1

WASTE WATER MINIMIZATION IN PETROLEUM REFINERY USING PINCH

TECHNOLOGY

OKAFOR INNOCENT IFEANYI

B.ENG (HONS) (YOLA)
11/PG/EG/CE/004

OCTOBER, 2014
 2

WASTE WATER MINIMIZATION IN PETROLEUM REFINERY USING

PINCH TECHNOLOGY

BY

OKAFOR, INNOCENT IFEANYI

B.ENG. (HONS)(YOLA)
11/PG/EG/CE/004

A DISSERTATION IN THE DEPARTMENT OF CHEMICAL/PETROLEUM

ENGINEERING, FACULTY OF ENGINEERING,

PRESENTED TO

THE POST GRADUATE SCHOOL, UNIVERSITY OF UYO, UYO,

AKWA IBOM STATE, NIGERIA. IN PARTIAL FULFILMENT OF THE
REQUIREMENTS FOR THE AWARD OF MASTERS OF ENGINEERING (M.Eng)
DEGREE IN CHEMICAL ENGINEERING

OCTOBER, 2014
 3

DECLARATION

I hereby declare that this dissertation: Waste Water Minimization in Petroleum

Refinery using Pinch Technology has been written by me and it is the record of my own

research work. It has not been presented in any previous application for higher degree.

All sources of information are specifically acknowledged using references.

Okafor Innocent Ifeanyi

October, 2014.

CERTIFICATION
 4

This dissertation entitled “Waste Water Minimization in Petroleum Refinery using Pinch

Technology” by Okafor, Innocent Ifeanyi (11/PG/EG/CE/004) meets the regulations governing

the award of the degree of Masters of Engineering (M.Eng.) of the University of Uyo and is

approved for its contribution to knowledge and literary presentation.

------------------------- -----------------------
Prof, E N Bassey Date
Department of Chemical/Petroleum Engineering
Faculty of Engineering
University of Uyo, Uyo
(Supervisor)

--------------------------- -----------------------
Prof, Date
(Internal Examiner)

---------------------------- -----------------------
Dr, I. O Oboh Date
Department of Chemical/Petroleum Engineering
Faculty of Engineering
University of Uyo, Uyo
(Chief Examiner / HOD)

DEDICATION
 5

This work is dedicated to God almighty for giving me the grace to complete this task. It

is also dedicated to my only sister, late Mrs. Otokolo Rosemary Ekene who slept in the Lord

during the period of this research.

ACKNOWLEDGEMENT
 6

My profound gratitude goes to the owner of my life (Jesus Christ) whom by his grace

favored me through the successful completion of my master’s programme. Great thanks to my

able supervisor Professor E N Bassey for his unquantifiable contributions to the success of this

work. Without his encouragement, direction and suggestions it would not have been possible, he

was indeed my supervisor cum ‘father’.

My special thanks to my family members, most especially, my wife, Mrs. Okafor Rume,

the incomparable companion of mine, the love of my heart. And to my son mike Okafor whose

presence with me in Uyo during the research gave me extra zeal to push further. Also, thanks to

my beloved parents Chief and Mrs. Stephen Okafor for their special role in my life. To my

brothers, Chukwudi, Chris, and Steve, I say thanks to you in bundles for supporting me. My

only sister Mrs. Rose Otokolo, I cannot thank you enough for your immense support during this

work.

A million thanks to the families of Mr. & Mrs. Elijah Ebong and Mr. & Mrs. Ita Eyo

also sister Mercy and sister Naomi, you were more than a family to me, thanks a lot. To my

pastor, Mr. Uduak Essien, thanks more than a million times for your prayers. The members of

RCCG Jehovah Shalom Parish Uyo, special thanks to you all.

The special contributions made by Dr. S B Alabi and Mr. C.S Okoli is noted and

appreciated, special thanks to my Head of Department Dr. I. O. Oboh for his encouragement.

I shall not forget to appreciate my friend Mr. Akpan Ime Elijah, ’my brother from a

different mother’ for paving the way for me to start and finish this programme also my good

friends Effiong S. Kemudeme and Etteh E. Ekereobong thanks once again.

Many, who have contributed to the success of this work but do not have their names on

this page, should note that it is not a sign of ingratitude; God who is greater than me has noted

them and shall reward them appropriately.

ABSTRACT
 7

Waste water generation in the petroleum refinery and the stringent environmental disposal
regulations have called for an intensive waste water management. This work has described how
water pinch technology can be used to minimize the waste water generation by reducing the
freshwater demand in the petroleum refinery. The work focused on the application of water
reuse and regeneration reuse technique for the design of an integrated water using network that
achieved a reduced flow rate of fresh water supply and wastewater generation in the petroleum
refinery while the water-using operation still received adequate water for their mass transfer
operations. Three key contaminants including Hydrogen sulphide, Suspended solids and oil
were considered based on the single contaminant and multiple contaminant approaches.
Analyzing both methods, it was clearly demonstrated that the amount of the required fresh
water in an operation was determined by mass transfer of the chosen reference contaminant
(key contaminant). In addition, the method based on multiple contaminants gave more precise
results than that based on the single contaminant, giving a fresh water saving of about
23.1percent using the single contaminant approach and a corresponding 13.2 percent with the
multiple contaminants approach.
 8

TABLE OF CONTENTS

CHAPTER TITLE PAGE

Cover Sheet----------------------------------------------------------- i

Title Page ------------------------------------------------------------- ii

Declaration------------------------------------------------------------ iii

Certification----------------------------------------------------------- iv

Dedication-------------------------------------------------------------- v

Acknowledgements---------------------------------------------------- vi

Abstract------------------------------------------------------------------ vii

Table of contents-------------------------------------------------------- viii

List of tables ----------------------------------------------------------- xi

List of figures -------------- ------------------------------------------- xii

List of Appendices ---------------------------------------------------- xiii

Nomenclature----------------------------------------------------------- xiv

CHAPTER ONE: INTRODUCTION

Background of the Study---------------------------------------------------- 1

Water and Petroleum/chemical Process Industry---------------------------- 1

Pinch Analysis------------------------------------------------------------------- 2

1.1.3 Water Pinch Technology Concept--------------------------------------------- 2

Statement of the Problem------------------------------------------------------- 2

Research Objective/Aims------------------------------------------------------- 3

Significance of the Study--------------------------------------------------------- 4

Scope and Limitation ---------------------------------------------------------- 4

Lay out of the Research-------------------------------------------------------- 4

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CHAPTER TWO: REVIEW OF RELATED LITERATURE

2.1 Pinch Technology---------------------------------------------------------------- 5

2.1.1 Water Pinch Technology-------------------------------------------------------- 6

2.2 Development of Water Pinch Technology----------------------------------- 7

2.3 Challenges of Water Pinch Technology---------------------------------------- 7

2.4 Technique of Solving Water Pinch Technology Problems----------------- 8

2.4.1 Composite Curve----------------------------------------------------------------- 8

2.4.2 Automated Procedure----------------------------------------------------------- 9

2.4.3 State Space Approach------------------------------------------------------------ 10

2.4.4 Limiting Water Profile------------------------------------------------------------ 10

2.4.5 Concentration Interval Diagram------------------------------------------------ 11

2.4.6 Water Surplus Diagram----------------------------------------------------------- 11

2.4.7 Water Cascade Table--------------------------------------------------------- 12

2.5 Application of the Technology in Refinery Operations---------------------- 12

CHAPTER THREE: RESEARCH METHODOLOGY

3.1 Areas of Pinch of Technology-------------------------------------------------- 18

3.2 The Refinery Operation as a Mass Transfer Operation----------------------- 18

3.2.1 The Steps Involved in the Conventional Water Reuse Approach----------- 18

3.2.2 The mass transfer problem------------------------------------------------------- 19

3.3 Determination of Limiting Water Flow rate---------------------------------- 19

3.3.1 Minimum Fresh Water Requirement Without Reuse-------------------------- 20

3.3.1a Graphical Approach------------------------------------------------------------ 21

3.3.1b Tabular method------------------------------------------------------------------ 22

3.3.2 Minimum Fresh Water Requirement with Regeneration------------------- 22

3.4 Driving Force Violation------------------------------------------------------ 23

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3.5 Design Equation for Network Simplicity with Full Regeneration----------- 23

3.6 Minimum Fresh Water Requirement with Regeneration Recycle---------- 25

3.7 Limitation of Single Contaminant Approach in finding Minimum

Fresh Water------------------------------------------------------------------------- 26

3.8 Multiple Contaminants Problem------------------------------------------------ 26

3.8.1 Concentration Shift-------------------------------------------------------------- 27

3.8.2 Design Equation for Multiple Contaminants------------------------------------ 28

3.8,3 Pinch Interval Water Reuse----------------------------------------------------- 32

CHAPTER FOUR: DATA PRESENTATIONAND ANALYSIS

4.1 Minimum Fresh Water and Network Design -------------------------------- 37

4.2 Cost Analysis -------------------------------------------------------------------- 49

CHAPTER FIVE: SUMMARY, CONCLUSION AND RECOMMENDATIONS

5.1 Summary------------------------------------------------------------------------- 51

5.2 Conclusions----------------------------------------------------------------------- 52

5.3 Recommendations --------------------------------------------------------------- 52

REFERENCES------------------------------------------------------------------------- 53

APPENDICES ------------------------------------------------------------------------- 56

LIST OF TABLES

TABLE TITLE PAGE

1 The Limiting Process Data for the Refinery--------------------------------- 37

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2A Concentration Interval Diagram for Oil ------------------------------- 38

2B Concentration Interval Diagram for Suspended Solid(S.S) ------------- 39

2C Concentration Interval Diagram for H2S ------------------------------------- 40

3A Cost Flow Comparism for before and after Pinch Analysis--------------- 49

3B Cost Flow Comparism for before and after Pinch Analysis--------------- 50

LIST OF FIGURES

FIGURE NAME PAGE

1 Composite curve to determine pinch point temperature --------------- 6

2a Composite curve to determine fresh water pinch point concentration----- 9

2b Flow chart of water network of a typical refinery------------------------------- 14

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3a Water minimization through (i) Reuse (ii) Regeneration reuse

(iii) Regeneration-recycle -------------------------------------------------------- 17

3b Contaminant rich process stream representation of water using operation--- 19

3c The relationship between the limiting water profile and water supply line--- 21

4a General Concentration interval below the pinch interval boundary----------- 29

4b General Concentration interval below the pinch interval boundary with

Pinch interval water reuse----------------------------------------------------------- 36

4c Water using network for oil as a reference contaminant without

regeneration ------------------------------------------------------------------------- 41

4d Water using network with full regeneration------------------------------------- 42

4e Block diagram of water net with full regeneration ---------------------------- 43

4f Limiting water profile for contaminant H2S ----------------------------------- 44

4g Limiting water profile for contaminant H2S with outlet concentration shift

on operation 3 ---------------------------------------------------------------------- 45

4h Water network for the multiple contaminant system prior to pinch

interval water reuse ---------------------------------------------------------------- 46

4i Water network for the multiple contaminant system with Interval water

Reuse -------------------------------------------------------------------------------- 47

4j Block diagram of the simplified water network using the pinch Interval

water reuse ----------------------------------------------------------------------- 53

LIST OF APPENDICES

APPENDIX TITLE PAGE

Calculation for the Minimum Fresh Water Requirement for the

Multiple Contaminant Problems without Pinch Interval Reuse ----------- 56

Calculation for the Minimum Fresh Water Requirement for

 13

the Multiple Contaminant Problems with Pinch Interval Reuse ----------- 61

NOMENCLATURE

Ci,in,lim Contaminant level in the inlet streams, ppm

Ci,out,lim Contaminant level in the outlet stream, ppm
∆mi,tot Total mass load of contaminant to be transferred, kg/hr
fi,lim Limiting water flowrate for operation i, te/hr
Ci,w,supply Contaminant concentration of the freshwater supply, ppm
Ci,w,out Contaminant concentration of the water stream leaving operation i
Fin Flow rate (te/hr) of fresh water supplied to operation i at concentration interval
boundary n.
fi*,n Total flow rate to operation i at concentration interval boundary n
Fmin Minimum freshwater flow rate required, te/hr
 14

