the speed of the fan of Air Fin Fan Cooler Is varied to meet the constant
lean MDEA temperature. The control action is simple, since the temperature usually has a
sluggish response so a PID controller is more suitable.

120
Chapter 6 Instrumentation & Process Control

6.2 Process Instrumentation Diagram for Amine plant:

121
Chapter 7 Cost Estimation
Chapter 7 Cost Estimation

7.1 Plant Cost Estimation:


As the process design is completed it becomes possible to make accurate cost estimation
because detailed specification can thus be obtained from various manufactures. However
no design project should proceed to the final stages before costs are considers and the cost
estimation should be made throughout all the early stages of the design when complete
specifications are not available. Evaluation of costs in the preliminary design is said pre
design cost estimation. Such estimation should be capable of providing a basis for company
management to decide whether or not further capital should be invested in the project.

An evaluation of costs in the preliminary design phase is sometimes called as guess


estimation and often rule of thumb are used. A plant design obviously must present a
process that is capable of operating under conditions which will yield a profit.

A capital investment is required to any industrial process, and determination of necessary


investment is an important part of plant design project. The total investment for any
process consists of physical equipment and facilitates in the plant plus the working capital
for money which must be available to pay salaries. Keep raw materials and products on
hand and handle other special items requiring a direct cash layout.

7.2 Capital Investment:


Before industrial plant can be put into operation, large amount of money must be supplied
to purchase and install the necessary machinery and equipment, land services facilitates
must be obtained and plant must be erected, complete with all pipe control services. In
addition it is necessary to have money available for payment of expenses involved in plant
operation.

The capital needed to supply the necessary manufacturing and plant facilities is called fixed
capital. Fixed cost capital investment while necessary for the operation of the plant termed
as Working Capital. The sum of fixed capital investment and the working capital is known as
total capital investment.

Fixed capital investment classified into two subdivisions: namely

 Direct costs
 Indirect costs

7.2.1 Direct costs:


The direct cost items are incurred in the construction of planet in addition to the cost of
equipment:

 Purchase equipment
 Purchase equipment installation
 Instrumentation

122
Chapter 7 Cost Estimation

 Piping
 Electrical Equipment and materials
 Building (including services)
 Service facilities
 Taxes

7.2.2 Indirect costs:


These include:

 Design and engineering


 Contractors expanses
 Contractors fee
 Contingency

7.3 Types of Cost Estimation:


Various methods are employed for estimating capital investment are as follows:

 Preliminary estimate
 Definitive estimate
 Detailed estimate

In choosing the method for cost estimation following factors are considered:

 Amount of detailed information available


 Accuracy desired
 Time spent on estimation

7.4 Methods of Estimating Capital Investment:


Seven methods of estimating capital investment are outlined below:

 Detailed item estimate


 It cost estimate
 Percentage of delivered equipment cost
 “Lang” factor for approximation of capital investment
 Power factor applied to plant capacity ratio
 Investment cost per capacity
 Turnover ratio

7.5 Percentage of Delivered Equipment Cost:


This method for estimating the fixed or total capital investment requires determination of
the delivered equipment cost. The other items included in the total direct plan cost are then
estimated as Percentage of Delivered Equipment Cost.

123
Chapter 7 Cost Estimation

The percentage used in making an estimation of this type should be determined on the basis
of type of process involved, design complexity required, material of construction, location of
the plant, past experiences, and other items depend on the particular unit under
consideration.

Purchased equipment cost for common plant equipment = Ce = E

Ce= a + b (S)n

Where a & b are cost constants

S = size parameter

n = exponent for that type of equipment

(these all above values have been obtained from table # 6.6, Coulson vol.6, Ed.5. for year
2007 )

1. Cost of Absorber:
We know that

C= a+b(S)n

Diameter of Absorber = 2.4 m

sizing factor (S) = 2.4


46
a = 110, b = 380, n= 1.8 (for year 2007)

so,

C = 110+380(2.4)1.8

= $1947 ( Cost/Tray)

Total cost of one absorber = 1947 x 27

= $52569

As we have used two absorber, so

Cost of both Absorbers = $52569 x 2

124
Chapter 7 Cost Estimation

= $105138

This cost is for year 2007, so by applying inflation rate of 3.3% per year, we can find cost in
2013.

