TABLE OF CONTENTS

Subject Page

ABSTRACT 7

ACNOWLEDGEMENTS 9
CHAPTER ONE : 10

1.1 INTRODUCTION
1. 2 Aim of the Present Work 17
CHAPTER TWO REVERSE OSMOSIS 18

2.1- Introduction 19
2.2 – Applications of Reverse Osmosis 21
2.3- Types of Membranes 24
2.4- Reverse Osmosis Theory 29
2.5 -Principles of Reverse Osmosis Processes 30
2.6- Basic Equation used in Reverse Osmosis 32
2.7 - Factors Affect Reverse Osmosis Performance 35

2.8 Pretreatment for Reverse Osmosis and Water Chemistry 42

2.8.1 - Introduction 42
2.8.2 Feed Water Analysis 43

2.9 Fouling Scale Problems and Control 44

2.9.1 Fouling in Reverse Osmosis Systems 44

2.9.2 Types of Fouling: 44
2.9.3 How Fouling Occurs in Reverse Osmosis 46
2.9.4 What Scale Is 46
2.9.5 Effects of Fouling Compounds on Reverse Osmosis Membranes 50
2.9.6 Effects of pH and Recovery on Fouling Compounds 51

1
 Subject Page
2.10 -Methods Of Scale Control 53

2.10.1 -Acid Addition 54

2.10.2 -Scale Inhibitor Addition 54
2.10.3 - Lime Softening 56
2.10.4 -Preventive Cleaning 57
2.10.5 - Adjustment of Operating Variables 58

CHAPTER THREE : LITERATURE SURVEY 59

CHAPTER FOUR : RESULTS AND DISCUSSION 70

4.1 Introduction 71

4.2 Permacare Program 73

4.3 - Effect of CaSo4 Concentration 78
4.4 - Effect of CaCo3 Concentration 81
4.5 - Effect of Silica Content 83
4.6 Effect of PH on various Fouling Compounds 86
4.6.1 Effect of PH on CaCO3 Scale 86
4.6.2 Effect of PH on CaSO4 Scale 88
4.6.3 Effect of PH on IRON Scale 90
4.6.4 Effect of PH on SILICA Scale 92
4.7 - Effect of Process Recovery on the scalling potential of various Foulants 94

4.7.1 Effect of Recovery on the Fouling tendency of CaCO3 95

4.7.2 Effect of Recovery on the Fouling tendency of CaSO4 97
4.7.3 Effect of Recovery on the Fouling tendency of SILICA 99
4.7.4 Effect of Recovery on the Fouling tendency of IRON 101

2
 Subject Page
103
4.8 - ACTUAL CASE STUDY ON FOULING PROBLEM FOR ONE OF RO
PLANTS

4.8.1 Introduction 103

CHAPTER FIVE CONCLUSIONS AND RECOMMENDATIONS 120

5.1 CONCLUSIONS 121

5.2 RECOMMENDATIONS 124

REFERENCES 125

APPENDEX 132

3
 SCHEDULE OF TABLES

No. Title Page

Table 1 Drinking water Membrane Separation Technologies 13
Table 2 Factors Affect RO performance 41
Table 3 Operation Conditions of Considered RO plant 102
Table 4 CaSO4 Concentration Table 127
Table 5 CaCO3 Concentration Table 130
Table 6 SiO2 Feed Concentration Table 131
Table 7 PH on CaCO3 Scale Table 133
Table 8 PH on CaSO4 Scale Table 135

Table 9 PH on Iron Scale Table 136

Table 10 PH on SiO2 Scale Table 137
Table 11 Recovery on CaCO3 Scale Table 138
Table 12 Recovery on CaSO4 Scale Table 139
Table 13 Recovery on Iron Scale Table 140
Table 14 Recovery on SiO2 Scale Table 141
Table 15 Actual Case Study Phase 1 Table 143
Table 16 Actual Case Study Phase 2 Table 144
Table 17 Actual Case Study Phase 3 Table 145

4
 SCHEDULE OF FIGURES

No. Title Page

Figure 1 Membrane and Conventional Process overview 23
Figure 2 Spiral Wound Membrane 25
Figure 3 Hollow Fine Fiber 26
Figure 4 Schematic Diagram of a Reverse Osmosis Membrane Element 27
Figure 5 Perma Care Program 31
Figure 6 Effect of CaSO4 Concentration 31
Figure 7 Effect of CaCO3 Concentration 32
Figure 8 Effect of Silica Content 42
Figure 9 Effect of PH on CaCO3 Scale 42
Figure 10 Effect of PH on CaSO4 Scale 43
Figure 11 Effect of PH on IRON Scale 43
Figure 12 Effect of PH on SILICA Scale 51
Figure 13 Effect of Recovery on the Fouling tendency of CaCO3 75
Figure 14 Effect of Recovery on the Fouling tendency of CaSO4 77
Figure 15 Effect of Recovery on the Fouling tendency of SILICA 79
Figure 16 Effect of Recovery on the Fouling tendency of IRON 81
Figure 17 Schematic Flow sheet of plant ( use in case study ) 83
Figure 18 Flux Decline (Product Flow Rate during the first phase of this case 85
study )
Figure 19 Recovery Decrease ( During this phase of the problem). 87

Figure 20 Pressure drop Increase ( during the first phase of the 90

problem)
Figure 21 Conductivity of the feed water to the Plant(during of the first 92
phase of the problem ).

Figure 22 PH of the Processed water of the Plant(during of the first phase of 94

the problem).

Figure 23 Flux increase after washing (during the second phase of this 96
problem).

Figure 24 Recovery Increase after Membranes Washing (during of the second99

phase of the problem).

5
No. Title Page

Figure 25 Pressure Drop Decrease after Washing (during of the second 100
phase of the problem ).

Figure 26 Recovery Decrease(during of the there'd phase of the problem) 101

Figure 27 Product decline (during of the third phase of the problem) 102

Figure 28 Pressure drop (during of the third phase of the problem) 104

6
 ABSTRACT

Membrane applications in water technology have acquired significant importance

within the Kingdom as a result of its large use in sea water desalination and

brackish water treatment plants .

These membranes are facing serious problems that cause its deterioration or

failure. The most important of these problems are fouling on its surface This

fouling consists of deposition of undesired substances such as micro particles,

calcium salts, magnesium, metal silica as well as the organic substances on its

surface This fouling leads to significant reduction in the water production capacity

and increases the pressure drop inside the membranes .

In the present work, this fouling problem is investigated . The various fouling salts

like CaSO4 , CaCO3, , silica and iron compounds are studied concerning their

concentration effects on the membrane fouling . Moreover the process parameters

like recovery and pH of water are also investigated to clarify their effects on

membrane fouling .

An actual case study of a fouling problem occurring in one of water treatment

plants in Riyadh City was also investigated and discussed .

7
The obtained results in the present work identified the high fouling potential of

silica , iron compounds as well as Ca++ and Mg-- salts .

It is found that , the fouling tendency of these compounds is highly dependent on

its pH range which has to be considered during the pretreatment steps of RO

plants.

The data also revealed the significant effect of the process recovery on the fouling

potential of the fouling compounds . It is recommended that recovery is kept

between 70 and 80 % to avoid fouling troubles .

The case study considered in the present work showed the importance of precise

monitoring and observation of the RO process especially water analysis , ΔP

measurements and production rate ( or flux decline ) .

8
 ACNOWLEDGEMENTS

I am greateful to my research advisor , Dr. Malik I . Al -Ahmad for his

encouragement and guidance through the course of research .

Special thanks are also due to Dr. Farag Abdul Aleem for his valuable help and

encouragement and Suggestions .

Last but not least .I would like to thank my parents for their sincere encouragement

and unfailing support over the years

9
CHAPTER ONE

INTRODUCTION

10
 Chapter 1
1.1 Introduction

Kingdom of Saudi Arabia has a population of about 21 million, and an area of

2262000.Km2. Most of the country is within the arid or semiarid zones and has

long hot, dry summers and short cold winters, some areas of Saudi Arabia have a

little or not rain and the kingdom may be the world's largest country without any

perennial rivers or streams. Even though, the country doses not have dependable

supplies of surface water (lakes, rivers or streams).

Saudi Arabia is a fast growing country with limited drinking water resource, Most

of this water is required for domestic and industrial and daily needs. Ministry of

Water and Electricity- Riyadh Region is a governmental department to contact

water treatment up to suitable level of treatment satisfying standards and

requirements. It is depending on two sources of water desalinated seawater and

brackish water. Desalinated sea water which is pumped from Jubail to Riyadh area

across tow major pipes (with total full capacity of 850000 m3/day) is mixed with

well water (total full capacity 250000 m3/day) in big tanks, the mixed water has a

TDS concentration 250 ppm approximately.

Reverse osmosis membranes have recently acquired a potential interest in Saudi

Arabia due to its wide application in both desalination plants and waste water

11
treatment processes. Riyadh region has five large water treatment plants (Buwaib

Plant, Sulbukh, Manfouha, Shmessy and Malaz) They account for about 40% of

Riyadh water supply.

Scarcity of water resources is one of the stiffest challenges facing the kingdom

of Saudi Arabia as its population, and agricultural and industrial bases continue

to grow. To meet this challenges, Saudi Arabia invested heavily in the fields of

sea and brackish water desalination and water reuse from wastewater and

industrial effluents. As result, Saudi Arabia leads the world in desalination

capacity, producing about 30% of the world's total, and its experts have gained

considerable operating experiences with the various separation processes used

for desalination and, improving the performance of these separation processes is

a key factor in determining Saudi Arabia's ability to meet its increasing demand

in water in future. Reverse osmosis is one of the main separation processes as

shown in (Table 1) . It shows a growing potential usage for desalination water

reuse in Saudi Arabia. It is a simple process that uses hydrophilic

semipermeable membranes to separate water from dissolved solids as well as

organic and suspended solids without phase change as in the conventional

thermal separation processes. Reverse osmosis plants in Saudi Arabia produce

12
25% of the combined total production of desalination of sea and brackish water,

and reclaimed water from waste streams [1].

Reverse osmosis suffer from scaling problems. Commonly encountered scalants

in desalination processes fall into the following three basic categories:

 Inorganic Scale

 Suspended/colloidal matter

 Biological material

Table ( 1 ) Drinking water Membrane Separation Technologies

13
Each will be looked at separately with a review of the causes, prevention, and

restoration of performance.

This thesis will focus on scaling only. Scaling is caused by the precipitation of

sparingly soluble salts dissolved in the feed water. During the desalination

process, the solubility of the sparingly soluble salts can be exceeded which will

lead to precipitation. Common scales encountered include calcium carbonate,

calcium sulfate, silica, metal silicates, oxides/hydroxides of aluminum, iron, and

manganese. Other less commonly encountered scales include calcium fluoride,

barium sulfate, strontium sulfate, and cupric sulfide.

Calcium carbonate is an important naturally occurring compound. It occurs in

colloidal and amorphous states as well as in at least three polymorphs: calcite,

vaterite, and aragonite. Many feed waters contain high concentrations of

calcium bicarbonate. The primary mechanism leading to the deposition of

calcium carbonate on membrane surface is the conversion of soluble calcium

bicarbonate salt into sparingly soluble calcium carbonate due to pressure drop

and /or increase in temperature. The scale may be easily removed by cleaning

with an acid.

14
Calcium sulfate is another mineral scale frequently deposited by brines. Calcium

sulfate can crystallize from solution in three forms: dihydrate (CaSO 4•2H2O,

gypsum), hemihydrate (CaSO 4•1/2H2O, plaster of Paris), and anhydrite (CaSO 4).

Most calcium sulfate deposits in the RO systems are gypsum (the predominant

form

at temperatures below 40 oC) whereas anhydrite and hemihydrate are the sulfate

deposits commonly found on heat exchangers in the distillation processes.

Though this scale is more soluble than calcium carbonate, once it has formed it

is more difficult to remove. The predominant method of removing this scale

involved the use of chelating agents.

Silica, a common constituent of most natural waters, can occur at extremely

high levels in well water supplies. At present, solubility is used to predict silica

scaling. The precipitation of silica from solution is strongly affected by

insoluble metal hydroxides/oxides present in the feed water. Silica, once

deposited on the membrane, is difficult to remove and should be treated with

caution. Two approaches which are often used to control silica in RO include

lime softening and running the RO system at low recovery to keep the soluble

silica concentration in the brine below the saturation point.

15
Iron in feed water may be present as colloidal or soluble species. The ferrous

(Fe++) form is quite soluble at pH ranges commonly encountered in RO. Ferrous

iron is not a problem as long as it remains in that form. Upon oxidation to the

ferric form, iron hydroxide can deposit on the membrane. It has been reported

that iron present in feed water, if not properly controlled, can co-precipitate with

soluble silica present in water which poses a completely different type of

fouling problem.

Aluminum based compounds have been used for years as coagulant aids to

clarify RO feed waters. Depending on the pH and mode of operation, high

concentrations of aluminum ions can be present in the feed water. Aluminum

hydroxide precipitation can occur when its solubility is exceeded or when an

acid is used to eliminate calcium carbonate scaling potential.

Manganese, although not as common as iron, is often found in iron-containing

water. Like iron, manganese can cause fouling problems when oxidized and

precipitated in RO systems. Iron and manganese bacteria are not common and

are usually not correctly identified, but where they occur, they may be factors in

deposition of iron and manganese-based foulants.

16
1.2 Aim of the Present Work :

Due to the significant importance of fouling and scale problems on the

performance of any RO process , the effects of certain salts like CaSO 4 , CaCO3,

SiO2 and iron on the scalling potential of water are investigated in the present

work . More over the effect of pH of feed water as well as the designed recovery

of RO on its fouling problems is also studied and discussed .

17
 CHAPTER TWO

THE REVERSE OSMOSIS PROCESS

18
 Chapter 2
The Reverse Osmosis Process

2.1 Introduction

Reverse osmosis (RO) is a process used to separate solvents, most of the time

water, from solutes (dissolved solids). It also removes several ions and metals and

other contaminants—organic, inorganic and even bacteria. In addition, reverse

osmosis can also help in removing microorganisms, but this is seldom

recommended due to the strain it puts on the membrane [ 2]

Reverse osmosis is the finest level of filtration available. The RO membrane

acts as a barrier to all dissolved salts and inorganic molecules, as well as

organic molecules with a molecular weight greater than approximately 100.

Water molecules, on the other hand, pass freely through the membrane creating

a purified product stream. Rejection of dissolved salts is typically 95 to greater

than 99%.