Cpinch Concentration at the pinch, ppm

Cregen Regeneration concentration, ppm
C0 Regeneration outlet concentration, ppm
Δmregen Mass load of contaminant transferred to the freshwater stream prior to
Regeneration, kg/hr
 15

Δmpinch Mass load of contaminant transferred to the regenerated water stream between
regeneration outlet concentrations C0 and the freshwater pinch
qli,m≤ n Flow rate (te/hr) of water from operation i at concentration interval boundary n
that is supplied by operation l at a concentration interval boundary < n
Tin Water flowrate reused within operation i at concentration-interval boundary n.
te/hr
Tin+1 Water flow rate available for reused within operation i at concentration interval
boundary n+1, (te/hr.)
Wijn Concentrations (ppm) of contaminant j in operation i in water streams available
for reuse within operation at concentration interval boundary n
Wijn+1 Concentrations (ppm) of contaminant j in operation i in water streams available
for reuse within operation at concentration interval boundary n+1
Wijm ≤ n Concentration of the contaminant j in the stream with flow rate qli,m ≤ n.
θi,n Ratio of the actual flowrate to operation i at concentration interval boundary n,
ΔFli,n<pinch, Flow rate of fresh water that can be saved by reusing water from operation l at
the pinch interval boundary to operation i at concentration interval boundary n

CHAPTER ONE

INTRODUCTION

1.1 Background of the Study

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Water and energy are intimately connected in a complex relationship of

production/consumption. The concerns for the environment and the water stress occasioned by

climate change have made this interrelationship a crucial issue on the international scene. As

increase in energy demand will inevitably increase the demand for water, it is evident that

adopting a sensible approach to using these two resources is vital for sustainable economic,

social and ecologically friendly development. Consequently, water is increasingly becoming a

resource that must be saved and protected, since there is no alternative to it, unlike other

resources like oil.

1.1.1 Water and Petroleum/Chemical Process Industry

Production and utilization of hydrocarbons impact on water resources in two ways, first,

during processing and then coping with planets water stress resulting from global warming.

Management of water within the context of petroleum and chemical process industries has

become a major issue

In this respect, the paucity of good quality industrial water and the stringent discharge

regulations have resulted in higher costs for fresh water and the treatment of waste water

respectively. The increasing costs of handling water have prompted companies to look for means

of water conservation to save cost

One of these approaches is the development of a systematic method to the design of

water recovery network aimed at the minimizing freshwater and waste water requirement for the

process industry.

1.1.2 Pinch Analysis

Pinch analysis is a rigorous, structured approach that has been used to tackle a wide

range of problems related to process and site utility. This involves opportunities such as capital

investment planning, efficiency improvement, and cost reduction (Dhole, Ramchandani, Tainsh
 17

and Wasilewski, 1996)

The success of pinch technology is due to the underlying simple basic concepts. This

technique analyses a commodity on the basis of both quality and quantity as the cost of a process

is a function of both. In general, process use high value utilities and reject waste at a lower

value. Thus in the case of water, pure water is fed to processes and contaminated waste water is

rejected to treatment plants.

In designing the network, individual demand for a commodity is matched with a suitable

supply quality by maximizing the match between demand and supply; and by which means the

import of utilities is minimized.

1.1.3 Water –Pinch Technology Concepts

Water-pinch technology is a type of mass exchange integration between water –using

operations, which enables practicing engineers to answer a number of important questions when

retrofitting existing facilities and designing new ones. The technology incorporates graphical

analysis for setting targets and realizing the design of the network.

1.2 Statement of the Problem

The increasing cost of freshwater and the treatment of wastewater has compelled the

process plants (refineries inclusive) to focus on the minimization of freshwater consumption,

Given that there is a shortage of available raw water in many locations, and the fact that a typical

refinery produces anywhere from 188 to 1125 metric tonnes of waste water per cubic meter of

crude processed (www.ipieca.org, 2010). The generation of such vast quantities of wastewater

demands that methods be developed to minimize the freshwater requirements of these processes

(Mann and Liu, 1999), the reuse of refinery wastewater is the focus of this research. A direct

consequence of this step is a reduction in generation of effluent and reduced treatment costs.
 18

Hence, the systematic approach to design of water recovery network has become a topic of

interest in the field of research in the past few years.

The synthesis of a water network for a set of water-using processes from the refinery is to

determine a network of interconnections of water streams among the water-using processes so

that the overall fresh water consumption is minimized while the processes receive water of

adequate quality.

An effective strategy for segregation of refinery waste water is by the amounts of solids

and/or salts, also referred to as total suspended solids (TSS), total dissolved solids (TDS) and

turbidity of the wastewater.

One of the most practical tools that have been developed for the design of water recovery

networks in the past 20 years is pinch analysis, which is used to improve the efficient use of

water resources in process industries.

1.3 Research Aims / Objectives

i. To identify the minimum fresh water consumption and waste water generation in the

water- using operations.

ii. To simultaneously minimize the fresh water consumption and waste water generation via

maximization of the internal water reuse, in the operations.

iii. To design a simplified water network that can achieve the desired mass exchange with

the targeted minimum fresh water requirement.

1.4 Significance of the Study

Successful application and good understanding of this technology in the Refinery

operation shall enable practicing Engineers when retrofitting existing facilities and when

designing new network for water-using processes to predict the maximum water reuse targets
 19

and minimum waste water generation targets in the process. It shall also guide the engineers on

how to design the network that can achieve a set target.

1.5 Scope and Limitations of the Study

This work shall be limited to designing of an integrated water using network that should

reduce the flow rate of fresh water supply and wastewater generation in the petroleum refinery

while the water-using operations still receive adequate water for their mass transfer operations,

through the application of water reuse and regeneration recycle. It is also limited to mass transfer

based water-using processes, which do not take into account the various non-mass transfer-based

processes e.g. reactor, cooling tower make-up, etc.

1.6 Layout of the Research

In this work, some water-using operations involving mass exchange were analyzed and

then the freshwater and wastewater flow rates for those systems were compared with and

without water reuse. The concepts of regeneration and recycle were introduced for further

reduction of the freshwater requirements. The methodology was used for a single contaminant

solution and then extended to handle the more complex process dealing with multiple

contaminant problems. The concepts were then used to design a simplified water network of the

system with the assumption that input and output flow rates were at all time constant

CHAPTER TWO

REVIEW OF RELATED LITERATURE

2.1 Pinch Technology Principle

Pinch technology was initially used for the process of heat integration for the design of

heat exchange networks to transfer energy from a set of hot streams to a set of cold process

streams. Linnhoff, Boland and Hewitt, (1982) applied the principles of the dynamics and energy

balance to systematically analyze heat flow across various temperature levels in a process. A
 20

major break through in this field was the identification of the pinch temperature (Linhoff and

Flower, 1978) at the point the exchange network is divided into two independent parts; above the

pinch and below the pinch. With the understanding of the pinch point, the use of utilities is

subject to certain constraints. Firstly, no heat is transferred a cross the pinch. Secondly, heat is

added only above the pinch and lastly, cooling is done only below the pinch. In other words, hot

process streams can be cooled more cost effectively above the pinch temperature by cold process

streams as compared to cooling utility streams. Similarly, cold process streams can be heated

below the pinch more effectively by using hot process streams than by using hot utility streams.

Linnhoff (1993) has illustrated the use of pinch technology to calculate energy “targets,”

such as the minimum hot and cold utilities required. A sample composite curve to illustrate the

process is shown in Figure 1. This ‘shortcut’ approach can help in choosing the best alternative

before designing the network. The pinch analysis methodology to achieve the maximum heat

recovery target assumes that no individual heat exchanger should have a ∆T smaller than ∆Tmin.

Once this assumption has been made, the actual performance (A) will only meet the Targets (T)

if there is no heat transfer across the pinch (XP). (Querzoli, Atoadley, Andrew, Dyson andTony

2003)

∆Tmin.is defined as the ∆T between the hot and cold composite curves at the pinch point.

It is a key design parameter in deciding the trade-off between capital and energy costs. A heat

exchange network (HEN) with a smaller ∆Tmin will require a larger exchanger area to

compensate for less temperature driving force, and this result in higher capital cost. But in

return, this will incur lower energy costs due to improved heat recovery and decreased hot and

cold utility requirements. The HEN capital cost can be calculated by using the cost of capital at

the discount rate. The capital and energy costs can then be added to calculate the total cost of the

HEN. (Querzoli et al., 2003) The above principle formed the basis for water pinch technology.
 21

Hot composite curve

Pinch point (ΔTMin )

Cold composite curve

Q
Figure 1 Composite Curve to determine Pinch Point Temperature (Mann and Liu, 1999)

2.1.1 Water Pinch Technology

In the mid-1990s, water pinch technology emerged as a significant new approach to the

problem of industrial water reuse, water minimization and effluent-treatment system design.

This technology allows engineers to analyze water –using process prior to design and thereafter

design to minimize both fresh water consumption and waste water generation.

When Monsanto Company (Wales) first implemented this technology in 1994-1995, it

reduced fresh water usage by 30 percent, saved $11.5million by lowering the capital expenditure

for its new waste water-treatment facility from $15million to $3.5million, and saved additional

$1million annually in operating costs and raw materials. As a result, Monsanto was awarded the

1995 excellence in safety and environment award by the British Institute of Chemical Engineers

(Mann and Liu, 1999)

Water pinch technology is seen as a Mass exchange integration that deals with pollution,

resource recovery, waste reduction etc. mass integration is a systematic methodology that

provides a fundamental understanding of the global flow of mass within a manufacturing process
 22

and employs this holistic action and routing of species through the process (El-Halwagi, 1997).

2.2 Development of Water Pinch Technology

Inspired by the success of heat integration, researchers have spread the pinch idea to

other areas, in particular to mass exchange. Most of the methods used in water pinch analysis are

based on the mass exchange of one or several contaminants (Ataei and Panjehshashi, 2009). If

the mass exchange is based on mass transfer of one contaminant, the problem is solved as a

single contaminant. Nevertheless, if it includes mass transfer of two or more key contaminants,

the problem will be solved as multiple contaminants. Mathematical, graphical and computer

based methods have been developed for both cases, but each method has some advantages and

disadvantages. Graphical methods are more useful in solving single contaminant problems.

However, they are complicated and sometimes, impossible on multiple contaminants problems

(Alizadeh and Pishgahifard, 2010; Bhantnagar and sangwan, 2009; Hassani, Otadi, Javid and

Khiabani, 2009).

2.3Challenges of Water Pinch Technology

The principal challenge in water –pinch analysis is to consider all the water using

operations in a facility simultaneously when each may in fact involve completely unrelated piece

of equipment. As noted earlier, it may include physical components such as suspended solids or

chemical species and some other properties such as pH, conductivity etc. Thus, a single problem

may involve a series of both chemical and mechanical operations. In addition, factors such as

solubility limits, reactivity and other conditions may pose constraint to water reuse. A system of

water using operations being considered for water reuse may include for example a rinse that

requires very pure water for a final rinse but can accept a relatively contaminated water stream

for the first rinse.

2.4 Techniques for Solving Water Pinch Problem

Various techniques and concepts have been developed for solving the water pinch
 23

problems and these include the following:

2.4.1. Composite Curve

El-Halwagi and Manousiouthakis (1989) showed how mass transfer composite curves

could be plotted using a minimum composition difference, θ (analogous to ∆Tmin in HENS).

Using this plot, the mass transfer pinch can be located and the targets for the minimum flow

rate of lean stream, i.e .mass separating agent (MSA) can be determined. A sample composite

curve which illustrates it is presented in Figure 2a. The design of the network to achieve the set

targets was carried out in a way similar to HENS pinch design method.