C = 105138(1.033)6 = $127750.21

2. Cost of Exchanger:
We know

C= a+b(S)n

Sizing parameter of exchanger (S) = 584 m2

a = 1350, b = 180, n = 0.9547 (for year 2007)

so,

C = 1350+180(584)0.95

= $73313

This cost is for year 2007, so by applying inflation rate of 3.3% per year, we can find cost in
2013.

C = 73313(1.033)6 = $89080.

3. Cost of Inlet Gas Separator:


Diameter = D = 2.06 m

Length = L = 6.34 m

From Graph48

C = 22000

Pressure Factor = 1.4 (at 30 psia)

So,

C = 22000 x 1.4 = $30800

This cost is for year 2004, so by applying inflation rate of 3.3% per year, we can find cost in
2013.

C = 30800(1.033)9 = $41253.

125
Chapter 7 Cost Estimation

4. Cost of Lean Solvent pump:


Capacity of Pump = 3919 GPM

From Graph

C = $25000

This cost is for year 1988, so by applying inflation rate of 3.3% per year, we can find cost in
2013.

C = 25000(1.033)21 = $49436.

5. Cost of MDEA Surge Tank:


Capacity of tank = 81 m3

We know that

C = C= a+b(S)n

a = 5000, b = 1400, n = 0.7 (cone roof)49 (for year 2007)

so, C = 5000+1400(81)0.7

= $35343

This cost is for year 2004, so by applying inflation rate of 3.3% per year, we can find cost in
2013.

C = 35343(1.033)9 = $47337.

E = $354856

7.6 Direct Cost: 50


Component % of E Cost ($)

Purchased Equipment Installation 0.25E 88714


Instrumentation installation 0.07E 24840
Piping 0.08E 28388
Electrical 0.05E 17723
Building 0.05E 17723
Yard improvement 0.02E 7097
Service facilities 0.15E 53228
Land 0.01E 3549
Total direct cost = D = 241262

126
Chapter 7 Cost Estimation

7.7 In-Direct cost:


Engineering & Supervision = 0.33E = $117102 (1)

Construction Expenses = 0.41E = $145490 (2)

Total in-direct Cost = $262592

Total Cost = direct Cost + indirect cost

= $503855

Contactor’s Fee = X = 0.05 (D+I) = $12063

Contingency = Y = 0.10 (D+I) = $24126

Fixed Capital Investment = (D+I+X+Y) = $540043

Working Capital Investment = 0.15(D+I+X+Y) = $81006

127
Chapter 8 HAZOP Study
Chapter 8 HAZOP Study

8.1 HAZOP study:


A Hazard is something which may cause harm and is an undesired event. The word HAZOP
refers to the detail study regarding operability and hazards. It’s a formal procedure to identify
hazards in a chemical process facility. This systematic study is used to find out operability
problems and equipment hazards or all plant hazards. The method for doing HAZOPS study
involves detail examination of each equipment (instruments, piece of equipment, pipeline) and
the finding out all possible deviation from normal operating conditions. Before the HAZOP
study is started, detailed information on the process must be available. This includes up-to-date
process flow diagrams (PFDs), process and instrumentation diagrams (P&IDs), detailed
equipment specifications, materials of construction, and mass and energy balances.
A HAZOP study is conducted in the following steps

 Specify the purpose, objective, and scope of the study. The purpose may be the analysis of a yet
to be built plant or a review of the risk of unexisting unit. The scope of the study is the
boundaries of the physical unit, and also the range of events and variables considered. The
initial establishment of purpose, objectives, and scope is very important and should be precisely
set down so that it will be clear, now and in the future, what was and was not included in the
study. These decisions need to be made by an appropriate level of responsible management.
 HAZOP team is selected.
 For the collection of data following materials are needed:

 Process description
 Process flow sheets
 Data on the chemical, physical and toxicological properties of all raw materials,,
intermediates, and products.
 Piping and instrument diagrams (P&IDs)
 Equipment, piping, and instrument specifications
 Process control logic diagrams
 Layout drawings
 Operating procedures
 Maintenance procedures
 Emergency response procedures
 Safety and training manuals