Membrane separation systems are widely used to purify water of different

qualities including brackish water, seawater and wastewater. Dissolved and

suspended particulate matter in the feed water can deposit on the membrane

surface. This phenomenon is identified as fouling. Several types of fouling can

19
occur in the membrane systems, e.g. inorganic fouling or scaling, particulate and

colloidal fouling, organic fouling and finally biological fouling or biofouling.

During the process, the membrane concentrate absorbs salts. Inorganic salts, such

as calcium carbonate and barium sulphate, which are water-insoluble, can become

over-saturated. This causes them to precipitate. The precipitation of water-

insoluble salts on the membrane is more likely to occur when conversion is high.

Sodium hexametaphospahte (polyphosphate) is dosing to prevent calcium

sulphate deposition in the membrane

For the removal of small particles and dissolved salts, membrane separation

systems are utilized which use a different method than conventional grade

filtration. Termed crossflow membrane filtration ,this method uses a

pressurized feed stream which flows parallel to the membrane surface. A

portion of this stream passes through the membrane, leaving behind the

rejected particles in the concentrated remainder of the stream. Since there is a

continuous flow across the membrane surface, the rejected particles do not

accumulate but instead are swept away by the concentrate stream. Thus, one

feed stream is separated into two exit streams: the solution passing through the

membrane surface (permeate) and the remaining concentrate stream.

20
2.2 Applications of Reverse Osmosis

There are several industries that benefit from the use of reverse osmosis. The

various industries in which reverse osmosis is being used. RO can be used in

the preparation of various cosmetic products. It is also used in the desalination

of salt water in order to get potable water. RO also removes minerals in water

for the purposes of purifying drinking water. Moreover, RO helps reduce

impurities for manufacturing purposes in the electronics industry. It helps in

generating low sodium food preparation and in producing fruit juices. In

laboratories, it is also used in rinsing glassware. In the area of pharmaceuticals,

RO is used in the production of pure water. [3]

Reverse osmosis can be used in treating wastewater. Water with organic

pollutants as well as wastewater from the processes of electroplating, metal

finishing, paper processes, mining, textile and food processing, radioactivity,

and even contaminated wastewater may be treated using reverse osmosis. RO

is best used for this because designing and operating RO systems are simple,

low maintenance and modular. In addition, organic and inorganic pollutants

and contaminants can be removed easily by the membrane process used by the

RO process as shown in (Figure 1). In the process of recycling of waste

process, RO has no effect on the recovered material. The use of membrane in

21
RO process uses less energy and is set up with considerably less capital and

operating costs as compared with other treatment processes. Lastly, RO

reduces waste streams’ volume, thereby enabling a more efficient and cost-

effective way of treating them.[4]

The process of desalination becomes even more important for areas and

locations where potable water is scarce, such as in the Middle East. RO is the

most widely used desalination process. But 85% of desalinated water is still

produced in multi-stage plants. The Middle East, especially in Saudi Arabia,

due to the scarcity of surface water widely resorts to RO and multi-stage flash

desalination plants

During the process of reverse osmosis desalination, there are two

streams of products—one is pure water and the other is liquid with very high

concentration of saline. The challenge, therefore, is how to dispose of this

highly saline liquid [5]. In desalination plants near the sea, this poses no

problem as it can be put back into the ocean. However in inland sites, this can

be a problem. The common way of solving this is in dumping the concentrate

on available bodies of water, or injecting it to deep wells, or disposed in

publicly declared treatment areas. In addition, they may be disposed to saline

wetlands.

22
Figure ( 1 ) Membrane and Conventional Process overview

23
2.3 Types of Membranes
The type of membranes used in RO largely influences the outcome of the

separation ,The membrane should be chemical and microbe resistant,

mechanically and structurally stable for a long period and it should possess the

desired characteristics for separation. Furthermore, he identified the two types

of membranes that are being widely used as shown in (Figure 2) and (Figure

3 ): asymmetric membranes, which contains only one polymer and the other

one is thin-film, composite membrane, which consists of two or more layers of

polymer. Asymmetric membranes have thin skin layer supported by another

porous layer of the same material. The porous layer provides mechanical

support to the skin layer which selects the fluxes and selectivities of these

types of membranes. These asymmetric membranes are usually formed through

a phase inversion or the process of the precipitation of polymer.

On the other hand, thin film, composite membranes are constructed from

interfacial polymerization [6]. This process is done by coating a highly porous

membrane with a monomer or polymer and then combining it with a cross-

linking agent. The selectivities and water fluxes of these thin, highly cross-

linked polymer membranes can be higher compared with the asymmetric type.

This is because their layers are thinner. An example of this would be

24
composite membranes that consist of cross-linked aromatic polyamide on a

polysulfone support layer.

Among the most important materials used in RO membranes are the

cellulosic polymers (cellulose acetate and cellulose triacetate), linear and

cross-linked aromatic polyamide, and aryl-alkyl polyetherurea. Asymmetric

cellulose acetate membranes are still widely used despite to its susceptibility to

hydrolysis, biological attack, compaction, and lower upper temperature limits.

Other types of composite membranes include polyamide and polyurea which

possess higher fluxes and salt and organic segregations. They can also resist

higher temperature better and their pH variations are higher. Moreover, they do

not easily succumb to biological attack and compaction. These membranes,

however, are less chlorine-resistant and prone to oxidation [6]

Prior to the RO process, it is important for water to be tested first to determine

what types of contaminants and pollutants are present. Moreover, pre-treatment

is important because of the fragility of the membranes and the way they are

wound spirally. Moreover, most membranes are designed such that the flow of

water is one way only—water cannot be pulsed back. Moreover, accumulated

material cannot be recovered from the membranes because they may lose their

production capacity. There are four components of pre-treatment [7]. The first

25
component is that the solid particles in the water should be removed first and

water should be treated. This will ensure that the membranes will not be fouled

by very fine particles. The second significant factor is that microorganisms be

dealt with in order to avoid the fouling of membranes. Third, the acidity of the

water should be adjusted as well since this may also have negative effect on

the membrane and on the overall RO process. And lastly, the cartridge should

also be filtered.

26
Figure (2 ) Spiral Wound Membrane

27
Figure (3 ) Hollow Fine Fiber

28
2.4 Reverse Osmosis Theory
Reverse osmosis, as its name implies, is a process whereby the natural

phenomenon of osmosis is reversed by the application of pressure to a

concentrated solution in contact with a semipermeable membrane. If the

applied pressure is in excess of the solution's natural osmotic pressure, the

solvent will flow throw the membrane to from a dilute solution on the opposite

side and a more concentrated solution on the side to which pressure is applied.

If the applied pressure is equal to the solution's natural osmotic pressure, no

flow will occur, there will be flow from the dilute solution to the concentrated

solution.

The rate of water transport across the membrane depends on the membrane

properties, the solution temperature, and the difference in applied pressure,

across the membrane, less the difference in osmotic pressure between the

concentrated and dilute solutions. Osmotic pressure is proportional to the

solution concentrated and temperature and depends on the type of ionic species

present. For solutions of predominantly sodium chloride at ambient

temperatures. A role of thumb is that osmotic pressure is 10 psi (0.7 atm) per

1000 mg/1 concentration). [ 8 ]

29
2.5 Principles of Reverse Osmosis Processes :
The phenomenon of osmosis which a semipermeable membrane is placed

between two compartments. "Semipermeable" means that the membrane is

permeable to some species, and not permeable to others. Assume that this

membrane is permeable to water, but not to salt. Then, place a salt solution in

one compartment and pure water in the other compartment. The membrane will

allow water to permeate through it to either side. But salt cannot pass through

the membrane. As a fundamental rule of nature, this system will try to reach

equilibrium. That is, it will try to reach the same concentration on both sides of

the membrane. The only possible way to reach equilibrium is for water to pass

from the pure water compartment to the salt-containing compartment, to dilute

the salt solution. Osmosis can cause a rise in the height of the salt solution.

This height will increase until the pressure of the column of water (salt

solution) is so high that the force of this water column stops the water flow.

The equilibrium point of this water column height in terms of water pressure

against the membrane is called osmotic pressure. If a force is applied to this

column of water, the direction of water flow through the membrane can be

reversed. This is the basis of the term reverse osmosis. Note that this reversed

flow produces a pure water from the salt solution, since the membrane is not

30
permeable to salt. water diffuses through a semi-permeable membrane toward

region of higher concentration to equalize solution strength, while the Ultimate height

difference between columns is called "osmotic" pressure , and the applied pressure in

excess of osmotic pressure reverses water flow direction. Hence the term "reverse

osmosis."

31
2.6 Basic Equation Used in Reverse Osmosis :

Figure ( 4) Schematic Diagram of a Reverse Osmosis Membrane Element

The water transport (at constant temperature) through a semipermeable membrane is

described by the following equation The recovery of RO Process is given by :

Q W = K W (   )   /
QW = water flow rate through the membrane
KW = membrane permeability coefficient for water
 = hydraulic pressure differential across membrane
 = osmotic pressure differential across membrane
A = membrane surface area
 = membrane thickness

32
Osmotic pressure depends on solute concentration, solution temperature, and

the type of ions present, for dilute solutions, osmotic pressure is approximated

using the van't Hoff equation.

 i  ci  RT
Where

 = osmotic pressure

ci = molar concentration of the solute

i = number of ions formed if the solute dissociates (e.g., for NaCl , i

=2)
R = gas constant
T = absolute temperature

The salt transport across a membrane is proportional to the concentration

difference across the membrane and is described by the following equation :

Qs  Ks(C ) * A /
Qs = salt flow through membrane

Ks = membrane permeability coefficient for salt

C = salt concentration differential across membrane

33
A = membrane surface area

 = membrane thickness

In this equation salt transport across the membrane is dependent only on the

concentration differential and is independent of applied pressure.

The transport of salt across a membrane is commonly expressed as salt passage

or salt rejection. Salt passage is the percentage of the salt in the feed that

passes through the membrane into the permeate, and is calculated as follows :

SP  Cp /Cf *100
Where

SP = % salt passage

Cp = salt concentration in product stream

Cf = salt concentration in feed stream

The percentage of salt rejection is 100 percent minus the percentage of salt

passage . Salt Rejection (%) = 100 - Salt Passage which the recovery is given

by the ratio of permeate and feed flows . it can be given as :

Recovery (%)=( (Permeate Flow) / (Feed Flow) ) × 100

34
2.7 Factors Affecting Membrane Performance :
Over the past two decades reverse osmosis (RO) has grown to one of the most

widely chosen point-of-use (POU) and commercial water treatment categories

domestically and internationally. During this period, RO membrane and

system technologies have evolved to increase product reliability, improve

total dissolved solids (TDS) and contaminant rejection, and optimize

operation efficiency. Despite these important advancements, the fundamental

rules governing the proper selection and applications of RO systems must still

be observed. Whether working on a residential or commercial RO system,

always review the following checklist of water-quality parameters to ensure

satisfactory system performance .Permeate Flux' and salt rejection are the key

performance parameters of a reverse osmosis process. They are mainly

influenced by variable parameters which are as follows: Pressure ,

Temperature ,Feed water quality , Recovery and pH as show in Table (1)

Not to be neglected are several main factors which cannot be seen directly in

membrane performance. These are maintenance and operation of the plant as

35
well as proper pretreatment design. Consideration of these three 'parameters',

which have very strong impact on the performance of a reverse osmosis system

A ) Recovery

Recovery or conversion is commonly used to define the percentage of the feed

water is converted to permeate it is calculated as follows :

Y  Qp /Qf *100

Y = % recovery or conversion

Qp = Product stream flow

Qf = Feed stream flow rate

In the case of increasing recovery, the permeate flux will decrease and stop if

the salt concentration reaches a value where the osmotic pressure of the

concentrate is as high as the applied feed pressure. The salt rejection will drop

with increasing recovery. Fouling and Scaling problems will also increase by

increasing the recovery.

36
The brine will contain most of dissolved solids in the feed and will be

approximately four times more concentrated than the feed .To conserve energy

, it is desirable to operate at as high a recovery rate as possible to minimize

upstream capital costs. Excessively high recovery can create high brine

concentrations, which reduce permeate flow and increase salt passage. This

may lead to membrane fouling or scaling resulting from the precipitation of

sparingly soluble salts from the concentrated brine

B ) Pressure of the feed water

For a given set of feed conditions; increasing pressure results in increased

water flow per unit of membrane area. Although the transport of salt (Q)

across a membrane is not affected by pressure, increased water flow with

pressure dilutes the salt passing through the membrane, which results in a

lower permeate salt concentration (a reduction in salt passage).

With increasing effective feed pressure, the permeate TDS will decrease while

the permeate flux will increase .

The effect of pressure on the RO process refers to the net pressure or

differential pressure across the membrane :

Net pressure =feed pressure -back pressure -osmotic pressure Where :

37
Feed pressure is the water pressure measured with a pressure gauge at the

installation site under static conditions and what acts on the tapwater side of

the membrane. Back pressure acts on the product side of the membrane,

opposing the feed pressure. For RO systems, it results from the pressurized

water in the storage tank and increases as the tank fills to capacity. Osmotic

pressure is due to the presence of TDS in the water which opposes the feed

pressure. The more TDS in the water, the greater the pressure requirements to

achieve the same productivity. As a general rule, for every 100 ppm of TDS,

about 1 psi of osmotic pressure must be overcome before water starts

permeating the membrane. Clearly, a higher feed water pressure to overcome

it. For example, if the TDS is 2,000 ppm, the osmotic pressure is

2,000/100=20psi. This has the effect of subtracting 20 psi from the feed

pressure. RO production rate is directly proportional to net pressure : Doubling

the net pressure doubles the production rate; halving the pressure halves the

production rate .

C ) Temperature of the feed water

Temperature changes affect both osmotic pressure and water flux (K w )The

effect on osmotic pressure . (K w ) is also directly proportional to temperature

and is usually proportional to the variation in the water viscosity from one

38
temperature to another. A rule of thumb is that membrane capacity increases

about 3 percent per degree Celsius increase in water temperature.

If the temperature increases and all other parameters are kept constant, the

permeate flux and the salt passage will increase .

Feed temperature also determines RO production rate because of the effect it

has on the viscosity of water. The industry standard for determining production

rate is 77ْ F ( 25ْ C ). For predicting the production rate at higher or lower

temperatures, refer to a temperature conversion supplied with the particular

membrane being used .

The water temperature must be known to ensure that the maximum operating

temperature is not exceeded, or membrane degradation will occur over time.

D ) Compaction

The water transport, or flux, through a clean membrane can decrease with

time as a result of membrane compaction. Compaction is caused by creep

deformation of polymeric membranes over time and is dependent on the

membrane material, applied pressure, and temperature. As pressure and

temperature increase, the tendency to creep is greater. This tightens the

membrane's rejecting layer and reduces its water transport as a log function of

time. versus time at a given temperature and pressure produces a straight

39
line. This effect is more pronounced in asymmetric homogeneous membranes.