However, unlike HENS, there was no way of getting the minimum capital cost for the

network. This is because the driving force for mass transfer is more complex than that for heat

transfer. In HENS, the driving force is merely the temperature difference and is clearly shown

on the composite curves. However, in mass exchange network (MENS), the driving force

involves both concentration difference and the equilibrium relations which must all be

represented, (Hallale and Fraser, 2000). However, with respect to cost estimation, El-Halwagi

and Manousiouthakis, (1989) then recommended using the minimum number of units in the

design of the network to minimize the capital costs.

Pinch point
Concentration (ppm)

Concentration composite curve

Water supply line

 24

Mass load (kg/h)

Figure2a: Composite curve to determine Freshwater Pinch Concentration (Mann and Liu, 1999)

2.4.2 Automated Procedure

In further work, El-Halwagi and Manousiouthakis (1989) later presented an automated

synthesis procedure. This procedure first determined the pinch points and minimum utility

targets using linear programming. All possible networks having minimum number of units were

then synthesized using mixed integer linear programming. The cost of the final networks was

calculated and the one with the lowest. This was carried out iteratively for arrange of θ values to

minimize the annualized total cost of the network. A vector of stream-dependent θ values could

also be used if necessary.

They later showed how mass-load loops in an evolved design of the network could be

simplified, in order to improve the total cost. This evolutionary approach depends on the initial

network structure and is unlikely to give a true optimum. No amount of evolution will reach the

optimum design if its topology is different from that of the initial network. This is termed a

`topology trap’ (Mann and Liu, 1999).

Papalexandri, Pistikopoulos and Floudas (1994) pointed out that the main drawback of this

procedure was its sequential approach. As the capital and operating costs were not considered

simultaneously, the determination of optimum trade-off between them may not be possible. They

applied mixed integer non linear programming (MINLP) to the MENS problem. Their approach was

to minimize the TAC by optimizing a network hyper structure containing many mass exchange

alternatives without using pinch division.

2.4.3 State -Space Approach

Bagajewicz, Pham and Manousiouthakis (1998) presented state-space approach for heat

and/or mass exchange network synthesis to overcome some of the limitations of the MINLP

Approach. This approach is analogous to process control systems and is based on the notion that the
 25

behavior of any system can be characterized by a set of input variables, a set of output variables a n d

i n p u t -output relations. The representation for a heat/mass e x c h a n g e network is characterized by

two operators: a distribution network where stream mixing and splitting occur and a process operator

where heat or mass transfer takes place. This approach was used to tackle the problem of minimizing

the TAC of heat or mass exchange networks and it was claimed that it guarantees a global optimum.

2.4.4 Limiting Water Profile

Wang and Smith (1994) applied the water pinch technique on the more generalized problem

of mass exchange network synthesis (MENS). The basic concept underlying their approach was the

treatment of water using-operation as mass exchange problems. They introduced the concept of

limiting water profile, concentration composite curve and concentration interval diagram to

determine the fresh water pinch concentration. The graphical approach was then used to calculate the

minimum freshwater flow rate of a system. The methods of regeneration reuse and regeneration

recycle were also included. They extended the approach of single contaminant problem to multiple

contaminant problems with multiple constraints by incorporating inlet and outlet concentration

shifts. They concluded that the optimum regeneration concentration was the freshwater pinch

concentration.

2.4.5 Concentration Interval Diagram

Wang and Smith (1994) also proposed the concentration interval method for the design of

mass exchange networks. The limiting concentration composite curve can be used to determine the

mass load in each interval for the preliminary design of the network. This network can be simplified

by the process of loop breaking by the shifting of mass loads from one interval to the other. Two

simple design methods have been proposed by them. The first method maximizes the use of the

available concentration driving forces in individual processes. These methods allow the minimum

number of water sources to be used for individual processes through bypassing and mixing.

The mass transfer model-based approach in analyzing the water using network might not

always be adequate. Many operations in the process industry, such as boiler blowdown, cooling
 26

tower make-up and reactor effluent are typical examples where the quantity of water used is more

important than the water quality. The mass transfer-based approach fails to model these operations.

Dhole et al. (1996) later corrected the targeting approach, by introducing new water source and

demand composite curves. They also showed that the fresh water consumption could be further

reduced by proper mixing and bypassing.

2.4.6 Water Surplus Diagram

Hallale et al. (2000) showed that the water source and demand composite curves may not

give a clear picture of the analysis. The targets obtained may not be a true solution, as they greatly

depend on the mixing patterns (supposed to be a part of the network design) of the process streams.

In turn, a water surplus diagram is presented (Hallale, 2002) for the targeting of minimum fresh

water consumption and waste water generation in a water recovery network. This is till date the most

appropriate targeting technique in locating the utility in a water recovery network. It overcomes the

limitations of the mass transfer-based approach and yet, this new representation automatically builds

in all mixing possibilities to determine the true pinch point and reuse target.

However, it is noted that use of water surplus diagram involves tedious graphical drawing in

locating the minimum water target of the network. Apart from the inaccuracy associated with the

normal graphical approach, the major limitation of the water surplus diagram is that, the diagram is

generated based on an assumed freshwater value. Often, this water surplus diagram has to be drawn

for a few times before the correct fresh water flow rate is finally located.

2.4.7 Water Cascade Table

Tan, Manan and Foo (2002) later introduced a tabular-based numerical approach called

the water cascade table (WCT) to overcome the limitations associated with the graphical water

surplus diagram (Foo et al., 2006)

In addition, Foo, et al., (2005) presented a two stage procedure for the synthesis of a

maximum water recovery network (MNR) for the batch process system, covering both mass

transfer –based and non-mass transfer based water using operations .mathematical method s are
 27

more exact in the case of multiple contaminants (Ataei et al., 2009).

2.5 Application to Refinery Operation

The water used in refineries can be broken down as

1 Process water: This includes Desalter make up water, Coker quench water, Coker cutting

water, flare seal drum, FCC scrubbers, Hydrotreaters etc. This accounts for a significant

portion of the total waste water generated from the refinery.

2. Boilers feed water: This water is required for generation of steam in the refinery

3. Cooling water make up: This water is required for condensers, coolers and other heat

exchangers.

4. Potable water: This is required for kitchen, wash areas and bathrooms.

5. Fire water: This is required for emergency situations like fire outbreak.

6. Utility water: This is used for miscellaneous washing operations such as cleaning of

operation areas.

A water network for a typical petroleum refinery is shown in Figure 2b below

Takama Kukriyama, Shiroko and Umeda. (1980) first addressed the problem of

optimization of water use in a petroleum refinery. The approach was to first generate a

superstructure of all possible re- use and regeneration possibilities. The super structure was then

optimized by removing the less economic features of the design. El-Halwagi and

Manousiouthakis (1989) addressed the more general problem of mass exchange (MEN) between

a set of rich process streams and a set of lean streams. Their approach was adapted from the

methodology developed for heat exchanger networks by Linnhoff and Hindmarsh (1983).The

method was only applied to a single key component. Later, they automated the approach and

introduced the concept of regeneration and applied it to the specific problem of phenol treatment

in petroleum refinery wastewater.

Wang and Smith (1994), provided graphical techniques such as segregation, recycle;

interception and unit manipulation for mass integration. Alva Argaez, Kokossis and Smith
 28

(2007) introduced a systematic methodology that empowers conceptual engineering and water –

pinch with mathematical programming methods. The method focuses on petroleum refineries

explaining piping costs and environmental constraints on the discharge.

Gouws, Majozi and Gadalla (2008) used mathematical technique for water minimization

in multipurpose batch process .Oliver, Podgriguez and Udaquiola (2008) used water pinch

analysis and mixed integer linear programming (MILP) to synthesize the water network for

batch process. Muhammad Nejad, Nabi Bidhendi and Mehrdadi (2010) studied the optimization

of water and steam allocation network based on mathematical methods. Consequently they

developed an algorithm to simplify the relevant calculations and applied it for reforming the

network in a petroleum refinery.

PROCESS STRIPPER DESALTER

DM BOILER WWT

FRESH WATER UTILITY

COOLING PROCES
TOWER UTILITY

PLANT,
POTABLE,
FIRE WATER

Figure 2b: Flow chart of Water Network of a Typical Refinery (NabiBidhendi et al 2010).

CHAPTER THREE
 29

RESEARCH METHODOLOGY

The general approaches to wastewater minimization include the following

1. Process Changes: These are modifications in the process which reduce the

inherentdemandforwater.Anexampleisthereplacementofwetcoolingtowers by dry air

coolers.

2. Water Reuse: Waste water can be directly used in other water using operations if the

contaminant concentration level permits its use in other operation. This reduces both

fresh water and waste water volumes but does not change the mass load of contaminant.

3. Regeneration reuse: Waste water can be regenerated by partial or total treatment to

remove the contaminants that prevent its reuse and can then be reused in other water-

using operations. Regeneration reduces both freshwater and wastewater volumes and

decreases the mass load of contaminant.

This work s h a l l deal with the basic principles for analyzing the water using operation

and then compare the fresh water and waste water flow rates for the systems with and

with out reuse. The steps involved are as follows:

• Firstly, the system shall be defined as a mass transfer problem in which the contaminant

is transferred from a contaminant rich process stream to a water stream.

• Secondly, the system shall be analyzed by treating each water-using operation separately.

• Finally, the minimum fresh water requirement for the integrated system shall be

determined by maximum water reuse.

For this analysis, the concentration composite curve, the concentration interval diagram

and the fresh water pinch shall be introduced. The limiting process data for the selected three

contaminants are as given in Table 1. Water can be regenerated using a foul water stripper. It is

assumed that there is no change in flow rate through regeneration; the flow rate is measured in

tonnes per hour (te/h). Also, in order to avoid buildup of inorganics in the equipment, recycling

in the system is not desired. The method of regeneration reuse is also discussed as shown in
 30

Figure 3.1.This research shall be based on the work of Wang and Smith (1994, 1995) and Mann

and Liu (1999).

Note: The unit te/h is used to represent the flowrate in metric tonnes (te) per hour (h). That is,

one metric tonne is equivalent to 1.102 tons.

Operation 1

Fresh Water Operation 2 Waste Water

 31

Fresh Water Operation 3

(i)

Operation 1

Fresh Water Operation 2 Regeneration Waste Water

Operation 3

(ii)

Recycle

Operation 1

Fresh Water Operation 2 Regeneration

Operation 3 Waste Water

(iii)

Figure 3a Water Minimization through (i) Reuse, (ii) Regeneration Reuse, and (iii) Regeneration recycle
(Mann and Liu, 1999)

3.1 Areas of Water Pinch Technology

Water pinch technology represents a novel approach to industrial water reuse, waste

water minimization, and effluent-treatment system design comprising the following three areas.

1. Water pinch analysis – identifying, apriori ,targets for minimum fresh water

consumption and minimum waste water generation in a water using operations

2. Water pinch synthesis- designing a water –using network that achieves these targets

through water reuse ,regeneration, and recycle

 32

3. Water-pinch retrofit- modifying an existing water using network to maximize water

reuse and minimize waste water generation through effective process changes.

3.2 The Refinery Operation as a Mass Transfer Operation

A simple and practical model for representing the mass transfer of contaminants in water

using operations is the counter current contacting of a contaminant –rich process stream and a

contaminant–lean water stream. This model provides the conceptual frame work for analyzing,

synthesizing, and retrofitting water-using operations involving water reuse, regeneration, recycle,

process changes, and multiple contaminants system.

3.2.1 The Steps involved in the Conventional Water Reuse Approach

• Establishing the boundary limits for the project

• Identifying water sources and water sinks

• Identifying and evaluating the factors that limit water reuse

• Preparing an engineering design and economic evaluation of a water-using network.

Water pinch technology contributes significantly to the fourth step in conventional

water-reuse design, supplementing the past experience of engineers and operators by identifying

minimum flow rate targets and water reuse opportunities.