128
Chapter 8 HAZOP Study

8.1.1 Objectives of HAZOP study:


 To find out those areas in design which can have significant hazard potential.
 To study and find out those aspect of design that effects the occurrences of hazardous
incidence.
 To make study team familiar with design information.
 To make sure that systematic study of areas involving hazard potential is made.
 To provide a mechanism for feedback to the client of the study team's detailed
comments

8.1.2 HAZOP Team:


HAZOP studies are carried out using a `brainstorming' approach by a team, chaired and
coordinated by a qualified person experienced in Team leadership Following are the members
of HAZOP team:

 Team Secretary
 Process Engineer
 Mechanical Engineer
 Commissioning/Operations
 Engineer/Manager
 Instrument Engineer

8.1.3 Strength of HAZOP:


• HAZOP is a systematic, reasonably comprehensive and flexible.

• It gives good identification of cause and excellent identification of critical deviations.

• The use of keywords is effective and the whole group is able to participate.

• HAZOP is an excellent well-proven method for studying large plant in a specific manner.

8.1.4 Weakness of HAZOP:


• HAZOP is very time consuming and can be laborious with a tendency for boredom for
analysts.

• It tends to be hardware-oriented and process-oriented, although the technique should


be amenable to human error application.

• HAZOP does not identify all causes of deviations and therefore omits many scenarios.

129
Chapter 8 HAZOP Study

8.1.5 Responsibility of HAZOP Team Members:


• Plan sessions and timetable

• Control discussion

• Limit discussion

• Encourage team to draw conclusion

• Ensure secretary has time for taking note

• Keep team in focus

• Encourage imagination of team members

• Motivate members

• Discourage recriminations

• Judge importance issues

8.1.6 Guide Words:

Guide Words Meaning Comments


No or Not Negation of intention No flow of A
More Quantitative increase Flow of A greater than design flow
Less Quantitative decrease Flow of A less than design flow
As well as Quantitative increase Transfer of some component
additional to A
Part of Quantitative decrease Failure to transfer all components of
A
Reverse Logical opposite of intention Flow of A in direction opposite to
design direction
Other than Compete substitution Transfer of some material other than
A

130
Chapter 8 HAZOP Study

8.2 HAZOP Study of storage Tank for MDEA:


A HAZOP study is to be conducted on MDEA storage tank, as presented by the piping and
instrumentation diagram show below.
In this scheme, MDEA is unloaded from tank trucks into a storage tank maintained under a
slight positive pressure until it is transferred to the process. Application of the guide words to
the storage tank is shown in Table (8.1) along with a listing of consequences that results from
process deviation.

Piping & instrumentation Diagram of MDEA storage Tank51

131
Chapter 8 HAZOP Study

Table 8.152
Equipment Deviations What event Consequences Additional Process Notes and questions
reference from operating could cause of implications of indications
and conditions conditions this this deviation this
operating deviation? on consequence
conditions item of
equipment
under
consideration
MDEA Level 1. Tank runs dry Pump Damage to LIA-1, Can reagent
Storage  Less cavitates pump, FICA-1 react/explode if over-
tank heated in pump?
2. Rupture 4-in. Reagent Potential fire LIA-1, Estimate release
discharge released FICA-l quantity. Consider
second LAL
shutdown on pump.
3. V-3 open or Reagent Potential fire LIA-1 Estimate release
broken released quantity.
4. V-l open or Reagent Potential fire LIA-1 Consider V-l
broken released protection
5. Tank rupture Reagent Potential fire LIA-1 What external events
released can cause rupture
 More 6. Unload too Tank overfills Reagent LIA-1 Is RV-1 designed to
much from tank released relieve liquid
truck via RV-1 atloading rate?
.Consider secondhigh
level shutoff.
7. Reverse flow Tank overfills Reagent LIA-1 Consider check
from process released valvein pump
via RV-1 discharge line.
Consider second LAH
shutdown on feed
lines.
Composition 8. Wrong Possible Possible tank Consider
Other than reagent reaction rupture samplingbefore
unloading.
As well as 9. Impurity in If volatile, Are other
reagent possible materialsdelivered in
overpressure trucks?
Pressure 10. Break l-in. Reagent Potential fire PICA-l Consider PAL to
 Less line to flare or l- released PICA- 1. Consider
in nitrogen line independent
PAL.
11. Lose nitrogen Tank implodes Reagent PICA-l Consider vacuum-
released break
Valve.
12. PV-2 fails Tank implodes Reagent PICA-l consider PAL on
closed released PICA-l
13. PICA-1 fails, Tank implodes Reagent PICA-l Tank not designed
closing PV-2 released for vacuum.