These. data, available from membrane manufacturers, are used to predict

performance at a future time to provide the design basis for RO system

capacity.Initially, an RO system has excess membrane capacity, which is

offset by lower operating pressures that are gradually increased to the design

pressure over time .

E ) Feed water quality

The level of TDS in feed water is a major factor that will determine the RO

product water quality, because RO membranes reject a percentage of the feed

TDS. There is a direct relation between TDS levels and the minimum feed

pressure required. TDS causes what can be best described as an osmotic "back-

pressure", which reduces the effective feed water pressure and must be

overcome before the RO process can take place . TDS in the feed water supply

is measured with a conductivity meter or from a water analysis.

F ) pH of the feed water

Also determines the type of membranes that can be used. Cellulose

membranes can slowly deteriorate by hydrolysis at high pH levels (typically

40
over 8.0 ) and gradually lose their rejection of TDS. By contrast, Thin Film

membranes can be safely subjected to higher pH levels up to 11.0.Membrane

rejection of certain dissolved solids such as arsenic is also affected by feed

water pH levels, as well as determining how some dissolved solids such as

iron, manganese and hardness minerals will remain in solution and whether

they pose a potential fouling /scaling problem.

Table (1) Factors Affect RO performance

:

Increasing of : Effect on Permeate flow Effect on Salt passage

Effective pressure Direct Proportional (↑) Inverse Proportional (↓)

Temperature Direct Proportional (↑) Direct Proportional (↑)

Recovery Inverse Proportional (↓) Direct Proportional (↑)

TDS Inverse Proportional (↓) Direct Proportional (↑)

41
2.8 Pretreatment for Reverse Osmosis and Water Chemistry

2.8.1 Introduction:

Pretreatment is the key to successful long-term RO performance, and its

importance in system design should not be underestimated. The purpose of

pretreatment is to guard against feed water upsets, remove suspended and

colloidal material, prevent membrane scaling resulting from precipitation of

sparingly soluble salts, and to prevent biological growth. Much has been

written about pretreatment throughout the years, and the techniques have

become state-of-the-art for RO practitioners. Membrane manufacturers,

systems designers and manufacturers and/or consulting engineering

organizations should be consulted about pretreatment requirements for

specific feed waters and membrane types and configurations . [ 9 ]

42
To increase the efficiency and life of a reverse osmosis system, effective

pretreatment of the feed water is required. Selection of the proper pretreatment

strategy will maximize efficiency and membrane life by minimizing: Fouling ,

Scaling and membrane degradation . The net result of the above will be the

optimization of :Product flow ,Salt rejection, Product recovery and Operating

costs. In this study, "fouling" will refer to the entrapment of particulates such

as iron floc or bio compounds, whereas "scaling" will refer to the precipitation

and deposition within the system of sparingly soluble salts such as calcium

sulfate (CaSO4) or barium sulfate (BaSO 4).

2.8.2 Feed Water Analysis:

The major water types being treated by RO are: low salinity brackish waters

with (TDS) of up to 5,000 ppm. , High salinity brackish waters with TDS in

the range of 5,000 -15,000 ppm. And Sea water with TDS in the range of

35,000 ppm. . Sea water with TDS of 35,000 mg/l is considered as "standard

sea water" as this constitutes by far the largest amount of water worldwide

,except the Arabian gulf and the red sea (45000 mg/l). The composition is

nearly the same all over the world. The actual TDS content may, however,

vary within wide limits from e.g. the Baltic Sea with 7,000 mg/L to the Red

Sea and Arabian Gulf with up to 45,000 mg/l. The actual compositions can be

43
proportionally estimated from the "standard sea water" composition. Be aware

that seashore wells depending on the soil, influx from inland, etc. can often

have salinity and composition quite different from that of a sample taken from

the sea itself. In sea water treatment the limiting factor is of a physical nature,

i.e. the osmotic pressure caused by the high TDS. In brackish water treatment

the limiting factor is mostly of a chemical nature, i.e. precipitation and scale

formation by e.g. calcium carbonate or sulfate.

2.9 Fouling and Scale Problems and Control :

2.9.1 Fouling in Reverse Osmosis Systems

As previously discussed, fouling is one of the major problems occurred

during the process of reverse osmosis. Fouling is defined as the accumulation

of debris and particles on the surface of the membrane used in reverse osmosis

such as insoluble corrosion products, scale deposits, mud, slit, clay, airborne

and process contaminants, and biological matters (e.g., insects, pollen). The

frequency of fouling depends on various reasons such as the system recovery

rate, reverse osmosis feedwater characteristics, pretreatment, and system

operation [10] .

2.9.2 Types of Fouling :

44
Membrane foulants are classified into three major types ( as show in Figure

( 5) ) depending on their physical type and location on the membrane, namely,

dissolved solids, suspended solids, biological organisms, and nonbiological

organics [10]

1. Dissolved solids – These materials form scales which are soluble in

feedwater like calcium and barium. Dissolved solids can be cations

(positively charged ions) or anions (negatively charged ions). These

dissolved solids settle and precipitate in the brine stream when their

concentrations increased during the process of reverse osmosis.

Calcium carbonate, calcium sulfate, barium sulfate, and strontium

sulfate are examples of precipitated cations or anions.

2. Suspended solids – These precipitates such as colloidal forms of

metal oxides (e.g., iron, aluminum, silica) retain their suspension on

the membrane through a process called repulsion by a double layer of

charge.

3. Biological foulants – These foulants include bacteria, fungus, algae,

and the metabolic wastes they produced. These foulants are anaerobic

and aerobic in nature. Biological foulants are produced in large

45
 numbers, which tend to be the cause of blockage of flow through the

membrane. These are also present in low concentrations.

Nonbiological organic foulants – These are nonliving organisms which have

carbon-based chemical structures such as oil, plant materials, cationic

surfactants, and hydrocarbons

2.9. 3 How Fouling Occurs in Reverse Osmosis :

Fouling occurs when dissolved solids increase their concentrations and

settle on the reverse osmosis membrane. It happens when a nucleus is formed

because the water elements become concentrated surpassing the point of

supersaturation. This formed nucleus will settle on the membrane or attached

itself to a then-fouled area of the membrane, which is called as the site of

nucleation. Ions like calcium and bicarbonate and barium and sulfate also form

a nucleus that precipitates on the membrane. It happens when the recovery

rates during reverse osmosis increased; thus, salts concentration in the brine

also increases. Other ions that precipitate on the membrane are magnesium,

aluminum, iron, and silica. Silica can block the flow of fluids through the

membrane and blind the membrane if a gel is formed and thickened due to

phosphates or phosphonates .

46
2.9.4 What Is Scale ?

Scale, as previously discussed, is also one of the major problems occurred in

reverse osmosis. It is the precipitates of water-soluble inorganic salts, which

are localized on the membrane surface. There are several factors that lead to

the formation of scales on the membrane: calcium and magnesium salts

concentration, pH and alkalinity, and total dissolved solids concentration.

Scale formation usually results in inability of the membrane to perform well

during the process of reverse osmosis.

Scaling of a reverse osmosis membrane may occur when sparingly

soluble salts are concentrated within the element beyond their solubility limit.

For example, if a reverse osmosis plant is operated at 50% recovery, the

concentration in the concentrate stream will be double the concentration in the

feed stream. As the recovery of a plant is increased, so is the risk of scaling.

Therefore, care must be taken not to exceed the solubility limits of slightly

soluble salts, or precipitation and scaling may occur. Scaling problems in

membrane filtration systems will most likely become more important in the

future due to emphasis on the use of lower quality water resources in order to

save and recycle water.

47
The most frequent scaling problems come from calcium carbonate (CaCO 3)

because it precipitates fast, once concentrated beyond its solubility limit and

also most natural waters are almost saturated with respect to CaCO 3.

CaCO3 Scaling can be prevented by acid addition, a scale inhibitor, softening

of the feed water, preventive cleaning and low system recovery. CaSO 4 scaling

is preventable by the same methods as CaCO 3 Scaling except the acid addition.

In fact, using sulfuric acid to lower pH for the prevention of CaCO 3 scaling

would increase the probability of the sulfate scaling. The successful operation of

any RO plant depends on how free the feed water is of particulate matter and

suspended solids. Most natural waters contain some suspended matter, and the

variation in size and type of such particles can be substantial. The particles can

be classified into two groups: colloidal and noncolloidal. A major fouling

problem with reverse osmosis systems is scale deposits on the membrane. Scale

buildup causes system performance to deteriorate. Drop in flow rate and an

increase in salt passage. It is usually indicated by an increase in pressure drop

across the filters.

The correct pH, inhibitor dosage and recovery rate depend on the feed water

chemistry and can vary considerably. This is why it's crucial to control these three

parameters as close to design standards as possible.

48
In a reverse osmosis system the most common sparingly soluble salts

encountered are CaSO 4 , CaCO3 and silica.

49
Figure ( 5 ) Scaling and Fouling

50
2.9.5 Effects of Fouling Compounds on Reverse Osmosis Membranes

Concentrations of fouling compounds like calcium sulfate, calcium

carbonate, silica, and iron greatly affect the integrity of the membrane. According

to recent studies, presence of high levels of silica in water results in stern

membrane fouling. High levels of silica often hinder to attain the level of reverse

osmosis recovery [11]. furthermore, when calcium carbonate and silica increased

concentration over their saturation values, they are deposited on the membrane

resulting in the loss of purified water production or loss of permeate flux through

the membrane [12] . Calcium sulfate also contribute to scale formation where

permeates flux decline and shortens the life of the membrane [13 ]. Presence of

iron on the membrane should also be measured because it also causes fouling

problem. It can cause oxidation to insoluble ferric salts even though it is soluble

[ 14]. Moreover, calcium carbonate impedes the fluid flow through the

membrane when it forms in the brine spacers just above the surface of the

membrane. Calcium sulfate, on the other hand, precipitated on the membrane

surface in small groups. Silica forms a gel that wets out and spreads in a thin

layer over the surface of the membrane, which causes the blinding off the

membrane.

51
2.9.6 Effects of pH and Recovery on Fouling Compounds

Reduced operating recovery and feedwater pH reduction are often used to

control membrane fouling caused by fouling compounds such as calcium

carbonate, calcium sulfate, silica, and iron. Reducing the pH of the feedwater

with acid (either sulfuric or hydrochloric acid) can decrease the concentration of

calcium carbonate. This method shifts equilibrium to the left that keeps the

calcium ions in solution [15] . However, it increases the growth of other foulants

like silica and is effective for carbonate scale only. Moreover, the use of sulfuric

acid can cause problem with sulfate scale because of the additional sulfate ions

the acid contributes. The solubility of silica decreases when lowering the pH to

less than 7; thus, it precipitates on the surface of the membrane. Reduction of

feedwater pH has also an effect on permeate water quality. When thw pH of feed

water below 8.2, carbon dioxide will be produced affecting the quality of

permeate water [15] . In this case, low pH and alkalinity should be used to attain

good permeate water quality and system performance.

Reducing system recovery is another way of preventing scale formation. It is

advisable to operate the process at lower recovery. The concentration of salts in

the brine steam decreases when the system recovery is also decreased; thus,

52
preventing precipitation. Operating at lower recovery produces less permeate and

more brine water [15] . Lower recovery reduces the concentrations of all fouling

compounds; thus, preventing or minimizing membrane fouling.

The integrity of reverse osmosis membranes are influenced by pH and alkalinity,

temperatures, recovery rate, salt passage, and pressures. It is necessary that the

membrane could withstand these factors to prevent membrane fouling and scale

formation. The performance of the membrane during the process of reverse

osmosis can be affected by the concentrations of dissolved and suspended solids.

If the concentration of the debris is high, the osmotic pressure is also high.

Therefore, there is a tendency that the suspended solids set and precipitate on the

membrane resulting in scale formation. In certain circumstances, temperatures

above 35°C can create hydrolysis and membrane degradation. Salt passage is also

affected if temperatures and pressures do not support the type of membrane being

used in reverse osmosis.

53
2.10 Methods Of Scale Control:

There are a number of ways to pretreated raw water to prevent or reduce

undesirable scaling. These include, for example, lime-soda softening and ion

exchange. Calcium carbonate is often termed an alkaline scale because high

pH favors the carbonate species in the equilibrium that exists between

bicarbonate and carbonate ions in water .The addition of hydrogen ions,

usually in the form of sulfuric or hydrochloric, increases the bicarbonate

concentration. The most common water pretreatment method for reducing

carbonate scale is acid dosing. Acid dosing invariably is used where the RO

membrane is cellulose acetate, which must operate in an acidic environment.

Acid dosing, however, is not effective against the sulfate scales. (In fact

sulfuric acid would contribute toward the problem were it used). Neither is

acid dosing effective for fluorides. Where acid dosing is used, often a second

chemical, SHMP (sodium hexametaphosphate) must be added to control

calcium sulfate deposition. A preferred approach - particularly where the RO

membranes are not of cellulose acetate and therefore have higher operational

pH limits - is to use a modern polymeric multifunctional additive.

54
2.10.1 -Acid Addition:

Most natural surface and ground waters are almost saturated with respect to

CaCO3. The solubility of CaCO 3 depends on the pH, as can be seen from the

following equation:

Ca++ + HCO3-↔ H+ + CaCO3

Accordingly, by adding H + as acid, the equilibrium can be shifted to the left

side in order to keep calcium carbonate dissolved. The acid used should be of

food grade quality. Sulfuric acid is easier to handle and in many countries

more readily available than hydrochloric acid, but on the other hand, additional

sulfate is added to the feed stream. This might be critical with respect to

sulfate scaling. In order to avoid calcium carbonate scaling, CaCO 3 should tend

to dissolve in the concentrate stream rather than to precipitate.

2.10.2 -Scale Inhibitor Addition:

Scale inhibitors (antiscalants) can be used to control carbonate scaling, sulfate

scaling and calcium fluoride scaling.

Scale inhibitors have a "threshold effect", which means that minor amounts

adsorb specifically to the surface of microcrystals thereby preventing further

55
growth and precipitation of the crystals. The most widely used scale inhibitor

is sodiumhexametaphosphate (SHMP). Food grade quality should be used.

Care has to be taken in order to avoid hydrolysis of SHMP in the dosing feed

tank. Hydrolysis would not only decrease the scale inhibition efficiency, but

also create a calcium phosphate scaling risk.

SHMP should be dosed to give a concentration in the concentrate stream of 20

mg/L. For example, the dosage into the feed stream of a system with 75%

recovery will be 5 mg/L.