3.2.2 Water Using Operation as a Mass Transfer Problem

The refinery water using operation shall be represented as a mass transfer problem from a

contaminant rich process stream to a water stream as shown in Figure 3b (Dhole et al,1996). The

contaminants include suspended solids, dissolved gases, hydrogen sulphide, hydrocarbons and

other such impurities whose concentration levels prevent the reuse of the effluent water in the

operation. In this case, the two streams approach from opposite directions in acounter-current

arrangement as shown in figure 3b

Contaminant rich
 33

Mass Transfer Process stream

Water Stream

Figure3b Contaminant-rich Process Stream representation of a Water using Operation (Dhole et al, 1996)

3.3 Determination of Limiting Water Flow Rate (fi, lim)

To analyze a water using operation, the constraints of the operation need to be identified. Based

on these constraints, the limiting water flow rate for that operation is determined. As stated, a

constraint is any thing that prevents a water stream from being reused. The basic constraints for

operation, i, are as follow:

1. The contaminant level in the inlet streams, 𝐶𝑖,𝑖𝑛,𝑙𝑖𝑚

2. The contaminant level in the outlet streams 𝐶𝑖,𝑜𝑢𝑡,𝑙𝑖𝑚

3. The total mass load of contaminant to be transferred ∆mi,tot.

The water reuse is maximized when the constraints are just satisfied.With these

constraints the limiting water flow rate for operation i shall be calculated as,
𝑘𝑔
𝑡𝑒 ∆𝑚𝑖,𝑡𝑜𝑡( ℎ𝑟 )
𝑓𝑖, lim ( ) = [𝐶𝑖,𝑜𝑢𝑡,lim − ∆𝐶𝑖,𝑖𝑛,lim]
× 103 ………………………………… (3.1)
ℎ

3.3.1 Minimum Freshwater Requirement without Reuse

The minimum Freshwater flow rate required for each operation can be determined by

using the limiting water profile. The limiting water profile is a plot of contaminant concentration

versus mass load for a given set of constraints on water reuse.

Figure 3.3 shows a general relationship between the limiting water profile and the water

supply line for operation. In the Figure, Ci,w,supply and Ci,w,out are the contaminant concentration of

the fresh water supply and the contaminant concentration of the water Stream leaving operation
 34

i, respectively.

𝑠𝑙𝑜𝑝𝑒 = ∆𝑪𝒊 (𝑝𝑝𝑚)⁄∆𝑚𝑖 , 𝑡𝑜𝑡(𝑘𝑔⁄hr)- (3.2)

𝑓𝑖(𝑡𝑒/ ℎ𝑟) = [(𝑚𝑖 , 𝑡𝑜𝑡 (𝑘𝑔/ ℎ𝑟)⁄∆𝐶𝑖(𝑝𝑝𝑚) ] × 103 (3.3)

= 1/𝑠𝑙𝑜𝑝𝑒 × 103 (3.4)

In the case of minimum freshwater flow rate, Ci,w,in= 0 and Ci,w,out=Ci,out,lim. Eq. 3.1

becomes

∆𝑚𝑖,𝑡𝑜𝑡(kg/hr)
𝑓𝑖, min(te/hr) = [𝐶𝑖,𝑜𝑢𝑡,lim ]
× 103 (3.5)

The total freshwater flow rate without reuse is simply the sum of the minimum

freshwater flow rates required by each operation:

𝑓𝑖 , min(𝑡𝑒/hr) = ∑ ∆𝑚𝑖,𝑡𝑜𝑡(kg/hr) 103 ) (3.6)

𝐶𝑖,𝑜𝑢𝑡,lim(𝑝𝑝𝑚)

𝐶𝑖,𝑜𝑢𝑡,𝑙𝑖𝑚 Contaminant rich process 𝐶𝑖,𝑤,𝑜𝑢𝑡 = 𝐶𝑖,𝑜𝑢𝑡,𝑙𝑖𝑚

Stream representing water
Using operation i

𝐶𝑖,𝑖𝑛,𝑙𝑖𝑚

Fresh water stream

𝐶𝑖,𝑤,𝑠𝑢𝑝𝑝𝑙𝑦

∆mi,tot

Concentration (ppm) vs. Mass Load (kg/hr)

Figure3c.The Relationship between the Limiting Water Profile and the Water Supply Line
(Mann and Liu, 1999)
 35

3.3.1a Graphical Approach: Composite Curve

In this method, the concentration composite curve of all water –using operations is

drawn, starting from an inlet contaminant concentration of zero for the fresh water supply to the

average outlet concentration of the contaminant of all operations. This curve consists of a series

of linear segments at increasing concentration intervals, representing the total mass load of the

contaminant for all operations The water supply line is then rotated counter clockwise about the

origin (i.e.at zero inlet concentration and zero mass load) until it becomes tangent to the

concentration composite curve to locate the freshwater pinch. This is illustrated in Figure 2 a, the

concentration at the pinch is given by Cpinch . The minimum freshwater flow rate becomes,

∆𝑚 𝑝𝑖𝑛𝑐ℎ(kg/hr)
𝑓𝑖, 𝑚𝑖𝑛(𝑡𝑒/ℎ𝑟) = [𝐶 𝑝𝑖𝑛𝑐ℎ(𝑝𝑝𝑚)]
× 103 (3.7)

3.3.1b Tabular Method: Concentration Interval Diagram

The tabular method is based on the concept of concentration interval boundaries

determinedfromthelimitinginletandoutletconcentrationsfromthelimitingprocess data. The flow

rate at each concentration interval boundary is evaluated from thecumulative mass load and the

interval boundary concentration.

The fresh water pinch occurs at the point with the greatest water supply flow rate. That

flow rate is then the minimum required flow.

∆𝑚 𝑝𝑖𝑛𝑐ℎ(kg/hr)
𝑓𝑘(𝑡𝑒/ℎ𝑟) =
𝐶𝑘(𝑝𝑝𝑚)
× 103 (3.8)

3.3.2 Minimum Freshwater Requirement with Regeneration Reuse

The process of regeneration reduces the contaminant concentration in the water stream

once it reaches the optimal regeneration concentration. All streams enter the regeneration

process at a concentration of Cregen. This concentration is reduced to the minimum outlet

Concentration of the regeneration process, C0. All streams exit at the same flow rate. The total
 36

flow rate is then constant before and after regeneration. For simple regeneration problems, the

optimum regeneration concentration is the pinch concentration (Wang and Smith, 1994). The

mass load of contaminant transferred to the fresh water stream prior to regeneration is,

∆𝑚𝑟𝑒𝑔𝑒𝑛 = 𝑓min𝐶𝑝𝑖𝑛𝑐ℎCpinch (3.9)

The mass load of contaminant transferred to the regenerated water stream between the

regeneration outlet concentration C0 and the freshwater pinch, Cpinch, is

∆𝑚𝑝𝑖𝑛𝑐ℎ − ∆𝑚𝑟𝑒𝑔𝑒𝑛 = 𝑓 min(𝐶𝑝𝑖𝑛𝑐ℎ − 𝐶0) (3.10)

Hence total mass load prior to fresh water pinch is

Δm𝑝𝑖𝑛𝑐ℎ = 𝑓 min 𝐶𝑝𝑖𝑛𝑐ℎ + 𝑓 min(𝐶𝑝𝑖𝑛𝑐ℎ − 𝐶0) (3.11)

Rearranging Equation (3.11) the minimum fresh water flow rate for simple full

regeneration problem in terms of the freshwater pinch, Cpinch and the regeneration outlet

concentration C0 is, as given below:

∆𝑚𝑝𝑖𝑛𝑐ℎ(𝑘𝑔/ℎ𝑟)
𝑓min(𝑡𝑒/ℎ𝑟) = × 103 (3.12)
[2𝐶𝑝𝑖𝑛𝑐ℎ−𝐶0](𝑝𝑝𝑚)

Lastly, the outlet concentration of the regenerated water stream or the outlet

Concentration of the water supply line is given by,

𝐶𝑝𝑖𝑛𝑐ℎ(ppm) +[Δmtot − ∆𝑚𝑝𝑖𝑛𝑐ℎ](kg/hr)

𝐶 out(ppm) = × 103 (3.13)
𝑓min(𝑡𝑒/ℎ𝑟)

3.4 Driving – Force Violation

In a case where the regenerated water may cause a portion of the concentration –

composite curve above the fresh water pinch to lie below the regenerated water stream, the

fresh water pinch is referred to as the pinch point created when fresh water is used and

regeneration is not allowed. In such case there is a driving force violation.

To eliminate the driving force violation, the flow rate of the fresh water has to be

increased until the regenerated water stream intersects the concentration composite curve above

the fresh water pinch. The intersection point represents a new pinch point called the regenerated

water pinch, as opposed to the fresh water pinch. This effect is seen when the fresh water
 37

supply line is not allowed to reach a high enough concentration prior to regeneration.

The design equation to eliminate the driving force violation has to do with specifying

the optimal regeneration concentration (in full regeneration) to eliminate the excess driving

force in the region surrounding the fresh water pinch at the expense of network simplicity.

3.5 Design Equations for Network Simplicity with Full Regeneration and Regenerated

Water Pinch.

The increase in the fresh water flow rate is explored to eliminate the driving force

violation above the fresh water –pinch concentration. This method is favored over increasing

the regeneration concentration due to the increased complexity of the water using network

associated with regeneration above the fresh water –pinch concentration.

The fresh water supply line at a flow rate f min is allowed to reach a concentration of

Cregen equal to the fresh water pinch concentration of C pinch prior to the regeneration to an outlet

concentration co. the mass load of contaminant transferred to the fresh water stream prior to

regeneration is referred to as Δmregen. The regenerated water stream proceeds at the same flow

rate through the regenerated water pinch to an outlet concentration C out.

The mass load of contaminants transferred below the fresh water pinch and below the

regenerated water pinch is Δmpinch and Δm*pinch, respectively, the concentration of the fresh

water pinch and regenerated water pinch points by C pinch and C*pinch respectively.

To determine the optimal fresh water flow rate while holding the regeneration

concentration constant at the fresh water pinch concentration, we use the mass load of

contaminant transferred to each water stream making up the water supply lines below the

regenerated water pinch concentration. i.e.

Δmregen = fmin Cpinch (3.14)

The stream is entirely regenerated once the contaminant concentration reaches the fresh

water pinch concentration. Similarly the mass load of contaminant transferred to the
 38

regenerated water between the regeneration outlet concentrations at a flow rate f min is

Δm ∗pinch − Δmregen = fmin (Cpinch ̶ Co) (3.15)

The mass load of contaminant transferred to the fresh water stream and the regenerated

water stream up to the regenerated water pinch is summed to give the cumulative mass load of

contaminant transferred up to the regenerated water –pinch concentration as

Δm ∗pinch = fmin c + fmin ( cpinch − co ) (3.16)

Rearranging the above equation to give the minimum fresh water flow rate when a full –

regeneration process creates a regenerated water pinch.

Δm∗pinch (kg/hr)
fmin (te/hr) = × 103 (3.17)
[cpinch − c∗pinch −c0 ](𝑝𝑝𝑚)

Consequently, this equation reduces to equation (3.12) when cpinch=c*pinch, and

Δm*pinch = Δmpinch. Also, the average outlet concentration Cout is related to the difference in

the mass loads transferred to the unregenerated water –pinch concentration by

∗ ∗
𝐶𝑃𝑖𝑛𝑐ℎ +[∆𝑚𝑡𝑜𝑡 −∆𝑚𝑝𝑖𝑛𝑐ℎ ](𝑘𝑔⁄ℎ𝑟)
𝐶𝑜𝑢𝑡 = × 103 (3.18)
𝑓𝑚𝑖𝑛 (𝑡𝑒⁄ℎ𝑟)

To determine the regeneration concentration that eliminates the driving force violation,

the key is to cause the regenerated water-supply line to just pinch at point above the fresh water

pinch.