132
Chapter 8 HAZOP Study

 More 14. PICA-l fails Reagent Tank rupture if PICA-l What is capacity of
closing PV-1 released RV-1 fails PV-l? RV-l? Consider
via RV-1 independent PAH.
15. PV-1 Reagent Tank rupture if PICA-l Consider
failsclosed released RV-1 fails independent PAH.
via RV-1
16. V-7 closed Reagent Tank rupture if PICA-l Is V-7 locked open?
released RV-1 fails Is V-S locked open?
via RV-1 Consider
independent PAH.
17. Overfill tank See Event 6 Tank rupture if PICA-l Consider second
RV-1 fails High-level shutoff.

18. Temperature Reagent Tank rupture if PICA-l What prevents high


of released RV-1 fails Temperature of
inlet is hotter via RV-1 inlet?
than normal

133
Chapter 9 Operational Problems
Chapter 9 Operational Problems

9.1 Problems occurring during operation:


One of the reasons that alkanolamine processes have become the predominant choice for both
refinery gas treating and natural gas purification is their comparative freedom from operating
difficulties. Nevertheless, several factors can result in undue expense and cause difficulties in
the operation of alkanolamine units. Chief among these, from an economic standpoint are
corrosion and amine loss. Other operating difficulties, which occasionally limit the capacity of
plant for gas purification, include foaming and plugging of equipment. In many cases, operation
can be significantly improved by daily monitoring of key plant operating variables and by proper
control and design of treating plant.

9.2 Foaming53:
Foaming of alkanolamine solution is probably the most common operating problem in amine
treating units. It is most frequently encountered in contractor, but may also occur in the
stripping column.

Causes of Foaming:
Specific cause of foaming includes the following:

 Water soluble surfactants in the feed gas (e.g. well treating compounds, pipeline corrosion
inhibitors) which lowers the amine solutions surface tension. Excessive antifoam can also
cause foaming.
 Liquid hydrocarbons e.g. entrained compressor lubricating oils in the feed gas or
hydrocarbons condensation within the amine absorber.
 Particulate contaminants (e.g. mill scale, FeS correction products, rust contained in the feed
gas or produced within amine treating units. Solids such as FeS do not cause foaming but
concentrate at liquid/gas interface and stabilize the foam by increasing the surface viscosity
retarding film drainage.
 Oxygen contamination of feed gas or amine unit (usually at the amine sump or amine
storage tank) and reaction of amine heat stable salts. Dissolved iron can catalyze the
reaction of amine with oxygen to foam carboxylic acid.
 Feed gas contamination such as carboxylic acid, which react with amine to form heat stable
salts.
 Contamination of amine unit with gases and oils during a turnaround.
 Amines filter elements that have been washed with surfactants or contaminated with oils
during manufacture.
 Contaminants in the amine plant makeup water such as boiler feed water treating
chemicals and corrosion inhibitors.

134
Chapter 9 Operational Problems

Prevention of Foaming:
Foaming can be reduced or controlled by proper care of the amine solution. The following
techniques reduce the amine solution contamination and minimize foaming:

 A properly designed feed gas inlet separator and filter should be provided. A feed gas
coalscer should be considered for feed gas stream contaminated with compressor
lubricating oils and other finally dispersed aerosols. A properly size slug catcher should be
provided if slugs can accumulate in the feed gas line.
 A feed gas water wash should be considered when the feed gas streams is severely
contaminated with carboxylic acid or water soluble, surface active contaminates. A feed gas
water wash can also remove aerosols and ultra fine chemicals.
 Onsite of offsite amine solution reclaiming to remove heat stable salts and amine
degradation products. No more than 10% of the amine should be tied up as stable salts.
 Caustic addition to neutralize heat stable salts to mitigate corrosion and thereby reduce
iron sulfite formation.
 A properly sized rich amine flash drum remove entrained and dissolved hydrocarbons.
 Liquid skimming facilitate in the absorber sump, the rich amine flash drum, the regenerator
sump and the amine regenerator overhead accumulator.
 New plants and old plants that have undergone a major turnaround or often contaminated
with oils, greases welding fluxes and corrosion inhibitors. A hot caustic wash (2-5 wt%
caustic soda) followed by a hot condensate wash can remove these impurities and help to
prevent foaming.
 Addition of antifoam is carried out.