Polymeric organic scale inhibitors are more effective than SHMP. However,

precipitation reactions may occur with cationic polyelectrolytes or multivalent

cations, e.g. aluminium or iron. The resulting gumlike products are very

difficult to remove from the membrane elements.

Overdosing should be avoided. In RO plants operating on sea water with TDS

in the range of 35,000 to 45000 mg/L, scaling is not such a problem as in

brackish water plants, because the recovery of sea water plants is limited by

the osmotic pressure of the concentrate stream to 30-45%. However, for safety

reasons using a scale inhibitor when operating above a recovery of 35% is

recommended .

56
2.10.3 - Lime Softening:

Lime softening can be used to remove carbonate hardness by adding hydrated

lime:

Ca(HCO3)2 + Ca(OH)2 →2CaCO3↓ + 2 H2O

Mg(HCO3)2 + 2 Ca (OH)2 → Mg(OH) 2↓ + 2 CaCO 3 + 2H2O

The noncarbonate calcium hardness can be further reduced by adding sodium

carbonate (soda ash):

CaCl2 + Na2CO3 →2NaCI + CaCO 3 ↓

The lime-soda ash process can also be used to reduce the silica concentration.

When sodium aluminate and ferric chloride are added, the precipitate will

include calcium carbonate and a complex with silicic acid, aluminium oxide

and iron. With the hot lime silicic acid removal process at 60-70°C, silica can

be reduced to 1 mg/l by adding a mixture of lime and porous magnesium

oxide. With lime softening, barium, strontium and organic substances are also

reduced significantly. The process requires a reactor with a high concentrdtion

of precipitated particles serving as crystallization nuclei. This is usually

achieved by up flow solids-contact clarifiers. The effluent from this process

needs media filtration and pH adjustment prior to the RO elements. Iron

57
coagulants with or without polymeric flocculants (anionic and non-ionic) may

be used to improve the solid liquid separation.

Lime softening should be considered for brackish water plants of capacity

larger than 200 m 3/h (880 gpm).

2.10.4 - Preventive Cleaning:

In some applications, scaling is controlled by preventive membrane cleaning.

This allows the system to run without softening or dosage of chemicals.

Typically, those systems operate at low recovery in the range of 25%, and the

membrane elements are replaced after 1-2 years. Accordingly, those systems

are mainly small single-element plants for potable water from tap water or sea

water. The simplest way of cleaning is a forward flush at low pressure by

opening the concentrate valve. Short cleaning intervals are more effective than

long cleaning times, e.g. 30 seconds every 30 minutes. Cleaning can also be

carried out with cleaning chemicals. In batch processes like in waste water

treatment it is common practice to clean the membranes after every batch. The

cleaning procedure, cleaning chemicals and the frequency of cleaning, has to

be determined and optimized case by case. Special care has to be taken not to

allow scaling layer to develop in the course of time.

58
2.10.5 - Adjustment of Operating Variables:

When other scale control methods do not work, the operating variables of the

plant have to be adjusted in such away that scaling will not occur. The

precipitation of dissolved salts can be avoided by keeping their concentration

below the solubility limit, that means by reducing the system recovery until the

concentrate concentration is low enough.

Solubility depends also on temperature and pH. In the case of silica, increasing

temperature and pH increases its solubility .Silica is usually the only reason for

considering adjustment of operating variables as a scale control method,

because these adjustments have economic drawbacks (energy consumption) or

other scaling risks (CaCO 3 at high pH).

For small systems, a low recovery combined with a preventive cleaning

program might be a convenient way to control scaling.

59
CHAPTER THREE

LITERATURE SURVEY

60
 Chapter 3
Literature Survey

Scaling or precipitation fouling occurs when a dissolved material comes out of

solution and deposits on the membrane surface. The precipitants are inverse

soluble salts and, most commonly, calcium carbonate. Precipitation fouling

usually follows a linear fouling curve. In general, for precipitation to occur, the

solubility limit at given conditions, particularly the temperature must be

exceeded, or in other words for the solution to be supersaturated. If the region of

supersaturation is at the membrane surface, then precipitation is likely. If the

supersaturation is away from the membrane surface, crystals will form in the

bulk fluid and deposit in the same manner as a particulate [16]. The degree of

supersaturation was found to affect what type of crystals form. Calcium

carbonate will crystallize in two forms, calcite and aragonite. Aragonite forms at

higher supersaturation ratios and has the greater effect on the fouling resistance,

while calcite forms at lower supersaturation ratios and has less of an effect on

the fouling resistance [17].

Exact knowledge of the solubilities of the most common minerals such as

calcium carbonate, calcium sulfates and silica, in brackish waters and seawater,

61
is vital since the solubility determines whether the brine is saturated or not. It is

necessary to calculate the solubility product constant for the sparingly soluble

salts in the concentrate stream to determine if they present a potential scaling

problem. The main factors affecting scale formation is salt concentration [18],

operating temperature [18-19], fluid velocity [19], pH of water environment [20]

and operating time [21].

Ritter conducted scaling tests for two salts, lithium sulfate and calcium sulfate

[22]. He found that the scaling rates of the different salts could be correlated

using the supersaturation and mass transfer coefficient among other parameters.

He also found that supersaturation was the most important parameter in

determining the fouling rate. The other parameters varied in importance

depending on which salt was tested. For example, the mass transfer coefficients

was the second most important parameter in correlating the fouling in calcium

sulfate and surface temperature in lithium sulfate.

Hasson lists three process conditions which lead to supersaturation [23]:

1 1. A solution is evaporated beyond the solubility limits of a dissolved salt.

62
1 2. A solution containing a dissolved salt of normal solubility is cooled

below its solubility temperature or a solution containing a dissolved salt of

inverse solubility is heated above its solubility temperature.

2 3. Mixing of different streams may also lead to the creation of

supersaturated conditions, as is the case of CaSO 4 scale formation in phosphoric

acid evaporators.

He also lists the significant parameters which determine the superaturation

potential that causes precipitation fouling:

1 1. The composition of the fresh water feed or of the process feed solution

2 2. The concentration effects occurring in the process through the

separation of near pure water by evaporation or by a single-phase diffusion

process

3 3. The temperature level of the process or operation which affects the

solubility limits of the scaling salts, many of which have inverse solubility

characteristics

4 4. The temperature gradient characterizing the heat-transfer operation to

which the solution is exposed and the heat transfer mechanism

63
Most of the research done in the field of precipitation fouling is on calcium

carbonate. Watkinson et al. investigated precipitation of calcium carbonate in

internally-finned tubes and spirally-indented tubes [24]. The experiments were

conducted on a shell-and-tube heat exchanger apparatus, which had water

flowing from a mixing tank through two tubes in parallel in the shell. One of the

tubes was plain, and the other was enhanced. Steam was condensed on the shell

side of the heat exchanger. The effects of salt concentration were briefly

studied, and the fouling resistance was found to increase as the concentration

increased. For the internally-finned tubes, the fouling resistance was found to be

between 15 and 35 % greater then in plain tubes for the same velocity. On the

other hand, the spirally-indented tubes showed a fouling resistance 25 to 50%

smaller than that of the plain tubes at water velocities greater then 3 ft/s.

Watkinson and Martinez [25] conducted tests on a competing brand of spirally

indented tubes from the ones used by Watkinson et al. [24]. The same set up and

experimental procedures were used. The water had 300 ppm suspended particles

and 3000 ppm dissolved solids. The tests were run at velocities between 0.5 m/s

and 3.0 m/s. They found that the spirally-indented tubes had roughly the same

asymptotic fouling resistances as the plain tubes under the same condition,

whereas in the previous study the fouling resistances were found to be less than

64
the plain tube. They also observed that there appeared to be no clear effect of

the pitch of the spirals on the fouling resistance.

Knudsen and a colleague conducted a series of experiments to determine the

factors affecting the formation of scale in cooling tower water [26]. The tests

were run by flowing the cooling tower water through a tube in which a heated

rod was inserted. The water quality was monitored by the Ryznor stability

index.

Most of the work published in literature concentrates on scale control and scale

prediction methods. Kelle, et.al investigated novel antiscalent monitoring

systems to optimize the antiscalent dose required and reported that effective

monitoring and control provided by the TRASAR technology which is based on

the use of a fluorescent molecule which provides a clear and identifiable

fluorescence that can be separated from the natural background [27].

Al-Ahmad et al investigated the main factors affecting biofouling in membrane

processes and recommended a mechanism for this type of fouling in RO

membranes used in either water treatment or waste water systems [28]. The

design of spiral wound membrane element makes them an ideal environment for

the growth of microorganisms that form a biofilm on the membrane surface and

65
on the spacing material in the narrow feed channels. This biofilm acts as a trap

for other particulate matter which quickly build up as a biomass. Michael et al

reported that: the most frequent scaling problems come from calcium carbonate

(CaCO3) because it precipitates fast, once concentrated beyond its solubility

limit and also most natural waters are almost saturated with respect to CaCO 3

[29]. CaCO 3 scaling including SrCO 3 and BaCO 3 can be prevented by acid

addition, a scale inhibitor, softening of the feed water, preventive cleaning and

low system recovery. CaSO 4 scaling including BaSO 4, SrSO4 and CaF2 are

preventable by the same methods as CaCO 3 scaling except the acid addition. In

fact, using sulfuric acid to lower pH for the prevention of CaCO 3 scaling would

increase the probability of the sulfate scaling.

David et al found that when there are only a few calcium and sulfate ions in a

solution, they won't form a permanent scale since it causes the salt to diffuse

away from the membrane surface and back into the brine [30]. However, as a

solution is concentrated, scaling occurs whenever certain parameters are met.

The point at which scaling occurs depends primarily on the concentration of the

particular cation making up the scaling compound, the concentration of the

particular anion making up the scaling compound, the temperature of the

solution and the ionic strength of the solution.

66
The Langelier Saturation index (LSI) is an equilibrium model derived from the

theoretical concept of saturation and provides an indicator of the degree of

saturation of water with respect to calcium carbonate.

Since scale formation is a problem often encountered in reverse osmosis, several

studies have been conducted to resolve this phenomenon. There are chemicals,

better known as scale inhibitors, which control the growth of scales on the

membrane. The chemicals used in controlling scale growth depend on the type

of scale predicted and system operating conditions. There are several methods

used in controlling scale growth. To name a few are the following: bleed-off or

blow-down to limit the cycles of concentration; converts calcium and

magnesium hardness to more soluble salts; and ion-exchange softening which

removes calcium and magnesium hardness salts.

Rahardianto et al found out that membrane scale formation increases as the level

of surface gypsum (calcium sulfate dihydrate) supersaturation increases [31].

They used the antiscalant treatment to study the membrane scaling

susceptibility.

Howe conducted a study aiming to substitute brackish water for the limited

supply of fresh water by desalination through the process of reverse osmosis

[32]. The salinity of brackish water is between 1 000 and 10 000 mg/L. The

67
feasibility of using a water source for a portable supply depends on the water

salinity, the lower the total dissolved solids, the more feasible the supply [32].

However, there are factors that limit the recovery in reverse osmosis such as

solubility and osmotic pressure. In terms of solubility, there are many ions

present in brackish water like calcium, barium, strontium, carbonate, fluoride,

and sulfate. Therefore, it will limit the recovery because ions tend to concentrate

more as recovery increases. Salts also precipitate on the membrane surface when

solubility limit is reached. In terms of osmotic pressure, the externally applied

pressure should overcome the osmotic pressure to produce water. Furthermore,

when recovery increases, osmotic pressure increases. Scale formation is another

factor that needs to be addressed in this study [32].

In recent years, low-pressure reverse-osmosis membrane desalination has been

explored as a viable technology for desalination of brackish water for potable

usage [33-38]. However, the problem of mineral salt scaling remains a serious

impediment to achieving high recovery in brackish water desalination. Mineral

salt scaling can occur when scale precursor ions (e.g. Ba 2+, Ca2+, SO42-, CO32-,

etc.) in the membrane brain stream are concentrated above the solubility limit of

various sparingly water soluble mineral scalants such as calcium sulfate

dihydrate (gypsum), calcium carbonate (e.g. calcite), and barium sulfate (barite).

68
Mineral salt scaling leads to permeate flux decline and eventually the shortening

of membrane useful life. The use of antiscalants can suppress mineral salt

precipitation to some extent, thereby partially alleviating mineral scaling.

However, even with the use of antiscalants, which can significantly increase the

cost of RO desalting, mineral salt scaling remains an impediment to achieving

high product water recovery, partially due to the increased potential of fouling

(including biofouling) when excessive dose of antiscalants is applied [39].

Accelerated precipitation (AP) by inducing calcium carbonate crystallization

through chemical dosing (e.g., lime, caustic, and soda ash) has been shown to be

a promising approach for desupersaturation of primary RO concentrate [40].

This approach is analogous to the lime-soda or caustic softening processes (i.e.

precipitation softening) [41, 42]. The basis of the process is the strong pH

dependency of CaCO 3 solubility that enables its precipitation through pH

control. Conventional precipitation softening, however, is characterized by the

production of fine suspension of mineral salt crystals that requires a long

sedimentation time (about 1.5 to 3 hours) and results in sludge that is of low

solids content (~2-30%) [43].

Precipitation softening technologies have been developed to improve both

precipitation kinetics and the efficiency of solid-liquid separation [44-46]. These

69
technologies are based on the concept of seeded precipitation softening (SPS).

Various studies have indicated that the use of crystal seeds in precipitation

softening can provide a preferential surface area for heterogeneous nucleation

and growth of mineral salts, thus accelerating the kinetics of mineral

precipitation [47]. In addition, control of the initial seed size, loading and type

provides a means of controlling the size of the final precipitates so as to

facilitate efficient liquid-solid separation. Variations of SPS reported in the

literature include fluidized-bed type reactors [48] and systems with slurry

recirculation through specially designed microfiltration units [49].

70
 CHAPTER FOUR

RESULTS AND DISCUSSION

71
 Chapter 4
Results And Discussion

4.1 Introduction
The first phase of the present work concentrates on the investigation of

the effect of the operating parameters like concentration of the main

fouling compounds as CaSO4 , CaCO3, SiO2 , iron salts and pH as well

as the process recovery on the fouling tendency of the processed water in

RO plants.

In order to clarify the significant effects of these operating parameters on

the fouling potential of the process, the PermaCare Simulation Program

was extensively applied ( due to its significant ability to analyze the

fouling phenomena in RO systems ) using single parameter each time and

finding its response on the fouling tendency as obtained by the program

( more explanations are given in the appendix for each case )

Scaling Tendency
The Scale Tendency ST is defined as the ratio of the activity product Q

for an equilibrium to the solubility product Ksp for the same equilibrium.

In other words, ST= Q / Ksp.