The mass load of contaminant transferred prior to the regenerated water pinch is the

equation3.14 and 3.15 which gives the following:

∗ ∗
∆𝑚𝑝𝑖𝑛𝑐ℎ = 𝑓𝑚𝑖𝑛 𝐶𝑟𝑒𝑔𝑒𝑛 + 𝑓𝑚𝑖𝑛 (𝐶𝑝𝑖𝑛𝑐ℎ − 𝐶𝑜 ) (3.19)

Rearranging (3.19) gives the regeneration concentration

∗
∗ ∆𝑚𝑝𝑖𝑛𝑐ℎ (𝑘𝑔⁄ℎ𝑟)
𝐶𝑟𝑒𝑔𝑒𝑛 (𝑝𝑝𝑚) = (𝐶𝑂 − 𝐶𝑃𝑖𝑛𝑐ℎ )+ × 103 (3.20)
𝑓𝑚𝑖𝑛 (𝑘𝑔⁄ℎ𝑟)

3.6 Minimum Fresh Water Requirements with Regeneration Recycle

 39

Regeneration circuit is used to supply a wide range of flow rate of regenerated water to

the region above the regeneration outlet concentration. The recycle flow rate can be greater than

the minimum fresh water flow rate that is determined by the concentration composite curve in

the region below co. the regenerated water flow rate is exactly equal to that required to pinch at

the fresh water pinch (Wang and smith,1994).The mass load of contaminant transferred prior to

regeneration is,

𝑓𝑚𝑖𝑛 (𝑡𝑒⁄ℎ𝑟)𝐶𝑝𝑖𝑛𝑐ℎ (𝑝𝑝𝑚)

∆𝑚𝑟𝑒𝑔𝑒𝑛 (𝑘𝑔⁄ℎ𝑟) = (3.21)
103

he flow rate of the waste to be regenerated is

∆𝑚𝑝𝑖𝑛𝑐ℎ − ∆𝑚𝑟𝑒𝑔𝑒𝑛
𝑓𝑟𝑒𝑔𝑒𝑛 (𝑘𝑔⁄ℎ𝑟) = 𝐶𝑃𝑖𝑛𝑐ℎ − 𝐶𝑂
(3.22)

And it is also

∆𝑚𝑝𝑖𝑛𝑐ℎ (𝑘𝑔⁄ℎ𝑟)−[𝑓𝑚𝑖𝑛 (𝑡𝑒⁄ℎ𝑟)𝐶𝑝𝑖𝑛𝑐ℎ (𝑝𝑝𝑚)⁄103

= × 103 (3.23)
[𝐶𝑝𝑖𝑛𝑐ℎ −𝐶𝑜 ]

The recycle water flow rate is simply the sum of the flow rate of fresh water and

regenerated water.

𝑓𝑟𝑒𝑐𝑦𝑐𝑙𝑒 = 𝑓𝑚𝑖𝑛 + 𝑓𝑟𝑒𝑔𝑒𝑛

The average outlet concentration of the water supply line is given by

𝐶𝑝𝑖𝑛𝑐ℎ (𝑝𝑝𝑚)+[∆𝑚𝑡𝑜𝑡 −∆𝑚𝑝𝑖𝑛𝑐ℎ ]

𝐶𝑜𝑢𝑡 (𝑝𝑝𝑚) = × 103 (3.24)
𝑓𝑚𝑖𝑛 (𝑡𝑒⁄ℎ𝑟)

NOTE: For a single regeneration problem, the optimal regeneration concentration is the fresh

water-pinch concentration .i.e. Cregen = Cpinch

The input parameters are the inlet limiting concentrations, the limiting flow rates and the

regeneration outlet concentration. The minimum fresh water requirement for the system is

obtained as the output.

3.7 Limitation of the Single –Contaminant Approach to Finding Minimum Fresh Water

Flow Rate.
 40

The water pinch analysis for the single contaminant system discussed previously may not

only be applicable to the simplest multiple contaminant system. Hence the need for using a more

general approach which allows for the transfer of additional contaminants related to the key

contaminants this is achieved through the proportional mass transfer assumption where the

transfer of one contaminant will lead to the transfer of other related contaminant by same

percentage.

3.8 Multiple Contaminant Systems

Most of the real life water using systems encounters the problem of multiple

contaminants limiting the possibility of reusing the effluent from one operation in another water

usingoperation.Theapproachtosinglecontaminantproblemscanbeappliedto multiple contaminants,

taking one of the contaminants as a reference contaminant, provided other contaminants do not

interfere with the transfer of the reference contaminant.

The approach to a multiple contaminant problem is to target and design for the key

contaminant and simulate the performance for non-key contaminants (Wang and Smith, 1994).

The approach to single contaminant is extended to develop an approach to multiple contaminant

systems with multiple constraints.

The basic concepts of waste water minimization in multiple contaminant systems are

provided in the appendix to the article by Wang and Smith (1994). The approach has been

extended and developed into a mathematical code to determine the minimum freshwater

requirement of a multiple contaminant system using computer programming.

The concentrations of contaminant j at the inlet, nth concentration interval boundary and

outlet of water using operation i is denoted as Cij,in, Cij,n and Cij,out, respectively. For two

contaminants A and B, the proportional mass transfer relationship holds good (Mann and Liu,

1999).

𝐶𝑖,𝐴,𝑛 −𝐶𝑖,𝐴,𝑖𝑛 𝐶𝑖,𝐵,𝑛 −𝐶𝑖,𝐵,𝑖𝑛

= (3.25)
𝐶𝑖,𝐴,𝑜𝑢𝑡 −𝐶𝑖,𝐴,𝑖𝑛 𝐶𝑖,𝐵,𝑜𝑢𝑡 −𝐶𝑖,𝐵,𝑖𝑛
 41

The approach to single contaminant is extended to multiple contaminant systems by

ensuring that the reuse of water leaving an operation is feasible with respect to other

contaminants.

3.8.1 Concentration Shift.

To accomplish the feasibility of water reuse in the multiple contaminant system, the

concentration levels of each operation is shifted when plotting the limiting water profile, with

respect to a reference operation and a reference contaminant, to ensure that all the contaminant

levels are in the feasible limit to be used in the next interval .This technique is called

concentration shift (Wang and Smith, 1994).

Types of Concentration Shift: There are two types of concentration shift

1. Inlet Concentration Shift: This involves shifting the inlet concentration of a reference

contaminant in the receiving operation to a feasible point within the operation from

which water will be reused.

2. Outlet Concentration Shift: This involves shifting the outlet concentration of the

receiving operation until either of the contaminants becomes limiting.

3.8.2 Design Equation for Multiple Contaminants

In the concentration composite curves, and water-supply lines, the resulting fresh water

flow rate is called the apparent minimum fresh water flow rate. It is important to recognize that

the CID may not give the true minimum fresh water flow rate for the multiple contaminant

system; this is because some water that has reached the pinch concentration may not be reused in

another operation below the pinch –interval boundary. In most cases only one of the streams

may be reused in another operation that is pinched in a different contaminant considering the

general concentration interval depicted in the figure 4a below

 42

Concentration
Interval boundary

n+1
Reuse within operation i
from interval n to n+1
Ti n+1 (te/hr)
Wijn+1 (ppm)

Reuse from l to i (te/hr)

Wlim ≤ n qli ,m < n

Reuse within operation I

From interval n-1to n
Tin (te/hr)
Wijn (ppm)
 43

Fresh water.
Fin (te/hr)

n-1

Operation 1 operation i
Figure 4a: General Concentration Interval below the Pinch Interval Boundary

Operations may begin at; end at or cross this concentration –interval boundary. In figure

2, Tin and Tin+1 represent the flow rate (te/hr)of water available for reuse within operation i at

concentration boundary n and n+1,respectively,Wijn and Wijn+1 denotes the concentrations (ppm)

of contaminant j in operation i in water streams available for reuse within operation i with flow

rates Tin and Tin+1 ,respectively Fin is the flow rate (te/hr) of fresh water supplied to operation i

at concentration interval boundary n. qli,m ≤ n is the flow rate (te/hr) of water from operation i at

concentration interval boundary n that is supplied by (or reused from) operation l at a

concentration interval boundary smaller than n and Wijm ≤ n is the corresponding concentration of

the contaminant j in the water stream with flow rate qli,m ≤ n.

To allow for the maximum reuse of water, the flow rate of each operation is evaluated at

concentration interval boundary n. If the water entering the operation is at the exact

concentration of the limiting contaminant, as calculated following the inlet/outlet concentration

shift, the operation must be supplied with limiting flow rate, fi. However, if all contaminants

entering the operation are below this exact limiting concentration, the mass transfer may be

achieved with a reduced flow rate. The fraction θi,n is defined as the ratio of the actual flow rate
 44

to operation i at concentration interval boundary n, fi*,n to the limiting flow rate of operation i

(Wang and Smith,1994);

∗
𝑓𝑖𝑛
𝜃𝑖,𝑛 = (3.26)
𝑓𝑖

The required water flow rate for operation i is then

𝑓𝑖𝑛∗ = 𝜃𝑖,𝑛 𝑓𝑖 (3.27)

When considering which water source to satisfy this flow rate, the first choice is to use

water that leaves operation i from the previous concentration interval at a flow rate Tin. This

water is available at a concentration of Wijn

The second alternative is to reuse water available from operation l in operation i at a flow

rate qli,m≤ n ,which has already ended at concentration interval boundary m (m≤n). this water is

available at a concentration of Wijm,≤n the final option is to satisfy the water requirement with

fresh water at a flowrate Fin. the sum of these three sources gives the required water flowrate for

operation i.

𝑓𝑖𝑛∗ = 𝑇𝑖,𝑛 + 𝑞𝑙𝑖,𝑚≤𝑛 + 𝑓𝑖 = 𝜃𝑖,𝑛 𝑓𝑖 (3.28)

The ratio θi,nis determined by examining the true concentration of each contaminant at

this concentration interval and the following interval when compared to those calculated

duringinlet/outlet concentration shift. To identify the contaminant j that requires the greatest

fraction 𝜃𝑖,𝑛 of the limiting flowrate fi,

𝐶𝑖𝑗𝑛−1 −𝐶𝑖𝑗𝑛
𝜃𝑖,𝑛 = max (3.29)
𝑗 𝐶𝑖𝑗𝑛+1 −𝜛𝑖𝑗𝑛

Where ijn is the flow rate weighted average concentration of the three sources of water.

𝑇𝑖,𝑛 𝑤𝑖,𝑗,𝑛 +∑𝑖 𝑞𝑙𝑖,𝑚≤𝑛 𝑤𝑖,𝑗,𝑚 ≤𝑛

𝜛𝑖𝑗𝑛 = (3.30)
𝑇𝑖,𝑛 +∑𝑖 𝑞𝑙𝑖,𝑚≤𝑛+𝐹𝑖,𝑛

That is, the product of the fresh water flow rate Fin and its concentration (ppm) is zero

and hence do not appear in the numerator.

 45

Turning attention to the second water sources discussed earlier, it is certain that water

leaving operation l can be reused in operation i. in a case where this water may be used in

several other operations, then the operation which will reuse the existing water source and

which will use fresh water is determined.

To maximize water reuse, it is right to use water at the lowest available contaminant

concentration first. Equation (3.27) and (3.30) are then solved for the minimum fresh water

flowrate required by each operation at this interval

To calculate the minimum fresh water required by each operation beginning at the lowest

concentration interval boundary (n=1), equation (3.28) and (3.29) reduces to (3.31) and(3.32) for

the first concentration –interval boundary because fresh water must completely satisfy the

minimum flowrate requirement of each existing operation.