9.3 Corrosion:
By far the most serious operating problem encountered with amine gas purification process
is corrosion as would be expected this problem has been given widest attention. Generally,
it occurs in regenerator heat exchanger and pumps. The extent and type of corrosion has
been observed to depend upon such factors as the amine used, the presence of
contaminants in the solution leading with acid gas, the temperature and pressure,
prevailing in various part of the plant, the velocity with which the solution flows and others.
However, it appears that the principal corroding agents are the add gases. The rate of
corrosion increases with increase acid gas concentration n solution.
Corrosion due to hydrogen sulfide and carbon dioxide is frequently observed a filter shell
and the hot end heat exchanger tubes. To minimize corrosion by hydrogen sulfide and
carbon dioxide, the acid gases must be held in a relatively corrosive form until regeneration
of amine solution is stripping still.

135
Chapter 9 Operational Problems

Overloading the amine solution will increase the chance for corrosion due to pressure
reduction or high temperature in the heat exchanger. This danger can be remedied
bymaintaining sufficient pressure on the foul amine solution and by operating the unit at as
low and acid gas alkanolamine ratio as possible. This ration should not exceed 0.05 moles of
acid gas per mole of alkanolamine and should be event less of condition permits.

Mechanism of Corrosion:
It is known that free or “aggressive” carbon dioxide causes severe corrosion particularly at
elevated temperature and in the presence of water.
It is believed that the metallic iron with carbonic acid which results in the formation of stable
iron bicarbonate. Further heating of solution may cause the release of carbon dioxide and the
precipitate of the iron as the relatively insoluble carbonate.
Hydrogen sulfide attacks steel as an acid with the subsequent formation of insoluble ferrous
sulfite. This compound forms a coating on the metal surface which does not adhere tightly and
therefore affords little protection from further corrosion. There is no satisfactory correlation
available for carbon dioxide, hydrogen sulfide mixture, which relates the corrosive attacks to be
expected with any given ratio of hydrogen sulfide to sulfur dioxide.
However, certain generalized observation has been made. It appears that in plant handling
predominantly carbon dioxide, very small quantity of hydrogen sulfide may actually reduce
corrosion. On the other hand, each of the acid gases increases the corrosive attacks of the
other.

Methods of Minimizing Corrosive Attacks:


Corrosion can be reduced by various methods, including certain protection in the operation and
process design of purification plants. Use of more expensive corrosion resistant material and
continues or periodic removal of corrosion promoting agent from the solution. A combination
of several of these measures usually leads to most satisfactory and economical to reduce
corrosion attacks;

 The temperature of the solution in the reboiler and the temperature of the steam used in
the reboiler should be kept as low as possible.
 Use of high temperature heat carrying media, such as oil, should be avoided to maintain the
lowest possible skin temperature of metal.
 Pressure regenerator with its accompanying high temperatures results in severe corrosion
of reboiler tubes; it is, therefore, good practice to maintain the lowest possible pressure on
the stripping column and reboiler.
 To prevent oxygen from entering the system, it is advisable to maintain a blanket of inlet
gas over all portion of the solution, which could be exposed to atmosphere and to ensure
the pressure the suction side of all pumps.

136
Chapter 9 Operational Problems

 Continuous removal of suspended solids (by nitration) and the decomposition product (by
distillation of a side stream) generally helps to reduce corrosion.

9.4 Chemical Losses54:


The loss of a solvent can be a serious operating difficulty in alkanolamine gas purification
plants. Corrosion can be incurred by entrainment of the solution in the gas stream vaporization
or chemical degradation of the amine. Loss of the solvent by entrainment or vaporization is
undesirable not only because of the cost of chemicals but also because of the contamination of
the pipelines by liquid deposited on the walls. In addition when alkanolamine solution are used
to purify the gas to be used in catalytic process, entrainment by vaporization of solvent result in
a serious poisoning of the catalyst.