72
When the ratio of Q/ Ksp is greater than 1.0, the salt is said to have a

thermodynamic driving force to form. When the ratio is less than 1.0, the

solid does not have the driving force to form. When the ratio equals 1.0,

the solid is considered to be at saturation.

The solubility product, usually represented as Ksp, is the thermodynamic

equilibrium constant, a function of temperature and pressure. The

equilibrium constant, Ksp, can be estimated as a function of temperature

and pressure, for all salts in the solution.

73
4.2 Perma Care Program

This program is regarded to be the most important program used in evaluating

the feed water of RO membranes, and determining the scaling level, which is

expected to happen in the membranes. It is suitable for producing antiscalant

proposals for brackish water, sea water/high salinity waters, process water,

waste water and recycle systems .

It helps in calculating scaling easily. Moreover, through this program, the

occurrence of scale problems in the RO membranes system can be monitored

For the purpose of dealing with this program, adding a chemical analysis of the

water for these elements is required The program will accept data for the

following ionic species:

Anions: Ca, Mg, Na, K, Ba, Sr, Fe, Al and Mn

Cations: SO4, Cl, F, HCO 3, CO3, NO3, SiO2, PO4

As the species are entered the anion/cation balance is shown as milli equivalents

(meq/litre) are given and the total dissolved solids (TDS) .

In addition to that, the program requires determining the type of the used

membrane and its model, To select a membrane, The desired manufacturer’s

74
button should be click and the list will open up with the first membrane of the

selected manufacturer highlighted. Scroll down and The desired membrane and

the list will close with the chosen membrane selected. Once selected the

‘assumed % salt passage’ (ASP) for the membrane will be displayed at the

bottom of the screen. and this done through the program choices. Then, the

program requires the insertion of plant operation data, which is Pressure ,

Temperature, Recovery , Product Flow , pH , Hours per Day

Operating Data Limitations

Operating parameters must be within the limits set as follows:

Pressure: The pressure must be between 5 - 100 bar or between 73.5 - 1470 psi.

Recovery: The recovery must be between 1- 95%.

Product Flow: The product flow rate must be <500,000 m 3 / day or the

equivalent in the chosen units.

pH: The raw water and feed water pH must be between 4 and 10.

By the previous inputs, the program give us a table that illustrates the scaling

Tendency of the following salts( CaCO 3 , CaSO4 , iron , silica …. )

75
Through this primary evaluation, we can detect the types of scaling that occur,

and the level at which they happen.

Units available:

Flow: I/min, m3/hr, m3/d, gal/d, USgal/d, USgal/min.

Concentration: mg/l as ion, ppm as CaCO 3, meq/l as ion, mmole/l, degress

French and degrees German.

Pressure: psi, bar.

Sample Scaling Calculations

Scaling calculations have to be carried out in order to determine whether a

sparingly soluble salt presents a potential scaling problem in a reverse osmosis
system
To determine the scaling potential, one has to compare the ion product IPc of
the considered salt in the concentrate stream, with the solubility product Ksp of
that salt under conditions in the concentrate stream.

The solubility product K sp is generally also expressed in molal concentrations

and is dependent on ionic strength and temperature .

The temperature in the concentrate stream is about the same as in the feed

stream.

76
The ionic strength of the feed water is:

Ic = 1/2 Σ(mi x Zi2)

where:

mi = molal concentration of ion i (mol/kg)

zi = ionic charge of ion i

With the ionic strength of the concentrate stream, the solubility product K sp of
scaling salt can be obtained
CaSO4 → Ca++ + SO4 --

0.01 Mole of CaSO4

The ionic strength of the feed water is:

IC = 1/2 Σ(mi x Zi2)

= (1 / 2) ([Ca++] (2)2 + [SO4--] (2)2 ) =(1 / 2) ([0.01] (2)2 + [0.01] (-2)2 ) = 0.04 Mole
Debye – Huckel Equation :
2
0.511* Z * Ic
i
 log  
i ( 1 3.3* Ic )

γ = Activity Coefficient
α = ion size from tables α Ca++ = 0.60 nm α SO4-- = 0.35 nm

for [Ca++ ] Zi = +2 α Ca++ = 0.60 nm

- log γ Ca++ = 0.511(+2) 2 ( 0.04) 1/2 / ( 1+3.3*0.6*(0.04) 1/2 = 0.293
γ Ca++ = 0.51

77
 » activity of [Ca++ ] = γ Ca++ * [Ca++ ] = 0.51 * 0.01 = 0.005 M
Find Activity [SO4--] = γ SO4-- * [SO4--]

for [SO4--] Zi = - 2 α SO4-- = 0.35 nm

- log γ SO4-- = 0.511(-2) 2 ( 0.04) 1/2 / ( 1+3.3*0.35 * (0.04) 1/2 = 0.332
γ SO4-- = 0.487
» activity of [SO4--] = γ SO4-- * [SO4--] = 0.487 * 0.01 = 0.00487 M
Compare
If γ Ca++ * [Ca++ ] . γ SO4-- * [SO4--] > Ksp CaSO4 will
precipitate
If γ Ca++ * [Ca++ ] . γ SO4-- * [SO4--] < Ksp no scale in
expected
If γ Ca++ * [Ca++ ] . γ SO4-- * [SO4--] = Ksp Saturation

In this case
γ Ca++ * [Ca++ ] . γ SO4-- * [SO4--] = Ksp = 4.93 × 10 -5 for CaSO4
0.51 * 0.01 * 0.487 * 0.01 = 0.005 * 0.00487 = 2.435× 10 -5 < 4.93 × 10 -5
for CaSO4 no scale expected

78
4-3 : Effect of calcium sulfate Concentration :-

It is aimed by this experiment to study the effect of CaSO4 salt on the

performance of membrane and through knowledge of its concentration at start

of this type of deposition, Perm care program is used to study this salt, where it

is assumed that there is only CaSO 4 salt in feed water .

Hence , CaSO4 Concentration in the feed water was increased from 100 ppm to

1000 ppm ( Since this range depend on the actual practical conditions of water

quality in Riyadh ) then the corresponding fouling tendency " or Scalling

tendency " was obtained by the PermaCare Program .

Then a graph was plotted for the effect of CaSO 4 concentration on the scalling

tendency of the processed feed water . Fig (6) indicates this plot .

As shown in this figure , increasing CaSO 4 concentration in feed water affects

strongly the scalling tendency of water due to the expected increase in the over

saturation of CaSO 4. ( for more details see Appendix A )

It is worth mentioning that , some investigators [4,6,8,13] reported that the

dependence of scalling tendency on CaSO 4 concentration is not liner , but it is of

the second order type as it depends on both concentration of [ Ca++] and [So4

--
] i.e their product according to the following thermodynamic equilibrium

79
 CaSO4 → [ Ca++] [ SO4 --]

Ks = [ Ca++] [ SO4 --]

Ks is the reaction rate constant

As recently reported in literature, The degree of super saturation for CaSO 4 is

given by the following scaling index model solution
2 2
SIg  ( Ca )( SO 4 ) / Ksp

The solubility product K sp is generally expressed in molal concentrations and is

dependent on ionic strength and temperature .

80
 300

S c a llin g T e n d e n c y " P e r c e n ta g e O v e r S a tu r a tio n "

200

100
C aS O 4

0 200 400 600 800 1000

C a S O 4 in F e e d p p m

Fig.(6) Effect of CaSO4 Concentration on the Scalling Tendency of the Feed Water

81
4-4 : Effect of CaCO3 Concentration :-

In this experiment (experiments ) the aim is to study the effects of calcium

carbonate CaCO 3 salt on the performance of membranes using Perm care

program where several different values for the concentration of salt start from

10 to 200 ppm since this range depend on the actual practical .

The same previous procedure was applied here to find the effect of CaCO3

concentration in feed water on its scaling tendency , but the concentration range

selected for CaCO 3 was smaller than CaSO 4 runs due to the expected lower

solubility of this salt . The extracted scaling tendency from the program are also

plotted below in Fig .(7) .

As shown in this figure , CaCO 3 concentration has strong effect on the scaling

tendency of water even at small concentrations ( 10 ppm to 200 ppm ) , which

reflects the numerous research activities conducted by other workers in fouling

studies ( 6). . ( for more details see Appendix B )

Moreover the dependence of fouling tendency on CaCO 3 concentration is due to

the ions concentration present in the solution like :-

Ca [HCO3] 2 → [ Ca ++] + 2 HCO3 –

82
Ks = [ Ca++] [ HCO3-] 2

Most probable , a third order dependence can be observed from the

thermodynamic point of view for this case [13,14,15,20]

100
C a C O 3 S c a llin g T e n d e n c y " P e r c e n t a g e O v e r S a t u r a t io n "

80

60

40

20

0 40 80 120 160 200

C aCO 3 IN F E E D p p m

Fig (7).Effect of CaCO3 Concentration on the Scalling Tendency of the Feed Water

83
4-5 Effect of Silica Content :-

Dissolved silica (SiO 2) is naturally present in most feed waters in the range of

1-100 mg/l. Supersaturated, SiO2 can be polymerized to form insoluble colloidal

silica or silica gel, which can cause membrane scaling. The maximum allowable

SiO2 concentration in the concentrate stream is based on the solubility of SiO 2.

The scaling potential for the concentrate stream will be quite different from that

of the feed solution, because of the increase in the concentration of SiO 2, and the

change in pH. It can be calculated from the feed water analysis and the reverse

osmosis operating parameters [28]

Due to the potential importance of Silica content on fouling problems as

suffered by most workers in RO treatment plants , these runs were carried out to

elucidate this significant effect . As previously done with CaSO 4 and CaCO 3 ,

the silica content of feed water was changed from 1 to about 30 ppm , and the

corresponding scalling tendency of these solutions was extracted by the

PermaCare Program .

Then the obtained results are plotted as usual in Fig(8) which indicates a linear

dependences of scalling tendency on the concentration of SiO 2 in the processed

water . ( for more details see Appendix c )

84
It is interesting to notice that ; the dependence here is linear ( different from the

case of CaSO 4 and CaCO 3) due to the thermodynamic deriving force to this salt

which is its physical solubility and not concentration of ionic species , as silica

does not ionize in water and only its saturation solubility affects its fouling

tendency .

85
 160

S iO 2 S c a lin g T e n d e n c y " P e r c e n t a g e O v e r S a t u r a t io n "

120

80

40

10 20 30
S iO 2 IN F E E D

Fig(8): Effect of silica Concentration on the Scalling Tendency of the Feed Water

86
4-6 Effect of pH on various Fouling Compounds :-

Due to the potential importance of this parameter on RO fouling problems ,

its effect was investigated on each foulant ( e.g. CaCO 3 ,CaSO4 , Silica ……
etc ) as follows :-

4-6-1 : Effect of pH on CaCO3 Scale :

In these runs , the PH of CaCO 3 water solution was changed from 6 to 9 and
the scalling tendency of that feed water solution was obtained by the
Program as previously mentioned (CaCO 3 concentration in feed water was
kept constant in all these runs , at ( 250 ppm ) .

The obtained results are plotted in Fig(9) as usual.

It is clear from this figure that; the PH increase has strong effect on
increasing the scalling tendency of CaCO 3.

This can be ascribed to the alkaline behaviour of CaCO 3 scale .

Hence , in practice , acid dosing is normally applied to reduce this type of

alkaline scale . ( for more details see Appendix D )

87
 C a C O 3 S c a llin g T e n d e n c y " P e r c e n t a g e O v e r S a t u r a t io n "

40
80
120
160
200

Fig(9):
6

88
pH
7
8

Effect of pH on calcium carbonate ( CaCO3 ) scale .

4-6 -2 : Effect of pH on CaSO4 Scale :

In this case , a feed water containing fixed concentration of CaSO 4 is used

(340 ppm ) while its pH is varied from 5 to 8 and the corresponding salling

tendency of them are obtained as the usual .Then a plot was carried out

between pH and scalling tendency as shown in Fig. (10) . In contrast to

CaCO3 scale , PH has small ( weak ) effect on the reduction of CaSO4 scale.

This scale can be considered as slightly acidic , hence alkaline medium can

reduce it . ( for more details see Appendix E )

89
 C aso4 S c a llin g T e n d e n c y " P e r c e n ta g e O v e r S a tu r a tio n "

80
82
84
86
88

Fig(10):
6

90
PH
7

Effect of pH on calcium sulphate ( CaSO4 ) scale.

8
4-6 -3 Effect of pH on Iron Scale :

This type of scale is usually encountered in RO plants especially those

dealing with Brackish water , it has also bad effect on the membrane

performance , hence it is investigated in the present work at various pH

values ( ranging from 5 to 8 ) by the same previous procedure and collected

results from program are plotted here below in Fig , (11) , As shown from

this figure , Iron scale increases by increasing pH due to its alkaline nature ;

this scale is usually deposited from the solution in the From of Fe(OH) 2 or

Fe(OH)3 .

More over, at higher pH like 8 , this scale reaches an asymptotic value " or

quasi equilibrium value " depending on the Solubility of iron scale at these

conditions. ( for more details see Appendix F )

More over , acid dosing is also helpful to reduce this type of scale.

91
 100
IR O N S c a lin g T e n d e n c y " P e r c e n ta g e O v e r S a tu r a tio n "

80

60

40

20

5 6 7 8
PH
Fig (11) : Effect of pH on Iron scale.

4-6 - 4 Effect of pH on silica Scale :

92
As previously mentioned , SiO 2 scale is very critical scale type for RO

plants , hence the effect of pH on it is conducted in this work using the same

procedure as before , and the obtained results from the program are plotted in

Fig (12) which indicates an interesting effect for pH on silica scale . By

increasing pH from 5 to about 6.5 the scale is increased , then it gives

maximum value at about ( 6.5) and starts to decrease more deeply in the

alkaline medium .This behavior reflects the amphoteric nature of SiO 2 .

SiO2 dissolves ( or reacts ) in both alkaline and acid mediums but with better

solubility in the alkaline medium .Hence , both lime-soda process and acid

dosing can reduce the fouling potential of silica .

. ( for more details see Appendix G )

93
 80

S c a lin g T e n d e n c y " P e r c e n t a g e O v e r S a t u r a t io n "

70

60

50
S IO 2

40

4 5 6 7 8
pH

Fig.(12): Effect of pH on silica scale.

4-7 Effect of Process Recovery on the scalling potential of various Foulants :-

94
Recovery is an important parameter of RO treatment plants, high recoveries are

desirable and attractive for most experts in this field , but fouling and scale

problems are the bottleneck for achieving high recovery target. Hence the actual

effect of increasing recovery on the fouling tendency of the processed water

needs to be carefully understood .