∗
𝑓𝑖.1 = 𝐹𝑖.1 = 𝜃𝑖.1 𝑓𝑖 (3.31)

𝐶𝑖,𝑗,2 −𝐶𝑖,𝑗,1
θ𝑖,1 = max[ (3.32)
𝑖 𝐶𝑖,𝑗,2

If anyCij.1is zero, we supply the operation with its limiting flowrate at the first

concentration- interval boundary. To calculate the concentration and flowrate of water leaving

each operation and entering the next interval as

𝑓𝑖 (𝐶𝑖,𝑗,𝑛+1 𝐶𝑖,𝑗,𝑛 )
𝜛𝑖,𝑗,𝑛+1 = 𝜛𝑖,𝑗,𝑛 + (3.33)
𝑇𝑖,𝑛+1

𝑇𝑖,𝑛+1 = 𝐹𝑖,𝑛 + 𝑇𝑖,𝑛 + ∑𝑖 𝑞𝑙𝑖, 𝑚 ≤ 𝑛 (3.34)

To proceed to the next concentration interval, it is required to determine which

operations end at this new interval. The first operation which ends at this new concentration

interval boundary is eligible one for reuse in operation i, at a flow rate qli,m ≤ n those reusable

water sources from other operations combine with the flow rate of water available for reuse from

the previous concentration interval, Tin, and the flow rate s of fresh water supplied to the

concentration interval Fin to supply the streams that begin at or cross this interval according to
 46

the mass balance. The same process is repeated in the next higher concentration interval until the

calculation of each stream that ends or crosses the pinch interval boundary is made.

3.8.3 Pinch- Interval Water Reuse

In some cases, it is confirmed that the design equations for multiple –contaminant

targeting may not be appropriate for concentration interval boundaries below the pinch. This is

usually because of the possibility of reusing water that has reached the pinch interval boundary

at the preceding interval boundaries. Therefore, there is need to consider the possibility of

reusing water that has reached the pinch –interval boundary in other operation in previous

intervals. This can also be stated as “there is an additional water source that may satisfy the

water demand by the concentration-interval boundaries preceding the pinch” this is shown in the

figure 4b below.

Design Equations for Pinch –Interval Water Reuse: When considering concentration –

interval boundaries below the pinch (n < pinch) there is the need to account for the possibility of

stream entering from the pinch interval boundary. The total flow rate of an operation i at this

interval is given by modifying equation (3.28) to give.

∗
𝑓𝑖,𝑛<𝑝𝑖𝑛𝑐ℎ = 𝑇𝑖,𝑛<𝑝𝑖𝑛𝑐ℎ + 𝑞𝑙𝑖,𝑚<𝑛 + 𝐹𝑖,𝑛𝑝𝑖𝑛𝑐ℎ + 𝑋𝑙𝑖,𝑛<𝑝𝑖𝑛𝑐ℎ = 𝜃𝑖,𝑛<𝑝𝑖𝑛𝑐ℎ 𝑓𝑖 (3.35)

Where the new water source xli,n<pinch (labeled 4 in the figure) is the flow rate returned

from operation l at the pinch interval boundary to operation i at the nth concentration interval

boundary(n < pinch).

To calculate the flowrate weighted concentration of contaminant j in i at the nth

concentration interval boundary, based on the four water sources, by modifying equation (3.23)

𝑇𝑖,𝑛<𝑝𝑖𝑛𝑐ℎ 𝑤𝑖,𝑗,𝑛<𝑝𝑖𝑛𝑐ℎ+ ∑𝑖 𝑞𝑙𝑖,𝑚<𝑛 𝑤𝑙𝑖𝑚<𝑛, +∑𝑖 𝑋𝑙𝑖,𝑛<𝑝𝑖𝑛𝑐ℎ 𝑤𝑖,𝑗𝑝𝑖𝑛𝑐ℎ

𝜛𝑖,𝑗,𝑛<𝑝𝑖𝑛𝑐ℎ = (3.36)
𝑇𝑖,𝑛<𝑝𝑖𝑛𝑐ℎ +∑𝑖 𝑞𝑙𝑖,𝑚<𝑛 +∑ 𝑋𝑙𝑖,𝑛<𝑝𝑖𝑛𝑐ℎ +𝐹𝑖,𝑛<𝑝𝑖𝑛𝑐ℎ
 47

As in equation (3.30) the product of the fresh water flowrate Fin<pinch and its concentration

(0ppm) is zero and does not appear in the numerator.

Determination of the flow rate of water to be recycled from the pinch interval boundary

requires consideration of several factors:

1. At the pinch interval boundary, fresh water cannot be used. An important implication of

the pinch concept is that at the pinch, the water using operations must be supplied

completely through water reuse. The flowrate of all streams that end at or across the

pinch interval boundary, minus the flow rates required to complete the next interval.

Therefore equation (3.30) and (3.32) reduces to (3.37) and (3.39) when no fresh water is

allowed
∗
𝑓𝑖,𝑝𝑖𝑛𝑐ℎ = 𝑇𝑖 𝑝𝑖𝑛𝑐ℎ + 𝑞𝑙𝑖𝑚<𝑝𝑖𝑛𝑐ℎ = 𝜃𝑖,𝑝𝑖𝑛𝑐ℎ 𝑓𝑖 (3.37)

𝐶𝑖,𝑗,𝑝𝑖𝑛𝑐ℎ−1 −𝐶𝑖𝑗,𝑝𝑖𝑛𝑐ℎ
𝜃𝑖,𝑝𝑖𝑛𝑐ℎ = max[ ] (3.38)
𝑗 𝐶𝑖,𝑗,𝑝𝑖𝑛𝑐ℎ−1 −𝜛𝑖,𝑗,𝑝𝑖𝑛𝑐ℎ

𝑇𝑖,𝑝𝑖𝑛𝑐ℎ 𝑤𝑖,𝑗,𝑝𝑖𝑛𝑐ℎ +∑𝑖 𝑞𝑙𝑖,𝑚<𝑝𝑖𝑛𝑐ℎ 𝑤𝑖𝑗𝑚<𝑝𝑖𝑛𝑐ℎ,

𝑤𝑖,𝑗,𝑝𝑖𝑛𝑐ℎ = (3.39)
𝑇𝑖,𝑝𝑖𝑛𝑐ℎ +∑𝑖 𝑞𝑙𝑖,𝑚<𝑝𝑖𝑛𝑐ℎ

2. The flowrate that may be accepted into concentration interval boundaries below the

pinch may also be limited by the contaminant level of the recycle and /or the

contaminant level of the operation at the concentration –interval boundary below the

pinch. The stream for reuse must be evaluated in each operation that uses fresh water at

concentration interval boundaries below the pinch. Those that are more concentrate in

the contaminant pinched in the receiving operation can be eliminated by assigning a

flowrate savings. ΔFli,n<pinch, of zero, where,ΔFli,n<pinch, is the flow rate of fresh water that

can be saved by reusing water from operation l at the pinch interval boundary to

operation i at concentration interval boundary n (below the pinch –interval

boundary).further investigation is required of the operations that have the possibility of

some flowrate savings. The flow rate is reduced if recycling of some amount of

operation l to operation i is possible (ΔFli,n<pinch> 0) and Өin<pinch can be reduced. in other

 48

words, it is required to reduce the fraction of the operation’s limiting flowrate that is

required in the pinch interval. The contribution from the interval below would remain.

So the required fresh water flow rate is decreased.

3. To decrease Өin< pinch, the average concentration must be decreased, i.e Cix,n<pinch of the

contaminant x in operation l, that is limiting at the concentration interval boundaries

below the pinch(n<pinch). To do this, one may recycle from the pinch interval boundary

any stream that is at a lower concentration of contaminant x. this can be done until

another contaminant j becomes limiting or the total flowrate reaches the limiting

flowrate of operation i. Another contaminant ,x ,will be just limiting when Өi,x< pinch is

equal to θi,j< pinch as shown in equation(3.40)

𝐶𝑖,𝑋,𝑝𝑖𝑛𝑐ℎ −𝐶𝑖,𝑥,𝑛<𝑝𝑖𝑛𝑐ℎ 𝐶𝑖,𝑗,𝑝𝑖𝑛𝑐ℎ −𝐶𝑖,𝑗,𝑛<𝑝𝑖𝑛𝑐ℎ

𝜃𝑖,𝑛<𝑝𝑖𝑛𝑐ℎ = = (3.40)
𝐶𝑖,𝑋,𝑝𝑖𝑛𝑐ℎ −𝜛𝑖,𝑋<𝑝𝑖𝑛𝑐ℎ 𝐶𝑖,𝑗,𝑝𝑖𝑛𝑐ℎ −𝜛𝑖,𝑗,𝑛<𝑝𝑖𝑛𝑐ℎ

Where𝜛𝑖,𝑗,𝑛<𝑝𝑖𝑛𝑐ℎ >pinch is determined from equation(3.35) when equations (3.38) and

(3.39)are solved, the recycle flow rate that is limiting for each operation is obtained.

4. Having the flow rates savings of each matches, it is required to rank them in order of

decreasing savings. To select which matches to employ, it is also required to consider

the effect of making a match on the matches. After matching the best candidates, the

additional limiting contaminant must be accounted for, the stream that is then limiting in

an additional contaminant may not be reused at its current ranking. It may be evaluated

for reuse at the higher concentration into the streams not affected by the first match. The

operation that has supplied the recycle is hence not allowed to receive a recycle stream

because any recycle to that stream would change its concentration at the pinch interval

boundary. The stream that received the recycle stream is then pinched in two

contaminants, if another stream is to be recycled into this stream, that stream must not be

pinched in either of this contaminant. The flow rate savings and rankings are updated

and the next match made. The matches and update of flow rate savings is continued until

no further match is available or maximum amount of recycle from pinch is mad

 49

Concentration
Interval boundary
(4) Reuse from operation l
At the pinch interval to Operation i

below the pinch n = pinch

xlin < pinch (te/hr) Reuse within operation i
wij pinch (ppm) from interval n to pinch interval
Ti pinch (te/hr)
Wij pinch (ppm)

(2)Reuse from l to i (te/hr)

qli,m<n n < pinch
wijm ≤ n

(1)

Reuse within operation I

From interval n-1to n
Tin (te/hr)
Wijn (ppm) (3)
Freshwater.
Fin (te/hr)

m<n

Operation 1 operation i
Figure 4b General Concentration interval below the pinch interval boundary with pinch interval reuse

CHAPTER FOUR
 50

DATA PRESENTATION AND ANALYSIS

4.1 Minimum Fresh Water and Network Design

This Refinery currently uses 40.05te/h of fresh water in the three operations, as shown in

the problem table of Table1 (the limiting process data for the refinery).

The problem table was treated as a single contaminant system by using the concentration

interval diagram (CID) and taking each contaminant as the only contaminant in the system as

shown in the tables 2(a, b, c). The contaminant, oil had the greatest minimum fresh water

requirement, it was selected as the limiting contaminant based on proportional mass transfer

assumption, the minimum fresh water flow rate obtained as 30.3te/h. The same system was studied

with placing waste water regeneration at an outlet CO of 10ppm using a full regeneration method

as shown in equation 3.12; it was observed that the fresh water requirement is 17.3te/h as shown in

figure 4c and 4d respectively.

Table1 The Limiting Process Data for the Refinery

Operation Flowrate(te/hr) Contaminant Concentration Concentration

in (ppm) out (ppm)

Distillation(steam 6.60 H2S 0 320

stripping) Oil 0 15
S.S 0 15
Hydro 3.45 H2S 200 1200
desulphurization Oil 20 120
unit (HDS) S.S 40 66
Desalter 30.00 H2S 15 40
Oil 10 100
S.S 20 95

Single contaminant approach

 51

Table 2A Concentration Interval Diagram for Oil

Table 2B Concentration Interval Diagram for Suspended Solid(S.S)

 52

Table 2C Concentration Interval Diagram for H2S

53
 54

Figure 4c. Water using Network with Oil as the Reference Contaminant
 55

17.3te/h wastewater

(2)
3.45 te/hr
10.7te/h n = 120
3.15te/h
Regeneration
0.07kg/h 17.35te/h
0.2te/h

(3)
30 te/hr
100
2.4kg/h

0.28kg/h 28.0te/h

3.25te/h

20

0.15kg/h

(1)
6.6 te/hr 15

15te/h 2.3te/h

0.033kg/h 0.15kg/h

10
17.3te/h regeneration

0.07kg/h 10te/h
6.6te/h
17.3te/h fresh water 0
,0ppm
Figure 4d. Water-using Network with full Regeneration-recycle
 56

Waste water

3.15te/h

Fresh water 6.6te/h Operation1 Operation 2 3.45te/h

7.3te/h 3.45te/h Waste water

10.7te/h

0peration 3 Regeneration

28te/h 17.3te/h

Waste water 10.7te/h

Figure 4e. Bock Diagram of Water Network for Minimum Freshwater requiremnt
with full Regeneration.