9.5 Losses due to Volatility:


Glycol volatility losses are usually significant in ethylene glycol, di-ethylene glycol but very less
in tri-ethylene and higher glycols, which have very high boiling points. Hence usually a very
small amount of glycol is lost by vaporization into gas stream in absorbers and also in
regenerators.

Prevention from Volatility Losses:


Volatility losses can be prevented by following methods:

 A cold water flux is provided at the top plate of regenerating column.


 Normally absorbers are operated at lower temperatures (80-1100F recommended) to
avoid losses.

9.6 Entrainment:
In many cases most of the glycol loss occurs as carry over of solution with the product gas.
Entrainment losses are caused either by inefficient mist extraction or by foaming and
subsequent carry over solution. Entrainment losses from glycol absorber vary considerably
depending on the mechanical design of both the upper solution of absorber and mist
elimination devices.

Prevention from Entrainment Losses:


Entrainment can be mi minimized by the following techniques:

 Using efficient mist elimination equipment.


 Application of the foam inhibitor.

137
BIBLOGRAPHY
BIBLOGRAPHY

1- TIM C.LIEUWEN & VIGOR YANG & RICHARD YETTER, “ Synthesis Gas Combustion
Fundamentals and Applications”, Page 19, Table 1.5

2- TIM C.LIEUWEN & VIGOR YANG & RICHARD YETTER, “ Synthesis Gas Combustion
Fundamentals and Applications”,Table 1.5

3- PETER HAUSSINGER & REINER LOHMULLER & ALLAN M. WATSON, “


Ullmann´sEncyclopaedia of Industrial Chemistry”, Page 340
4- PETER HAUSSINGER & REINER LOHMULLER & ALLAN M. WATSON, “ Ullmann´s
Encyclopaedia of Industrial Chemistry”, Page 345.

5- GAS PROCESSORS SUPPLIERS ASSOCIATION, “Engineering Data Book”, page 21-5,


Volume 2, Edition 12th.
6- GAS PROCESSORS SUPPLIERS ASSOCIATION, “Engineering Data Book”, page 21-10,
Volume 2, Edition 12th
7- ARTHUR KOHL & RICHARD NELSON , “ Gas Purification” , Page 53, Edition 5 th .
8- ARKEMA, “MDEA Proven Technology For Gas Treating Technology”, Page 3.
9- Adapted from DOE / NETL (Department of Energy / National Energy Technology
Laboratory), (2011), Advanced Carbon Dioxide Capture R&D Program: Technology
Update, U.S

10- ARTHUR KOHL & RICHARD NELSON , “ Gas Purification” , Page 1202, Table 14-1, Edition
5th
11- ARTHUR KOHL & RICHARD NELSON , “ Gas Purification” , Page 1048, Table 12-1, Edition
5th
12- ARTHUR KOHL & RICHARD NELSON , “ Gas Purification” , Page 1256, Table 15-2, Edition
5th
13- LUDWIG, “Applied Process Design for Chemical and Petrochemical Plants”, Page 303,
Volume 2, Edition 4th.
14- TENNEYSON, R.N. & SCHAAF, R.P, "Guidelines Can Help Choose Proper Process for Gas
Treating Plants", Oil and Gas Journal, January 10, 1977, page 78.

138
BIBLOGRAPHY

15- ARTHUR KOHL & RICHARD NELSON , “ Gas Purification” , Page 4, Edition 5th. 1979
16- Amine & Plasticizers limited,AN ISO 9001:2008 CERTIFIED COMPANY.

17- A.A.C.M BEENACKERS, “Methanol production from wood-Results of the EEC Pilot
Programme”, ,page 7, Table 1.1
18- NREL(national renewable energy laboratory),task 2:Gas cleanup design and cost
estimates-Wood Feedstock.
19- TOTAL FINAELF, “Oil and Gas processing plant Design and operation training course”,
“Gas sweetening process”, Page 9, 2002

20- SCHEIMAN A.D, “Horizontal Vapor and Liquid Separators, Hydrocarbon Processing &
Petroleum Refinery”, Page 155, May 1964.
21- GAS PROCESSORS SUPPLIERS ASSOCIATION, “Engineering Data Book”, Fig 7-20, Volume
1&2, Edition 12th .
22- http://www.amistco.com/spanish/tech105.htm
23- STANLEY M . WALAS, “Chemical Process Equipment “, page 649, edition 2nd .