For this reason , the present runs are conducted to clarify the effect of increasing

the recovery on each fouling salt of the present work as follows:-

4-7 -1 Effect of Recovery on the Fouling tendency of CaCO3 :-

95
In this case the recovery was changed from 30 to 85 % while the CaCO3

concentration in feed water was kept constant " at 250 ppm." and the scalling

tendency was obtained by the program for each recovery value investigated .

Then the collected results are plotted in Fig .(13) .

As shown in this figure , the recovery has strong effect on scalling tendency of

CaCO3 .

This effect is directly ascribed to the increase in salt concentration of water at

high pressure side ( brine) by extracting more product water from it .some

investigators reported the following equation for the effect of recovery on

increasing the concentration ratio CF(Cb/Cf) . [14,15,17,18]

1
CF  1  Rw1  Rs  
1  Rw CF = ø (Rw) non linear

CF = Cb\Cf Cb = brine concentration , Cf = feed concentration

Rw = water Recovery ( mass fraction )

Rs = Salt Rejection ( mass fraction )

Hence the effect has the same shape like the concentration effect .

96
 C a C O 3 S c a llin g T e n d e n c y
" P e r c e n ta g e O v e r S a tu r a tio n "

0
20
40
60
80

20
40

97
60
RECO VERY
80

Fig(13): Effect of Process Recovery on CaCO3 scale.

100
4- 7 -2 Effect of Recovery on the Fouling tendency of CaSO4 :-

Using the same pervious approach , the process recovery was varied from 30 to

85 % while the concentration of the feed water was kept constant " at 340 ppm

and corresponding scalling tendency was obtained by the program .

Then the collected results were plotted in Fig(14) which indicates the strong

dependence of fouling tendency on the process recovery .

The effect is similar to CaCO3 as previously mentioned .It is also clear from

this figure that sharp increase in scalling tendency is observed for recovery

values larger than 80 % .Hence in practice , most of RO plants are operated

around 80 % recovery " or between 70 and 80 % "

. ( for more details see Appendix I )

98
 90
C a S O 4 S c a llin g T e n d e n c y " P e r c e n ta g e O v e r S a tu r a tio n "

80

70

60

50

40

30

20

10

20 30 40 50 60 70 80 90
R ECO VER Y

Fig.(14) Effect of Process Recovery on CaSO4 scale.

99
 4 – 7 -3 Effect of Recovery on the Fouling tendency of Silica :-

In this case , the process recovery was varied from 30 to 85 % and silica

content of the feed water was kept constant at ( 15 ppm ) . as previously

done with other foulants . Then the corresponding scalling tendency was

obtained by the program . These results are plotted as usual in Fig (15) which

indicates the sensitivity of this scale to recovery. It is clear from this figure

that ; increasing the recovery higher than 80 % , lot of silica scale problems

are expected . . ( for more details see Appendix L )

100
 70

60

50
" P e r c e n ta g e O v e r S a tu r a tio n "
S IO 2 S c a llin g T e n d e n c y

40

30

20

10

20 40 60 80 100
RECO VERY

Fig(15): Effect of Process Recovery on Scalling Tendency of Silica.

101
 4 – 7 -4 Effect of Recovery on the Fouling tendency of Iron :-

The variation of recovery on iron scale is shown in Fig. (16). The saturation

varied from 3 % to 35 % depending on the recovery. At higher recovery, the

saturation of iron was also high and decrease in recovery yielded a decrease

in saturation. One important conclusion can be drawn from the simulation is

that the saturation increases steeply when the recovery was increased from 70

to 90%.. ( for more details see Appendix M )

102
 35
I R O N S c a llin g T e n d e n c y " P e r c e n t a g e O v e r S a t u r a t io n "

30

25

20

15

10

20 30 40 50 60 70 80 90
R EC O VER Y

Fig(16): Effect of Process Recovery on Scalling Tendency of Iron .

103
4 – 8 Actual Case Study On Fouling Problem For One Of RO Plants : -

4-8-1 Introduction :
This case Study is an actual fouling problem occurred in one of RO plants in

Riyadh which was established in 1986 with a designed capacity of 800 m3 / hr .

Then , RO plant has been recently up-dated by exchanging the old complete system

with new membrane modules .and applying a new control system in all its

operating steps .(as show in figure 17)

This plant , in general, consists of pretreatment part , RO membrane Section

consists of four units (Blocks) with total production capacity of 800 m3/hr, ( 200

m3/hr for each block) , The plant has been designed for Recovery of 85%, salts

passing rate not exceeding 5%, and its membranes consist of a number of layers for

each block, the first stage consists of 102 membranes, the second stage consists of

66 membranes, and the third stage consists of 36 membranes, feed Temperature

is 35 C o, , feed TDS is about 2500 ppm , feed pressure is 15 bar .

The membranes of this plant are of the spiral wound type ( BW30-400 FILMTEC

Membranes ) made of polyamide.,

The system is equipped by a washing unit, and it can conduct flushing for blocks

automatically.

The plant has been designed on the following operating conditions .

104
 RO. FEED
Analysis
Minimum Maximum

Temperature CO 30 40
PH 5.5 7
Hardness Calcium mg/l as CaCO3 150 240
Hardness Megnesium mg/l as CaCO3 130 250
Alkalinity Total mg/l as CaCO3 12 50
Salinity (TDS ) mg/l 1500 2500
Chloride mg/l 250 350
Sulphate SO4 mg/l 620 800
Nitrate as NO2 mg/l 0.5 2.0
Nitrate as NO3 mg/l 17 40
Iron mg/l 0.05 0.1
Aluminum mg/l 0.02 0.05
Silicate as SiO2 mg/l 15 30
Turbidity (NTU ) 0 1
SDI ‹ 3
The new system has been operated in the plant starting from 2005.

Table (2 ) Operating Conditions of the Considered RO Plant

105
 Ca(OH)2
Sodium aluminate Na2CO3
Polyelectrolyte Cl2

Raw water

Cooling
tower Sand
filter Buffer
tank

Clarifier H2SO4

Sand
filter

Blending Line

RO

mixing
champer High pressure Booster
Na2Co3 pump Cartridge pump
SBS filter
Anti-scalant
H2SO4

Fig 17 : Schematic Flowsheet of the Plant " used in case study "

106
During the first operation of this plant , the product started to decrease suddenly
and strongly from 200 m3/ hr to about 50 m3 / hr ( about 75 % reduction as shown
in Fig (18) .
This was strange behavior since the system is new and modern.

240

200
PRO DUCT FLO W RATE

160

120

80

40

0 10 20 30
DAYS
Fig(.18): Flux Decline (Product Flow Rate during the first phase of this case study )

107
The Recovery also decreased during this period from 85 % to about 50% as
shown in Fig (19)

90

80
RECO VERY

70

60

50

0 10 20 30
DAYS

Fig(.19): Recovery Decrease ( During this phase of the problem).

108
More over the Pressure drop increases during this period from 3 bar to about 5
bar , as shown in Fig.(20)

5
P re s s u re D ro p (B a r)

0 10 20 30
T im e (D a y s )
Fig(20): Pressure drop Increase ( during the first phase of the problem).

109
Then , it was started to think about the main reasons for this problem to find out

the suitable solutions for it .

It is quite clear that the type of the present problem is a fouling case due to the

sharp flux decline and the rise in the pressure drop .

Hence , it was decided to consider what changes occurred to the feed water

during this period .

Fig. ( 21) illustrates the variation of feed conductivity with number of days of

operation. It is very clear from this figure that the conductivity of the feed

varied from 1970 to 1990 ; i.e. no significant changes occurred to the feed

water

110
 2000

1980
F e e d C o n d u c tiv ity

1960

1940

1920

1900

0 10 20 30
T im e ( D a y s )

Fig.(21) Conductivity of the feed water to the Plant(during of the first phase of the problem ).

111
 Later on , PH values of the process water was considered to account for
any reason of the present problem .But , as shown in Fig( 22) , no significant
changes can be detected .

6
PH

0 10 20 30
T im e (D a y s )
Fig.(22): PH of the Processed water of the Plant(during of the first phase of the problem ).

112
Then , it was decided to wash the membranes .( as it is normal practice in such

cases ) , After washing , the product starts to rise directly to it is design values

shown in Fig.( 23)

200

160
PRO DUCT FLO W RATE

120

80

40

0 10 20 30
DAYS

Fig(.23) : Flux increase after washing (during the second phase of this problem).

113
 More over , the recovery started to increase directly after washing (as shown in

Fig (24)

90

80
RECO VERY

70

60

50

0 10 20 30
DAYS

Fig(24):Recovery Increase after Membranes Washing (during of the second phase of the problem).

114
 The pressure drop also decreased after washing (as shown in Fig.(25)

3 .2

2 .8

2 .4
P re s s u r D ro p ( B a r )

1 .6

1 .2

0 10 20 30
T im e ( D a y s )

Fig.(25): Pressure Drop Decrease after Washing (during of the second phase of the problem ).

115
 But , After about one month and during the third phase of this case , the plant

recovery and the product started to drop again ( the problem reappeared ) as

shown in Fig. (26) and (27).

90

80
R e c o v e ry

70

60

50

0 10 20 30
T im e ( D a y s )

Fig(26). Recovery Decrease(during of the there'd phase of the problem)

116
 240

200
P R O D U C T F L O W R A T E (m 3 /h r )

160

120

80

40

0 10 20 30
T im e (D a y s )

Fig(27). Product decline (during of the third phase of the problem)

117
 But pressure drop did not detect any significant change during this third phase
of the problem as shown in Fig.( 28)

3
P re s s u re D ro p ( B a r)

0 10 20 30
T im e ( D a y s )

Fig(28). Pressure drop (during of the third phase of the problem)

118
As previously mentioned , during the initial period “ 1 st Phase “ of this problem;

the drastic decline in the production rate of the plant and the significant decrease in

the process recovery as well as the pronounced increase in the pressure drop ; were

considered as a strong evidence that the plant was suffering from a harmful fouling

problem.

In order to find out the possible , reasons leading to this problem ; the feed quality

was reconsidered as expressed by its electrical conductivity ; but no significant

changes were observed in this feed water ( as shown in Fig .(21) then the SDI

index of the input water to the membrane section was also rechecked several times

during this period and again no detectable increases were found in that index .

More over , the PH of the process water of the plant was monitored during this

phase and no significant changes were observed ( as shown in Fig (22) ) .

Therefore , it was decided to do the routine washing of the membrane

section extensively , and consequently after that ; the productivity of the RO plant

starts directly to increase until it reached the designed capacity again ( as shown in

Fig .23) . both recovery and pressure drop started also to be as designed . ( as

shown in Fig .(24) (25) ). Hence , it was started to think about biofouling problem

(as it is the only type of the fouling which is not detectable by SDI or feed

conductivity , or pH).

119
Therefore, we have conducted bacterial examination for input water to the

membrane , and it showed that there is an over count in feed water, then we

controlled the chloration dosing to get rid of this problem

But after about one month of plant operation , the problem started again as

observed before ( Figs.(26) and (27) ) for flux decline and recovery decrease

In conclusion of this case study it has been clear to us that the problem is a

biofouling one and not scale, and we get rid of it by precise controlling of the

chlorine dosing to remove the bacterial growth in the feeding lines as well as

through washing of the membranes .

As previously mentioned the problem began to appear again according to the

following interpretation :

The operations of chlorine injection were not conducted in the proper required

way, where there are some areas in the system which are not taking its enough

dose, consequently, the bacteria has grown and appeared once again.

After dealing with this case study and also using ROSA and PermaCare programs,

it was clear that these programs are not giving bio fouling indications, but they are

only giving the indications of scaling problems, hence, it is now clear that ; there is

need from practical point of view to have other programs that deal with this type

of harmful fouling problem .

120
 CHAPTER FIVE

CONCLUSIONS AND RECOMMENDATIONS

121
 Chapter 5

Conclusions And Recommendations

5.1 Conclusions:
The Present work led to the following conclusion:-

1. CaCO3 salt has strong effect on the scalling tendency of water even at low

concentrations ( about 100 to 200 ppm ) ,which reflects the numerous

research activities on this salt in the fouling field .

2. CaSO4 salt has also similer effect like CaCO3 but at higher concentration

levels ( about 1000 ppm ) due to the increased solubility of it in water

medium . Both effects ( of CaCO3 and CaSO4 ) are non liner due to the

effects of their ionic concentration on the scalling tendency .

3. Silica effect on the scalling tendency was even deeper than other salts, and

its scale started to appear at lower concentrations ( about 20-30 ppm ). The

effect on the scalling tendency is of the liner type due to dependence on the

thermodynamic as a result of over-saturation and .It is not ionized in water .

4. The pH investigations for the scalling tendencies of various fouling

compounds revealed that :

122
 A. Direct increase in CaCO3 scale with increasing pH as it is an alkaline

scale .

B. Direct effect also in iron scale as it is also an alkaline scale ( as Fe(OH)2

C. Slight effect on CaSO4 Scale as it can be considered a neutral or slightly

acidic scale .

D. An interesting effect on silica scale in both acidic and alkaline range of

pH with an optimum value ( around pH~ 6 – 7 ) due to the amphoteric

nature of SiO2 it self . Moreover alkaline medium ( PH > 8 ) reduces

strongly silica scale .

5. The Process recovery investigations revealed strong effects on the

scalling tendency of fouling compounds due to the expected effect on the

over saturations of these salts by increasing the process recovery

especially after 80 % Recovery .

6. The case study on fouling revealed that the flux decline and pressure drop

are the significant operating factors indicating the presence of a fouling

problem .

But SDI and feed conductivity has nothing to detect the biofouling problem in

practice .

123
7. Precise monitoring of bacterial analysis of water entering the membrane

section as well as the proper chlorine dosing are only the significant

factors to overcome the biofouling problem in practice .

8. Biofouling problem , if start to happen , can be expected to reappear

again until the whole process flowsheet is free of any bacterial infection .

9. The present software programs ( or packages ) for RO plants , either ;

PermaCare or ROSA have nothing to do with biofouling as they

concentrate on the inorganic scale salts .

10. Precise membrane washing and proper pretreatment as well as efficient

monitoring of the RO production line are significant factors for

overcoming scale and fouling problems in these plants .

124
5.2 Recommendations

1. More attention has to be given to ; silica , iron and biological

fouling in RO plants either from the practical point of view or from

the research side .

2. An Actual need exists for a software program covering the

biofouling problems in practice similar to PermaCare and ROSA

programs .

3. The process recovery and pH of the processed water in RO plants

have to be given more consideration for their strong effects on

scale formation problems in these processes .

4. Proper monitoring and control of the process parameters in RO

plants are of vital importance to reveal early and overcome

properly the expected fouling and scale problems in this field .