Multiple Contaminants

When the same limiting process data was treated as a multiple contaminant system, as

shown in Figure8a, H2S was considered as the reference contaminant and operation1 chosen as

the reference operation, it was observed that H2S concentration could not allow the reuse of water

from operation1 in operation2 (at the inlet of operation2) due to the fact that water from

operation1 had reached its limiting contaminant concentration of 320ppmwhich is higher than

200ppm in operation2. Also, from the outlet of operation2, and operation 3 it was observed that

due to their concentrations, they (both) cannot be reused in any operation; hence the only

opportunity was to reuse water from operation1 at certain points above the inlet of operation2

Operation 2 does not require any outlet concentration shift, but operation 3 required an

outlet concentration shift to the concentration interval boundary created at the outlet of

operation1 as shown in Figure 4g

Figure 4g was used to design the simplified water network shown in Figure 4h which

gave the minimum fresh water requirement for the multiple contaminant refinery problems
 57

without utilizing the pinch interval water-reuse, the calculations are shown in the appendix 1

Also considering the pinch interval water reuse opportunity on the same Figure 4g, by

evaluating which water source could be reused from the pinch interval boundary, it was observed

that operation 1 and operation 3 ended at the pinch interval boundary. Operation 3 at the second

concentration interval boundary was the one with the greatest fresh water requirement, hence

reusing the outlet of operation 1 at the fourth concentration interval boundary was required. This

was done as shown in Appendix 2 and the simplified water network is shown in Figure 4j

(2)
[1200, 120, 66] 1200ppm

(1)
[320, 15, 15] 320

[200, 20, 40] 200

(3)
[40, 100, 95] 40

[15, 10, 20] 15

0
[0, 0, 0]
Figure 4f: Limiting Water Profile for H2S contaminant.
 58

(2)
[1200, 120, 66] 1200ppm

(1)
[320, 15, 15] (3) 320
[40, 100, 95]

[200, 20, 40] 200

40

[15, 10, 20] 15

0
[0, 0, 0]
Figure 4g Limiting Water Profile for contaminant (H2S) following outlet concentration shift on operation 3
 59

Wastewater
(2) 4.32te/h 3.45te/h 27.0te/h
3.45 te/h
[320,15,15] [1211.4,109.9,35.9] [27.8,100,83.3] n = 1200

2.28te/h

(1) (3)
6.6 te/h 30 te/h [320,15,15] [353.8,35.4,9.2] 320

[15.9, 57.2, 47.6]

[200, 9.4, 9.4] [17, 61.2, 51] 200

[15, 1.9, 1.9] 15

6.6te/h 1.17e/h 1.8te/h 25.2te/h

[0, 0,0] [0,0,0] [0,0,0] [0,0,0] 0

34.77te/h fresh water
,0ppm Problem prior to Pinch Interval Water Reuse
Figure 4h. Water Network for the Multiple Contaminants
 60

Wastewater
(2) 4.32te/h 3.45te/h 27.0te/h
3.45 te/h
[320,15,15] [1211.4,109.9,35.91] n = 1200

2.28te/h

(1) (3)
6.6 te/h 30 te/h [320,15,15] [353.8,35.4,9.2] [40.3,100.6,87.28] 320

[200,9.4,9.4] [28.44,61.75,51.54] 200

0.9te/h

[11.44,0.54,0.54]
[15, 19, 19] 15

6.6te/h 1.17e/h 1.8te/h 24.32te/h

[0, 0,0] [0,0,0] [0,0,0] [0,0,0] 0

33.87te/h Fresh water
,0ppm Problem with Pinch Interval Water Reuse
Figure 4i: Water Network for the Multiple Contaminants
 61

Waste water
33.87te/h

[320, 15, 15] [1211.4, 109.91, 35.91] [40.3, 100.6, 87.28]

(3)
(2)

0.9te/h

2.28te/h

(1)

6.6te/h 1.17te/h 26.1te/h

[0, 0, 0]
Fresh water 38.87te/h
Figure4j.Block Diagram of the Simplified Water Network using Pinch Interval-water reuse
 62

4.2 Cost Analysis

Table 3A and 3B illustrates the cost flow rate of the utilities in Naira before and after

Pinch analysis for the single contaminant (with regeneration) and the multiple contaminant

systems respectively. From the analysis, based on the 56.8 percent saving of fresh water the total

annual operating cost saving is about 194.4million Naira, where as for the 15.4 percent saving of

fresh water (multiple contaminants method) the annual operating cost saving is about 60.2

million Naira. In addition to this, there is also a reduction in the environmental impact using the

pinch technology method.

Table 3A Cost Flow Rate Comparison for Before and After Pinch Analysis

Utility Operating Original Pinch Change Difference Differential Original

Cost(N/te) Utility solution % (te/h) Cost Cost
Flow Utility (N/h)
(N /h)
(te/h) Flow
(te/h)

Fresh Water 850 * 40.05 17.3 -56.8 -22.75 -19.337.5 34,042.5

Effluent Discharge

Charges 20.5 ** 40.05 17.3 -56.8 -22.75 -466.38 821.03

Cost of Regeneration 181.6 0.00 17.3 -- +17.3 3,141.68 0.00

Effluent Water

Treatment Cost 256.5 ** 40.05 17.3 -56.8 -22.75 -5,835.34 10,272.83

Total Forecast Cost -22,497.5 45,136.36

 63

Table 3B Cost Flow Rate Comparison for Before and After Pinch Analysis

Utility Operating Original Pinch Change Difference Differential Original

Cost(N/te) Utility solution % (te/h) Cost Cost
Flow Utility (N/h)
(N /h)
(te/h) Flow
(te/h)

Fresh Water 850 * 40.05 33.87 -15.4 6.18 -5,253.00 34,042.5

Effluent Discharge

Charges 20.5 ** 40.05 33.87 -15.4 6.18 -126.69 821.03

Effluent Water

Treatment Cost 256.5 ** 40.05 33.87 -15.4 6.18 -1,585.17 10,272.83

Total Forecast Cost -6,964.86 45,136.36

*Akwa Ibom State Water Board

** Sze, F.E Mohammed., Ian, H and Khaled A.M (2008)
Note: All costs are in Nigerian naira.
 64

CHAPTER FIVE

SUMMARY, CONCLUSION AND RECOMMENDATIONS

5.1 Summary

Pinch technology was applied in the analysis of the water-using operations of the

petroleum refinery, taking into consideration that some selected contaminants (hydrogen

sulphide, Oil, and suspended solids) could limit the reuse of water from one operation in another

operation. The system was defined as a mass exchange problem and was analyzed by treating

each of the contaminants separately, using the single and multiple contaminants approaches. The

minimum fresh water requirement for the system was determined through maximization of

internal water reuse. The concepts of Regeneration and the Pinch interval water-reuse were

examined for the possibility of further fresh water saving before the final water-using network

that achieved the aim of the research was finally designed.

5.2 Conclusion

Pinch technology approach was applied to identify the minimum fresh water requirement

and key water reuse opportunities in the refinery process studies in this work. From the analysis

of the water – using operations it was found that by applying the single contaminant method,

there was a significant decrease in the minimum fresh water requirement. Thus, with this system,

it was found that the reduction of 23.1 percent and 56.8 percent of fresh water requirement was

possible for water reused only and waste water reused cum regeneration respectively. In this

system, oil was considered as the single reference contaminant. From the result, it was evident

the process of waste water reuse cum regeneration gave a higher level of reduction in fresh water

requirement as compared to only waste water reuse.

With the multiple contaminants approach, there was a fresh water saving of about 13.2

percent (from 40.05 te/h to 34.77 te/h) which when coupled with Pinch interval water reuse,

there was a further saving of about 0.9 te/h which gave a total reduction of about 15.4 percent.
 65

Hence, there is an opportunity to save 194.4 million Naira and 60.2 million Naira in the annual

operating cost based on the single contaminant and the multiple contaminants approaches

respectively. The result obtained compare favourably with similar work carried out by other

researchers. Nabi Bidhendi et al 2010, used Double contaminant approach and obtained 42%

reduction

5.3 Recommendations

From the result of this work, it is necessary to recommend that more contaminants

should be considered for analysis and design of water networks for water utility optimization.

Also regeneration of waste water should be given due consideration in the refinery operations

since it can possibly be carried using the foul water stripper to remove hydrocarbons, suspended

solids and so forth.

 66

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 69

APPENDIX 1

Calculation for the Minimum Fresh Water Requirement for the Multiple Contaminant
Problems without Pinch Interval Reuse
Step1
From the first interval boundary, operation (1) is the only operation existing hence Ѳ1.1 is
calculated using equation (3.22)
(15-0), (1.9-0), (1.9-0)
θ1.1 =Max
15 1.9 1.9

= Max [1.1.1] =1
The fresh water requirement of operation 1 at the first concentration interval boundary and
the flowrate available for reuse at the next interval from equation (3.24)

F1.1 = θ1.1f1 =T1.1

= T1.2 = 1. (6.6te/h)
= 6.6te/h
Using equation (3.26) to find the concentration of the available water for reuse at the
second concentration interval boundary
6.6𝑡𝑒/ℎ𝑟(15 − 0)𝑝𝑝𝑚
𝑊1.𝐻2𝑆.2 = 0𝑝𝑝𝑚 + = 15𝑝𝑝𝑚
6.6𝑡𝑒/ℎ𝑟
6.6𝑡𝑒/ℎ𝑟(1.9 − 0)𝑝𝑝𝑚
W1.oil.2 = 0𝑝𝑝𝑚 + = 1.9𝑝𝑝𝑚
6.6𝑡𝑒/ℎ𝑟
6.6𝑡𝑒/ℎ𝑟(1.9 − 0)𝑝𝑝𝑚
W1.S.S.2 = 0𝑝𝑝𝑚 + = 1.9𝑝𝑝𝑚
6.6𝑡𝑒/ℎ𝑟
Step2
This is at the second concentration interval, since no operation has ended at this point, qlim
≤n is not considered when solvingfor the fresh water requirement of operation (1) in the second
concentration interval boundary. Using equations (3.21), (3.22) and(3.23)
6.6te/h +F1.2 = θ1.2 (6.6te/h)
But
(200 − 15)𝑝𝑝𝑚 (9.4 − 1.9)𝑝𝑝𝑚 (9.4 −1.9)𝑝𝑝𝑚
θ1.2[ , , ]
200 − Ẁ1H2S.2 9.4 − Ẁ1.𝑜𝑖𝑙.2 9.4− Ẁ1.𝑠𝑠.
 70