24- T.KUPPAN, “ Heat Exchanger Design Handbook”, page 351, Table 2.


25- T.KUPPAN, “ Heat Exchanger Design Handbook”, page 351.
26- T.KUPPAN, “Heat Exchanger Design Handbook”, Page 349, Table 1
27- T.KUPPAN, “Heat Exchanger Design Handbook”, Page 355, Table 4
28- T.KUPPAN, “Heat Exchanger Design Handbook” , Page 356, Table 5
29- T.KUPPAN,” Heat Exchanger Design Handbook”, Page 354, Table 3
30- R.K SINNOTT ,”Coulson & Richardson`s Chemical Engineering” , Page 760, Figure 12.62,
volume 6 ,edition 4th.
31- R.K SINNOTT,” Coulson & Richardson`s Chemical Engineering” , Page 637 , Table 12.1,
volume 6 ,edition 4th.
32- T.KUPPAN,”Heat Exchanger Design Handbook”, page 368, Table 2.
33- R.K SINNOTT, Coulson & Richardson`s Chemical Engineering , Page 757 table 12.9,
Volume 6 , Edition 4th.

139
BIBLOGRAPHY

34- R.K SINNOTT, “Coulson & Richardson’s Chemical Engineering” page 558-561, Volume 6,
Edition 4th.
35- ERNEST E. LUDWIG, “Applied Process Design for Chemical & Petrochemical Plants”, page
109, Volume 2, Edition 3rd.
36- GAS PROCESSORS SUPPLIERS ASSOCIATION, “Engineering Data Book”, page 25-23,
Volume 1&2, Edition 12th.
37- R.K SINNOTT, “Coulson & Richardson’s Chemical Engineering” page 567-579, Volume 6,
Edition 4th.

38- R.K SINNOTT, “Coulson & Richardson’s Chemical Engineering”, Figure 11.27, page 568,
Volume 6, Edition 4th.
39- R.K SINNOTT, “Coulson & Richardson’s Chemical Engineering”, Figure 11.31, page 573,
Volume 6, Edition 4th.
40- R.K SINNOTT, “Coulson & Richardson’s Chemical Engineering”, Figure 11.30, page 571,
Volume 6, Edition 4th.

41- R.K SINNOTT, “Coulson & Richardson’s Chemical Engineering”, Figure 11.34, page 576,
Volume 6, Edition 4th.
42- R.K SINNOTT, “Coulson & Richardson’s Chemical Engineering”, Figure 11.29, page 570,
Volume 6, Edition 4th.
43- ERNEST E. LUDWIG, “Applied Process Design for chemical & petrochemical plants”, page
110, Volume 2, Edition 3rd.
44- APTHUR KOHL, “Gas Purification”. Page 205, Edition 5th.
45- APTHUR KOHL, “Gas Purification”. Page 204, Edition 5th.

46- RAY SINNOTT & CAVIN TOWLER, ”Chemical Engineering Design”, page 314, Table 6.6,
Volume 6, Edition 5th.
47- RAY SINNOTT & CAVIN TOWLER, ”Chemical Engineering Design”, page 313, Table 6.6,
Volume 6, Edition 5th.
48- R.K SINNOTT, ”Chemical Engineering Design”, page 256, Figure 6.5a,b.

140
BIBLOGRAPHY

49- RAY SINNOTT & CAVIN TOWLER, ”Chemical Engineering Design”, page 314, Table 6.6,
Volume 6, Edition 5th.
50- MAX S.PETERS & KLAUS D.TIMMERHAUS, ” Plant Design & Economics For Chemical
Engineer”, page 167, Table 4, Edition 4th.
51- MAX S.PETERS & KLAUS D.TIMMERHAUS , “Plant Design and Economics For Chemical
Engineers”, page 63, Edition 4th.

52- MAX S.PETERS & KLAUS D.TIMMERHAUS , “Plant Design and Economics For Chemical
Engineers”, page 64, Edition 4th.
53- APTHUR KOHL, “Gas Purification”. Page 224, Edition 5th.
54- ARTHUR KOHL, “Gas Purification”. Page 231, Edition 5th

141

S-ar putea să vă placă și