125
 REFERENCES

126
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 17- C. W. Turner, and D. W. Smith, “Calcium Carbonate Scaling Kinetics

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19- B. Hamrouni and M. Dhahbi, J. Soc. Chim. Tunisie, 4, 461, 1999.

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Handbook of Single Phase Convective Heat Transfer, S. Kakae, ILK.

Shah and W. Auny, eds., John Wiley, New York, 1987.

21- J.G. Knudsen, "Fouling in heat exchangers", In: Hemisphere Handbook

of Heat Exchangers Design, G.F. Hewitt, ed., 1990.

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105, May 374-378, 1983.

23- D. Hasson, “Precipitation Fouling,” Fouling of Heat Transfer

Equipment, E.F.C.

24- Somerscales and J.G. Knudsen, eds., Hemisphere, New York, 527-568,

1981 .

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52, 558-562, 1974.

26- A.P. Watkinson, and Martinez, O., “Scaling of Spirally Indented Heat

Exchanger Tubes,” Transactions of the ASME, 490-492, 1975.

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 28- E.H. Kelle Zeiher, Bosco Ho, Kevin D. Williams, "Novel Antiscalant

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on Membranes in Drinking Water Production, Paris, France, 3-6 October

2000, pp. 173-179.

30- Michael A. Finan and Denise A. Tracey, "Planning Needed to Prevent

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Science, 03 February 2006.

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33- K. J. Howe, "Technical Challenges to Concentrate Disposal from Inland

Desalination", site:

www.unm.edu/~cstp/Reports/H2O_Session_4/4-7_Howe.pdf

34- R.J. Petersen, "Composite reverse-osmosis and nanofiltration

membranes", J. Membr. Sci. 83, 81, 1993.

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treatment by reverse osmosis in Jordan", Desalination 164, 157, 2004.

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 36- S.P. Agashichev and M.E. El-Dahshan, "Reverse osmosis incorporated

into existing cogenerating systems as a sustainable technological

alternative for United Arab Emirates", Desalination 157, 33, 2003.

37- R.W. Atwater, L. Palmquist, and J. Onkka, "The west basin desalter

project: a viable alternative", Desalination 103, 117, 1995.

38- P. Gagliardo, S. Adham, R. Trussell, and A. Olivieri, "Water

repurification via reverse osmosis", Desalination 117, 73, 1998.

39- N. Hilal, H. Al-Zoubi, N.A. Darwish, A.W. Mohamma, and M. Abu

Arabi, "A comprehensive review of nanofiltration membranes:

Treatment, pretreatment, modeling, and atomic force microscopy",

Desalination 170, 281, 2004.

40- J.K. Kimes, "The regulation of concentrate disposal in Florida",

Desalination 102, 87, 1995.

41- J.S. Vrouwenvelder, S.A. Manolarakis, H.R. Veenendaal, and D. van der

Kooij, "Biofouling potential of chemicals used for scale control in RO

and NF membranes", Desalination 132, 1, 2000.

42- "Water quality and treatment", 4th Edition, Prepared by the American

Water works assosiation, McGraw-Hill, Inc., New York, 1990.

43- "Water Treatment Handbook", Degremont Company, 6th Edition,

1991.

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Chapter 4.2.8, 1982.

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Proceedings - Fifth World Filtration Congress, Societe Francaise de

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131
 46- "Handbook of Industrial Membrane Technology", M. C. Porter (editor),

Noyes Publications, Park Ridge, New Jersey, U.S.A. 1990.

47- J. E. Hobble, Daley, R.J.; Jasper, S., Appl. Environ, Microbiol., 33,

1225, 1976.

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Microbiol., 36, 1978, 926.

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von Trinkwasser. Vom Wasser 65, 257, 1985.

132
 APPENDICES

133
 Appendix A

A.1 Effect of CaSO4 Concentration :

1- Conditions
Feed Pressure = 15 bar
Raw Water pH = 8
Feed Water pH = 5.5
Product Flow = 100 m3 / hr
Recovery = 85 %
Temp = 30 C o
Membrane Type ( DOW FilmTec BW30-400 )

2- CaSO4 Solution :

CaSO4 → Ca++ + SO4 --

The Con. ( ppm ) of the Ca and SO4 was calculated from the
following equation :

Con.( ppm) of Ca    Con.( ppm) CaSO4 M .wt. of Ca  

.
M .wt. CaSO 4
Con.( ppm) CaSO4 M .wt. of SO 4  
Con.( ppm) of SO 4   M .wt. CaSO 4
.

3- Sample Calculation :-

Con. (ppm ) CaSO4 = 1000 ppm

M. wt. of CaSO4 = 40+32+(16*4 ) = 136
M. wt. of Ca = 40
M. wt. of SO4 = 32+(16*4 ) = 96

» Con. (ppm ) ca ++ = ( 1000/136 )* 40 = 294 ppm

» Con. (ppm ) SO4 -- = ( 1000/136 )* 96 = 706 ppm

134
 4- The Effect of the increase of calcium concentration ca++
and sulfate concentration SO4-- in supplement water alone
without any other factors was examined as these ions
represent calcium sulfate in supplement water and the results
showed the followings:

Table (4) CaSO4 Concentration

CaSO4
  scalling  
CaCO3 Tendency
scalling Tendency By
CaSO4 Feed SO4—( ppm ) Ca++( ppm ) By PermaCare PermaCare
  ppm By Equation By Equation Program Program  
  100 71 29 0.1  5.2  
  150 106 44 5.9 11.2  
  200 141 59 10 18.9  
  250 176 74 13.1 28.1  
  300 212 88 15.4 38.4  
  350 247 103 17.6 50  
  400 282 118 19.4 62.6  
  450 318 132 20.9 75.9  
  500 353 147 22.3 90.3  
  550 388 162 23.6 105.4  
  600 424 176 24.7 120.8  
  650 459 191 25.7 137.2  
  700 494 206 26.7 154.1  
  750 529 221 27.6 171.6  
  800 565 235 28.4 189.2  
  850 600 250 29.2 207.6  
  900 635 265 29.9 226.5  
  950 671 279 30.6 245.4  
  1000 706 294 31.2 265  

135
 PermaCare Program Results

CaSO4 Concentration

136
 Appendix B

B.1 . Effect of CaCO3 Concentration :

1- Conditions
Feed Pressure = 15 bar
Raw Water PH = 8
Feed Water PH = 5.5
Product Flow = 100 m3 / hr
Recovery = 85 %
Temp = 30 C o
Membrane Type ( DOW FilmTec BW30-400 )

2- CaCO3 Solution :

CaCO3 → Ca++ + CO3 --

The Con. ( ppm ) of the Ca and CO3 was calculated from the
following equation :
Con.( ppm) CaCO 3 M .wt . of Ca  
Con.( ppm) of Ca    .
M .wt . CaCO 3
Con.( ppm) CaCO3 M .wt. of CO3  
Con.( ppm) of CO3    .
M .wt. CaCO3

137
 3- Sample Calculation :-

Con. (ppm ) CaCO3 = 200 ppm

M. wt. of CaCO3 = 40+12+ (16*3) = 100
M. wt. of Ca = 40
M. wt. of CO3 = 12+(16*3 ) = 60

» Con. (ppm ) ca ++ = ( 200/100)* 40 = 80 ppm

» Con. (ppm ) SO4 -- = ( 200/100)* 60 = 120 ppm

4- The Effect of the increase of calcium concentration

Ca++ and carbonate concentration CO3 -- in supplement
water alone without any other factors was examined as
these ions represent calcium carbonate in supplement water
and the results showed the followings

:
138
  Table ( 5) CaCO3 Concentration  
   

CaCO3 CaSO4
CaCO3 Feed scalling scalling
  ppm Ca++ CO3-- Tendency Tendency  
  10 4 6 20.3    
  20 8 12 35.7    
  30 12 18 45.4    
  40 16 24 52.5    
  50 20 30 58.2 2.9  
  60 24 36 62.9 4  
  70 28 42 66.9 5.2  
  80 32 48 70.4 6.5  
  90 36 54 73.6 7.9  
  100 40 60 76.4 9.4  
  110 44 66 78.9 11.1  
  120 48 72 81.2 12.8  
  130 52 78 83.4 14.6  
  140 56 84 85.3 16.5  
  150 60 90 87.2 18.5  
  160 64 96 88.9 20.6  
  170 68 102 90.5 22.8  
  180 72 108 92.1 25  
  190 76 114 93.5 27.3  
  200 80 120 94.9 29.6  

139
 PermaCare Program Results

CaCO3 Concentration

140
 Appendix C

C.1 Effect of Silica Concentration :

The Effect of the increase of Silica SiO2 in supplement water

alone without any other factors and the results showed the
followings:
Table (6) SiO2 Feed Concentration
       

SiO2 Feed SiO2

  ppm scalling Tendency  

  5 23.1  

  8 37  

  10 46.2  

  12 55.5  

  15 69.3  

  18 83.2  

  20 92.4  

  22 101.6  

  25 115.5  

  28 129.3  

  30 138.5  

141
 PermaCare Program Results

SiO2 Concentration

142
 Appendix D

D1 Effect of PH on CaCO3 Scale :

1- Conditions
Feed Pressure = 15 bar
Raw Water PH = 8
Feed Water PH = range ( 5 to 8 )
Recovery = 85 %
Temp = 30 C o
Membrane Type ( DOW FilmTec BW30-400 )
CaCO3 Concentration in feed water = 250 ppm

2- The Effect of PH from 5 to 8 was examined in order to

know how the precipitates calcium carbonate salt is affected
and the results showed the following:

143
 Table (7) PH on CaCO3 Scale

144
 
     
CaCO3
  PH scalling Tendency  
  5 33.2  
  5.2 46  
  5.4 58.6  
  5.6 70.8  
  5.8 82.5  
  6 93.7  
  6.2 104.1  
  6.4 113.7  
  6.6 122.6  
  6.8 130.9  
  7 138.7  
  7.2 146.1  
  7.4 153.3  
  7.6 160.3  
  7.8 167.2  
  8 174.1  

145
 Appendix E

E.1. Effect of PH on CaSO4 Scale :

1- Conditions
Feed Pressure = 15 bar
Raw Water PH = 8
Feed Water PH = from 5 to 8
Product Flow = 100 m3 / hr
Recovery = 85 %
Temp = 30 C o
Calcium Sulfate Concentration in feed water = 340 ppm

2- The Effect of PH from 5 to 8 was examined in order to

know how the precipitates calcium sulfate salt is affected
and the results showed the following:

146
 Table ( 8) PH on CaSO4 Scale
CaSO4
  PH scalling Tendency  
  5 87.2  
  5.2 87.1  
  5.4 87  
  5.6 86.9  
  5.8 86.7  
  6 86.5  
  6.2 86.2  
  6.4 86  
  6.6 85.8  
  6.8 85.6  
  7 85.4  
  7.2 85.3  
  7.4 85.3  
  7.6 85.2  
  7.8 85.2  
  8 85.2  

147
 Appendix F

F .1 . Effect of PH on IRON Scale :

1- Conditions
Feed Pressure = 15 bar
Raw Water PH = 8
Feed Water PH = 5.5
Recovery = 85 %
Temp = 30 C o
IRON Concentration in feed water = .001 ppm
2- The Effect of PH from 5 to 8 was
examined in order to know how the
precipitates iron is affected and the
results showed the following:
Table (9 ) PH on IRON Scale
       
IRON
  PH scalling Tendency  
  5 14.2  
  5.2 20.8  
  5.4 27.3  
  5.6 33.8  
  5.8 40.4  
  6 46.9  
  6.2 53.5  
  6.4 60  
  6.6 66.5  
  6.8 73.1  
  7 79.6  
  7.2 86.2  
  7.4 92.7  
  7.6 98.2  
  7.8 98.2  
  8 98.2  

148
 Appendix G

G 1 Effect of PH on SiO2 Scale :

1-Conditions
Feed Pressure = 15 bar
Raw Water PH = 8
Feed Water PH = 5.5
Recovery = 85 %
Temp = 30 C o
Concentration in feed water = 15 ppm
2- The Effect of PH from 5 to 8 was examined in order to
know how the precipitates silica is affected and the results showed the
following:
Table (10) PH on SiO2 Scale
SiO2
  PH scalling Tendency  
  5 62.3  
  5.2 64.3  
  5.4 66.5  
  5.6 68.6  
  5.8 70.7  
  6 72.4  
  6.2 73.7  
  6.4 74.2  
  6.6 73.9  
  6.8 72.5  
  7 70  
  7.2 66.5  
  7.4 62  
  7.6 57  
  7.8 51.7  
  8 46.4  

149
 PermaCare Program Results

Effect of PH

150
 Appendix H
H1 . Effect of Recovery on CaCO3 Scale :
1-Conditions
Feed Pressure = 15 bar
Raw Water PH = 8
Feed Water PH = 5.5
Product Flow = 100 m3 / hr
Temp = 30 C o
2- The Effect of recovery rate from 30 to 85% was examined in
order to know how the precipitates calcium carbonate is affected
and the results showed the following

Table (11) Recovery on CaCO3 Scale

CaCO3
  Recovery scalling Tendency  
  30 3.2  
  35 6.3  
  40 9.6  
  45 13.1  
  50 17  
  55 21.3  
  60 26.1  
  65 31.5  
  70 37.6  
  75 44.9  
  80 53.6  
  85 64.8  

151
 Appendix I

I. 1 Effect of Recovery on CaSO4 Scale :

1-Conditions
Feed Pressure = 15 bar
Raw Water PH = 8
Feed Water PH = 5.5
Temp = 30 C o
2- The Effect of recovery rate from 30 to 85% was examined in
order to know how the precipitates calcium sulfate is affected
and the results showed the following

Table (12) Recovery on CaSO4 Scale

CaSO4
  Recovery scalling Tendency  
  30 7.7  
  35 8.8  
  40 10  
  45 11.6  
  50 13.6  
  55 16.2  
  60 19.6  
  65 24.3  
  70 30.9  
  75 40.9  
  80 57.1  
  85 86.9  

152
 Appendix M

M 1 . Effect of Recovery on IRON Scale :

1-Conditions
Feed Pressure = 15 bar
Raw Water PH = 8
Feed Water PH = 5.5
Product Flow = 100 m3 / hr
Temp = 30 C o
2- The Effect of recovery rate from 30 to 85% was examined in
order to know how the precipitates iron is affected and the
results showed the following

Table (13) Recovery on IRON Scale

IRON
  Recovery scalling Tendency  
  30 3  
  35 3.4  
  40 3.9  
  45 4.6  
  50 5.3  
  55 6.3  
  60 7.6  
  65 9.4  
  70 11.8  
  75 15.3  
  80 20.9  
  85 30.6  