Where
(6.6𝑡𝑒/ℎ )(15)𝑝𝑝𝑚
Ẁ1.H2S.2=
6.6𝑡𝑒/ℎ +𝐹1.2

(6.6𝑡𝑒/ℎ )(1.9)𝑝𝑝𝑚
Ẁ1.oil.2 =
6.6𝑡𝑒/ℎ +𝐹1.2

(6.6𝑡𝑒/ℎ )(1.9)𝑝𝑝𝑚
Ẁ1.SS.2 =
6.6𝑡𝑒/ℎ +𝐹1.2

Hence on solving the equations together

F1.2 = 0te/h
θ1.2 = 1
Ẁ1.H2S.2 = 15ppm
Ẁ1.oil.2 = 1.9ppm
Ẁ1.SS.2 = 1.9ppm
Operation 3 has also started at the second concentration interval boundary and must be
considered, it required fresh water since no water is available for reuse, hence using equation
(3.25) give
(29.29 − 15)𝑝𝑝𝑚 (61.44 − 10)𝑝𝑝𝑚 (62.87 −20)𝑝𝑝𝑚
θ3.2= [ , , ]
29.29 61.44 62.8

= Max [0.49, 0.84, 0.68] = 0.84

F3.2 = 0.84 (30te/h)
= 25.2te/h
The flow rate and water concentration is updated as available water in operation 3 at
interval boundary 3 as
T3.3=0te/h + 25.2te/h = 25.2te/h
30𝑡𝑒/ℎ𝑟(29.29 − 15)𝑝𝑝𝑚
𝑊3.𝐻2𝑆.3 = 0𝑝𝑝𝑚 + = 17.01𝑝𝑝𝑚
25.2𝑡𝑒/ℎ𝑟
30𝑡𝑒/ℎ𝑟(61.44)𝑝𝑝𝑚
W3.oil.3 = 0𝑝𝑝𝑚 + = 61.23𝑝𝑝𝑚
25.2𝑡𝑒/ℎ𝑟
30𝑡𝑒/ℎ𝑟(62.87 − 20)𝑝𝑝𝑚
W3.S.S.3 = 0𝑝𝑝𝑚 + = 51.04𝑝𝑝𝑚
25.2𝑡𝑒/ℎ𝑟
Step3
Considering all the operations, to calculate the flow rate and the concentration of water
leaving the interval boundary 3.the water flowrate through operation 1 is at its limiting flow rate
,hence using Ci,j,4 from the limiting water profile,with concentration shifts of figure……,
 71

T1,4= 6.6te/hr, Wi,H2S,4=320ppm, W1,oil,4=15ppm,W1,SS.4=15ppm

Hence,
(320 − 200), (32 − 20), (43.12 − 40)
𝜃2.3 = Max[ ]
320 20 43.12
Max(0.34,0.34,0.07)

F2.3= 0.34(3.45te/hr) = 1.17te/hr

Operation2 at fourth concentration interval boundary has T2.4= 0te/hr +1.17te/hr = 1.17te/hr
3.45𝑡𝑒/ℎ𝑟(320 − 200)𝑝𝑝𝑚
𝑊2.𝐻2𝑆.4 = 0𝑝𝑝𝑚 + = 353.8𝑝𝑝𝑚
1.17𝑡𝑒/ℎ𝑟
3.45𝑡𝑒/ℎ𝑟(32 − 20)𝑝𝑝𝑚
W2.oil.4 = 0𝑝𝑝𝑚 + = 35.38𝑝𝑝𝑚W2.S.S.4
1.17𝑡𝑒/ℎ𝑟
3.45𝑡𝑒/ℎ𝑟(43.12 − 40)𝑝𝑝𝑚
= 0𝑝𝑝𝑚 + = 9.2𝑝𝑝𝑚
1.17𝑡𝑒/ℎ𝑟

for operation 3
T3.3 +F3.3=θ3.3f3
25.2+F3.3=θ3×30te/hr
On solving the above equations by trial and error, using,
(40 − 29.29), (100 − 61.44), (95 − 62.8)
𝜃3.3 = Max[ ]
40 − 𝜛3.𝐻2𝑆.3 100 − 𝜛3.𝑜𝑖𝑙.3 95 − 𝜛3.𝑆.𝑆.3
Where
25.2𝑡𝑒/ℎ𝑟 × 17.01𝑝𝑝𝑚
𝜛3.𝐻2𝑆.3 =
25.2𝑡𝑒⁄ + 𝐹
ℎ𝑟 3.3

25.2𝑡𝑒/ℎ𝑟 × 61.23𝑝𝑝𝑚
𝜛3.𝑜𝑖𝑙.3 =
25.2𝑡𝑒⁄ + 𝐹
ℎ𝑟 3.3

25.2𝑡𝑒
×51.04𝑝𝑝𝑚
𝜛3.𝑆.𝑆.3 = ℎ𝑟
25.2𝑡𝑒⁄ +𝐹 l
ℎ𝑟 3.3

Hence,F3.3=1.80te/hr,𝜃3.3 = 0.90𝜛3.𝐻2𝑆.3 = 15.88ppm,𝜛3.𝑜𝑖𝑙.3 = 57.15,

𝜛3.𝑆.𝑆.3 = 47.64
These concentration and flowrate are sent to the available water at third concentration
interval boundary, hence,
T3.3=25.2te/hr +1.8te/hr =27te/hr
 72

30𝑡𝑒/ℎ𝑟(40 − 29.29)𝑝𝑝𝑚
𝑊3.𝐻2𝑆.4 = 15.88𝑝𝑝𝑚 + = 27.78𝑝𝑝𝑚
27𝑡𝑒/ℎ𝑟
30𝑡𝑒/ℎ𝑟(100 − 64.44)𝑝𝑝𝑚
W3.oil.4 = 54.15𝑝𝑝𝑚 + = 99.99𝑝𝑝𝑚
27𝑡𝑒/ℎ𝑟
30𝑡𝑒/ℎ𝑟(95 − 62.87)𝑝𝑝𝑚
W4.S.S.4 = 47.64𝑝𝑝𝑚 + = 83.34𝑝𝑝𝑚
27𝑡𝑒/ℎ𝑟
To calculate the fresh water requirement above the pinch and the a concentration of water
from operation 2 at the fourth concentration interval boundary,
Step4
Since no fresh water is required above the pinch, the fresh water of operation2 at this point
is 0 hence, F2.4=0
Water leaving operation1 is reused at this point using
𝐹2.3 + 𝑞1.2.4 = 𝜃2.4 × 𝑓2
1.17 + 𝑞1.2.4 = 𝜃2.4 × 3.45
(1200 − 320), (120 − 32), (66 − 43.12)
𝜃2.4 = Max[ ]
1200 − 𝜛2.𝐻2𝑆.4 120 − 𝜛2.𝑜𝑖𝑙.4 66 − 𝜛2.𝑆.𝑆.2
1.17𝑡𝑒
( × 353.8𝑝𝑝𝑚) + (𝑞1.2.4 × 320)
𝜛2.𝐻2𝑆.4 = ℎ𝑟
1.17𝑡𝑒⁄ + 𝑞
ℎ𝑟 1.2.4𝑡𝑒/ℎ𝑟

(1.17𝑡𝑒/ℎ𝑟 × 353.8𝑝𝑝𝑚) + (𝑞1.2.4 × 15)

𝜛2.𝑜𝑖𝑙.4 =
1.17𝑡𝑒⁄ + 𝑞
ℎ𝑟 1.2.4 𝑡𝑒/ℎ𝑟

1.17𝑡𝑒
( ×9.2𝑝𝑝𝑚)+(𝑞1.2.4 ×15)
𝜛3.𝑆.𝑆.3 = ℎ𝑟
1.17𝑡𝑒⁄ +𝑞 l
ℎ𝑟 1.2.4 𝑡𝑒/ℎ𝑟

Solving all the equation together,

𝑞1.2.4 = 2.28𝑡𝑒/ℎ𝑟
𝜃2.4 = 1
𝜛2.𝐻2𝑆.4 = 331.46𝑝𝑝𝑚
𝜛2.𝑜𝑖𝑙.4 = 21.91𝑝𝑝𝑚
𝜛3.𝑆.𝑆.3 = 13.03𝑝𝑝𝑚
At the fifth concentration interval,
3.45𝑡𝑒/ℎ𝑟(1200 − 320)𝑝𝑝𝑚
𝑊2.𝐻2𝑆.5 = 331.46𝑝𝑝𝑚 + = 1211.4𝑝𝑝𝑚
3.45𝑡𝑒/ℎ𝑟
 73

3.45𝑡𝑒/ℎ𝑟(120 − 32)𝑝𝑝𝑚
W2.oil.5 = 29.91𝑝𝑝𝑚 + = 109.91𝑝𝑝𝑚W2.S.S.5
3.45𝑡𝑒/ℎ𝑟
3.45𝑡𝑒/ℎ𝑟(66 − 43.12)𝑝𝑝𝑚
= 13.03𝑝𝑝𝑚 + = 35.91𝑝𝑝𝑚
3.45𝑡𝑒/ℎ𝑟

APPENDIX 2
Calculation for the Minimum Fresh Water Requirement for the Multiple Contaminant
Problems with Pinch Interval Reuse
Reevaluating the fresh water requirement of operation3 at the second concentration
interval boundary with flow rate of water leaving operation1 at the pinch interval boundary, X1.3.2
𝑋1.3.2 + 𝐹3.2 = 𝜃3.2 (30𝑡𝑒/ℎ𝑟)
 74

(61.44 − 10), (62.87 − 20)

𝜃3.2 = Max[ ]
61.44 − 𝜛3.𝑜𝑖𝑙.2 62.87 − 𝜛3.𝑆.𝑆.2
𝑋1.3.2 + (320𝑝𝑝𝑚)
𝜛3.𝐻2𝑆.2 =
𝑋1.3.2 + 𝐹3.2
𝑋1.3.2 + (15𝑝𝑝𝑚)
𝜛3.𝑜𝑖𝑙.2 =
𝑋1.3.2 + 𝐹3.2
𝑋1.3.2 + (15𝑝𝑝𝑚)
𝜛3.𝑆.𝑆.2 =
𝑋1.3.2 + 𝐹3.2
On solving all equations
𝑋1.3.2 = 0.9𝑡𝑒/ℎ𝑟
𝜃3.2 = 0.84
𝐹3.2 = 24.3𝑡𝑒/ℎ𝑟
𝜛3.𝐻2𝑆.2 = 11.43𝑝𝑝𝑚
𝜛3.𝑜𝑖𝑙.2 = 0.54𝑝𝑝𝑚
𝜛3.𝑆.𝑆.2 = 0.54𝑝𝑝𝑚
The flow rate and concentration for reuse at third concentration interval boundary are
T3.3 = 0.9+24.2 =25.2te/hr
30𝑡𝑒/ℎ𝑟(29.29 − 15)𝑝𝑝𝑚
𝑊3.𝐻2𝑆.3 = 11,43𝑝𝑝𝑚 + = 28.44𝑝𝑝𝑚
25.2𝑡𝑒/ℎ𝑟
30𝑡𝑒/ℎ𝑟(61.44 − 10)𝑝𝑝𝑚
W3.oil.3 = 0.54𝑝𝑝𝑚 + = 61.78𝑝𝑝𝑚W3.S.S.3
25.2𝑡𝑒/ℎ𝑟
30𝑡𝑒/ℎ𝑟(62.87 − 20)𝑝𝑝𝑚
= 0.54𝑝𝑝𝑚 + = 𝑝𝑝𝑚
25.2𝑡𝑒/ℎ𝑟

The flow rate of operation three I s obtained using

∗
𝑓3.3 = 𝑇3.3 + 𝑞1.3 + 𝐹3.3 = 𝜃3.3 𝑓3

𝑓3 (𝐶3𝑗4 − 𝐶3𝑗3 )
𝑊3.4 = 𝑊3.𝑗.4 +
𝑇3.4

𝑇3.4 = 𝐹3.3 + 𝑇3.3 ∑ 𝑞𝑙3𝑚<3

𝑖

Hence
𝐹3.3 = 1.8𝑡𝑒/ℎ𝑟
𝑇3.3 = 27𝑡𝑒/ℎ𝑟
𝑊3.𝐻2𝑆.4 = 40.03𝑝𝑝𝑚
 75

W3.oil.4 = 100.6𝑝𝑝𝑚 W3.S.S.4 = 87.28𝑝𝑝𝑚