153
 Appendix L

Effect of Recovery on SiO2 Scale :

1-Conditions
Feed Pressure = 15 bar
Raw Water PH = 8
Feed Water PH = 5.5
Product Flow = 100 m3 / hr
Temp = 30 C o
Membrane Type ( DOW FilmTec BW30-400 )
2- The Effect of recovery rate from 30 to 85% was examined in
order to know how the precipitates silica is affected and the
results showed the following

Table (14) Recovery on SiO2 Scale

SiO2
  Recovery scalling Tendency  
  30 13.3  
  35 14.4  
  40 15.7  
  45 17.2  
  50 19  
  55 21.3  
  60 24.1  
  65 27.7  
  70 32.6  
  75 39.5  
  80 50  
  85 67.5  

154
 PermaCare Program Results

Effect of Recovery

155
 PermaCare Program Pictures

156
 Appendix N

ACTUAL CASE STUDY ON FOULING PROBLEM FOR ONE

OF RO PLANTS : -

157
 ACTUAL CASE STUDY ON FOULING PROBLEM FOR ONE OF RO PLANTS :
TABLE ( 15 ) PHASE 1
FEED FEED FEED PRODUCT INLET _REJECT PRODUCT _INLET _REJECT CON_ TDS TDS TDS_
DAY PH COND TEMP COND FLOW FLOW FLOW PR PR dp RATE _STG1 _STG2 STG3
1 6.93 1986.89 32.89 42.01 29.94 29.12 208.00 14.00 11.09 2.91 86.00 20.42 35.78 77.28
2 7.04 1986.86 33.01 39.95 28.51 28.80 192.00 14.10 11.00 3.10 85.00 20.49 35.09 69.68
3 6.85 1985.12 33.29 63.06 29.49 29.60 185.00 14.30 11.00 3.30 84.00 38.49 37.05 96.13
4 6.98 1987.83 33.54 46.13 29.23 32.58 181.00 14.50 10.86 3.64 82.00 21.85 35.29 68.66
5 7.36 1989.16 34.05 93.52 29.99 33.25 175.00 14.70 11.00 3.70 81.00 22.20 36.32 73.51
7 6.61 1986.58 33.78 92.25 30.08 34.20 171.00 14.80 11.00 3.80 80.00 22.70 36.61 70.98
8 6.60 1983.32 33.59 93.41 30.34 33.20 166.00 14.85 11.00 3.85 80.00 21.44 34.22 64.11
9 6.58 1980.11 33.55 95.16 29.54 33.81 161.00 14.90 11.00 3.90 79.00 22.55 34.78 62.83
10 6.58 1981.58 33.81 87.72 29.12 33.00 150.00 15.00 11.15 3.85 78.00 23.29 35.49 61.88
11 6.80 1980.81 33.94 41.28 27.52 34.04 148.00 15.10 11.19 3.91 77.00 21.38 33.95 59.84
12 6.69 1979.28 34.36 43.54 28.24 36.00 144.00 15.40 11.01 4.39 75.00 22.94 34.76 60.67
13 6.78 1983.29 34.40 45.43 28.80 39.20 140.00 15.45 10.86 4.59 72.00 23.80 34.88 60.94
14 6.90 1987.83 34.57 46.71 29.52 40.80 136.00 15.50 11.10 4.40 70.00 23.48 35.94 67.54
15 6.70 1984.74 34.66 48.51 29.84 40.50 135.00 15.55 11.00 4.55 70.00 23.75 36.52 69.96
17 6.97 1983.87 35.30 52.30 34.85 40.61 131.00 15.55 11.18 4.37 69.00 26.45 44.55 91.92
18 6.72 1988.49 35.71 54.22 33.67 39.68 128.00 15.55 11.15 4.40 69.00 25.41 43.19 88.45
19 6.91 1988.90 34.93 56.22 31.93 40.92 124.00 15.60 11.00 4.60 67.00 23.41 38.17 73.50
20 6.80 1987.27 35.28 59.41 31.96 41.48 122.00 15.65 11.09 4.56 66.00 24.21 40.94 81.60
21 6.80 1990.14 35.41 62.73 32.65 42.12 117.00 15.68 11.11 4.57 64.00 24.86 41.65 84.00
22 6.85 1987.49 36.16 65.85 32.53 41.80 110.00 15.70 11.01 4.69 62.00 24.99 41.38 83.89
23 6.90 1989.09 36.27 67.75 32.75 40.56 104.00 15.71 11.03 4.68 61.00 25.41 41.60 84.25
24 6.88 1988.09 36.02 70.57 31.24 40.40 101.00 15.75 11.06 4.69 60.00 23.99 40.17 81.94
25 7.16 1989.45 35.45 72.89 31.81 41.00 100.00 15.78 11.29 4.49 59.00 24.07 41.65 86.75
26 6.98 1985.64 35.87 74.20 30.61 40.42 94.00 15.80 11.15 4.65 57.00 23.35 39.88 82.70
27 7.11 1987.41 35.65 76.18 30.24 39.16 89.00 15.85 11.12 4.73 56.00 23.61 39.66 80.72
28 7.11 1988.18 34.84 78.30 30.11 36.90 82.00 15.90 11.18 4.72 55.00 23.74 39.55 80.59
29 7.31 1988.27 35.24 80.34 30.02 32.90 70.00 15.95 11.37 4.58 53.00 22.95 40.36 86.56
30 7.34 1990.27 35.44 81.73 32.10 30.38 62.00 16.00 11.30 4.70 51.00 24.38 44.69 106.74

158
 ACTUAL CASE STUDY ON FOULING PROBLEM FOR ONE OF RO PLANTS :
TABLE ( 16 ) PHASE 2
FEED_ FEED FEED PRODUCT INLET REJECT INLET TDS_ TDS TDS_
DAY PH _COND _TEMP COND FLOW _FLOW PRODUCT_FLOW PR REJECT_PR dP CON_RATE _STG1 STG2 STG3
1 7.14 2624.53 38.84 1061.97 32.43 24.09 60.00 15.06 12.10 2.96 59.85 19.53 186.55 417.37
2 7.03 2600.30 39.00 218.65 32.43 25.94 65.00 15.05 12.27 2.78 60.10 19.53 186.55 420.16
3 7.14 2630.11 38.80 47.46 31.38 26.58 66.00 15.04 12.29 2.75 59.73 19.87 188.99 417.72
4 6.95 2573.13 38.51 47.35 31.03 27.09 67.00 15.05 12.31 2.74 59.57 20.22 190.73 423.30
5 7.43 2620.24 38.68 49.49 31.73 27.85 70.00 15.04 12.39 2.65 60.21 20.22 191.43 426.09
6 7.44 2641.18 39.16 50.69 32.43 28.09 75.00 15.04 12.42 2.62 62.55 19.87 191.78 428.53
7 7.29 2500.49 39.98 1058.32 33.12 29.26 77.00 15.06 12.41 2.65 62.00 19.87 192.47 428.53
8 7.15 2490.72 39.15 1059.30 33.82 27.65 79.00 15.05 12.44 2.61 65.00 19.87 192.82 425.74
9 7.30 2744.67 39.37 1058.81 32.43 26.40 80.00 15.08 12.48 2.60 67.00 19.87 192.12 423.30
10 7.02 2661.65 39.46 1060.28 32.78 28.90 85.00 15.04 12.45 2.59 66.00 19.87 188.99 415.28
11 7.27 2705.60 38.22 1059.30 31.73 30.80 88.00 15.05 12.46 2.59 65.00 19.87 187.24 404.82
12 7.18 2480.95 39.58 1055.88 32.78 29.44 92.00 15.04 12.47 2.57 68.00 19.53 185.50 405.52
13 7.15 2832.58 39.95 1053.93 30.68 28.50 95.00 15.07 12.49 2.58 70.00 19.18 185.15 402.73
14 6.99 2759.33 37.97 1057.84 32.43 30.90 103.00 15.06 12.50 2.56 70.00 19.18 184.45 400.99
15 7.02 2544.44 38.97 1059.79 32.08 30.80 110.00 15.07 12.52 2.55 72.00 19.18 184.10 401.33
16 7.23 2778.86 38.29 1065.16 31.73 33.35 115.00 15.07 12.53 2.54 71.00 19.53 184.45 396.80
17 7.08 2754.44 39.15 1066.13 31.38 32.94 122.00 15.03 12.53 2.50 73.00 19.18 184.45 395.76
18 7.10 2749.56 37.88 1065.16 31.73 33.75 125.00 15.07 12.57 2.50 73.00 18.83 183.76 396.10
19 7.26 2759.33 39.54 1064.18 31.38 33.54 129.00 15.06 12.55 2.51 74.00 18.83 183.76 398.20
20 7.26 2710.49 39.85 1064.67 31.73 30.96 129.00 15.04 12.53 2.51 76.00 18.83 182.71 394.36
21 7.37 2471.18 37.88 1064.18 30.68 32.00 128.00 15.06 12.56 2.50 75.00 18.83 182.01 390.53
22 7.18 2759.33 38.17 1063.69 29.64 37.24 133.00 15.11 12.58 2.53 72.00 18.83 182.01 387.04
23 7.33 2476.07 39.71 1063.69 30.68 35.62 137.00 15.06 12.55 2.51 74.00 19.18 182.36 383.20
24 7.34 2681.19 38.39 1062.72 29.99 33.60 140.00 15.06 12.56 2.50 76.00 19.18 182.36 384.95
25 7.27 2632.35 38.88 1062.23 31.03 31.90 145.00 15.06 12.60 2.46 78.00 19.18 183.76 386.34
26 7.19 2593.28 38.24 1062.72 31.38 30.00 150.00 15.09 12.70 2.39 80.00 19.18 184.45 389.48
27 7.06 2451.65 37.70 1062.23 31.03 28.99 165.00 15.04 12.75 2.29 82.43 19.18 185.85 388.43
28 7.06 2495.60 37.51 1060.28 30.34 28.07 170.00 15.07 12.75 2.32 83.49 19.53 187.24 387.04
29 7.26 2661.65 38.75 1062.72 31.03 30.09 177.00 15.07 12.76 2.31 83.00 20.22 187.24 387.04

159
 30 6.99 2490.72 39.56 1061.74 31.03 28.84 190.00 15.07 12.77 2.30 84.82 19.18 187.24 380.06

160
 ACTUAL CASE STUDY ON FOULING PROBLEM FOR ONE OF RO PLANTS :
TABLE ( 17 ) PHASE 3
FEED FEED PRODUCT _INLET _REJECT PRODUCT INLET_ REJECT_ CON TDS_ TDS TD
DAY FEED_PH _COND _TEMP _COND _FLOW FLOW _FLOW PR PR dp _RATE _STG1 STG2 ST
1 6.93 1986.80 32.89 42.01 29.94 32.11 210.00 14.19 11.09 3.10 84.71 20.42 35.78 77.
2 7.04 1975.08 33.01 39.95 28.51 29.91 200.00 14.18 11.00 3.18 84.00 20.49 35.09 69.
3 6.85 1978.01 33.29 63.06 29.49 30.23 180.00 13.65 10.35 3.30 83.21 38.49 37.05 96.
4 6.98 1979.96 33.54 46.13 29.23 43.95 168.00 14.18 10.86 3.32 83.00 21.85 35.29 68.
5 7.36 1979.47 34.05 93.52 29.99 27.72 166.00 14.14 10.73 3.41 83.30 22.20 36.32 73.
7 6.61 1992.17 33.78 92.25 30.08 25.50 170.00 14.17 11.11 3.05 82.00 22.70 36.61 70.
8 6.60 1985.33 33.59 93.41 30.34 28.88 185.00 13.09 10.31 2.77 82.00 21.44 34.22 64.
9 6.58 1999.00 33.55 95.16 29.54 30.15 190.00 13.78 10.73 3.04 80.00 22.55 34.78 62.
10 6.58 1979.96 33.81 87.72 29.12 27.66 175.00 14.34 11.15 3.19 80.00 23.29 35.49 61.
11 6.80 1978.50 33.94 41.28 27.52 28.59 180.00 14.41 11.19 3.22 80.00 21.38 33.95 59.
12 6.69 1976.06 34.36 43.54 28.24 27.70 175.00 14.38 11.01 3.37 79.00 22.94 34.76 60.
13 6.78 1991.68 34.40 45.43 28.80 27.21 165.00 14.18 10.86 3.32 77.00 23.80 34.88 60.
14 6.90 1975.57 34.57 46.71 29.52 24.59 160.00 14.18 11.10 3.08 74.00 23.48 35.94 67.
15 6.70 1992.17 34.66 48.51 29.84 22.06 140.00 13.74 10.61 3.12 73.00 23.75 36.52 69.
17 6.97 1977.03 35.30 52.30 34.85 20.60 131.00 13.93 11.18 2.75 73.00 26.45 44.55 91.
18 6.72 1987.77 35.71 54.22 33.67 20.72 130.00 14.07 11.15 2.93 70.00 25.41 43.19 88.
19 6.91 1976.55 34.93 56.22 31.93 21.59 125.00 13.28 10.32 2.95 70.00 23.41 38.17 73.
20 6.80 1985.82 35.28 59.41 31.96 22.38 135.00 14.17 11.09 3.08 70.00 24.21 40.94 81.
21 6.80 1980.45 35.41 62.73 32.65 19.63 120.00 14.17 11.11 3.05 69.00 24.86 41.65 84.
22 6.85 1960.00 36.16 65.85 32.53 20.68 125.00 14.18 11.01 3.16 68.00 24.99 41.38 83.
23 6.90 1970.00 36.27 67.75 32.75 19.71 120.00 14.18 11.03 3.15 68.00 25.41 41.60 84.
24 6.88 1980.00 36.02 70.57 31.24 18.18 110.00 14.17 11.06 3.11 65.00 23.99 40.17 81.
25 7.16 1993.14 35.45 72.89 31.81 18.69 115.00 14.18 11.29 2.89 63.00 24.07 41.65 86.
26 6.98 1996.56 35.87 74.20 30.61 21.85 130.00 14.17 11.15 3.03 61.00 23.35 39.88 82.
27 7.11 1978.50 35.65 76.18 30.24 23.60 135.00 14.18 11.12 3.06 61.00 23.61 39.66 80.
28 7.11 1986.31 34.84 78.30 30.11 22.15 125.00 14.17 11.18 2.99 60.00 23.74 39.55 80.
29 7.31 1996.56 35.24 80.34 30.02 17.57 100.00 14.17 11.37 2.81 60.00 22.95 40.36 86.
30 7.34 1977.52 35.44 81.73 32.10 15.38 90.00 14.18 11.64 2.54 60.00 24.38 44.69 106

161
162