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DESIGN OF SODA ASH PRODUCTION PLANT

Comprehensive Design Project


Department of Chemical and Process Engineering
University of Moratuwa
Supervised by
Dr.Padma Amarasinghe

Group members
Danushka D.G.

050069L

Gunasekara D.T.

050137U

Jayakody J.R.U.C. 050166G


Madurika B.N.

050254B

Weerasinghe D.T. 050472P

COMPREHENSIVEDESIGNPROJECT

PREFACE
This report gives a narrative of our final year comprehensive design project, which is the
production of Soda ash from the sea water and lime stone mines exist in number of places in the
country. The project is the part of curriculum of the final year B.Sc. Engineering Degree program of
the University of Moratuwa and in essence it consists of basic description of such attempt made by
five undergraduate students of Chemical and process Engineering Department, University of
Moratuwa. The content of this report are outlined here.

Chapter 1 gives a brief introduction to the report and the finding from literature survey is given
in chapter 2. This was conducted to study about the soda ash production. It gives general information
about soda ash, how it began, history of the production, the types of production, uses in industrial
sectors, etc.

Designing of compatible, large scale industry in a developing country like Sri Lanka is a big
task. Especially with matching technology and feasibility to the project in such situation is a heavy
work. Chapter 3 consists of the evaluation of the complete feasibility study under technical
economical, market.sectors.

Under chapter 4, we discussed the how we select most appropriate process for the Sri Lanka
through the various operate processes in the world considering the pros and cons of several models.
Chapter 5 is focused on the process description. It begins with the feed selection; and mainly this
chapter contents based on each and every unit operation of the selected process. Equipment layout is
enlightened at the end of this chapter.

The site selection and the plant layout are given in chapter 6. Chapter 7 contains the particulars
of the environmental impact assessment. This contains the major environmental impact from the
sodium bicarbonate process plant and the how to carry out processes of the effluent management.

Full details of the safety measures intended for the plant is given on chapter 8. After that the
safety aspects considering equipment is expressed in detail.

Material balance and energy/ heat balance done on behalf of each unit operation selected is
discussed in next two episodes chapter 9, 10. The overall material and energy flow sheets arranged for

COMPREHENSIVEDESIGNPROJECT

the plant is summarized within too. The detailed calculations as well as the assumptions made have
been appended.

The final chapter is presenting the conclusion of this report a summing up of the whole project
with the benefits of the selected process and technologies are imparted in this chapter, as well how it
helped us improve our skill and knowledge. A list of abbreviations and the list of references are
appended at the end of the report.
28/10/2008

ii

COMPREHENSIVEDESIGNPROJECT

ACKNOWLEDGEMENT
When doing our Final year Comprehensive Design Project, we had to face many hardships and
challenges. It was with the help of many people that we were able to complete this project. We would
like to express our heartiest gratitude to all those people.
First of all we would like to grant our heartiest gratitude to our project coordinator, Dr. Padma
Amarasinghe, (lecturer- Chemical & Process Engineering department, University of Moratuwa) for all
the valuable advice, guidance, support and encouragement given through out the time. Dear Madam,
Thank you very much for spending your precious time to share your priceless knowledge with us, we
owe you a lot.
Then we express our gratitude to the department of Chemical and Process Engineering , all the
staff members of Chemical & Process Engineering department, including Dr. Jagath Premachandra
(head of the department), for all the assistance and big hearted support given toward while doing many
activities of this project and for including a design project in the final year syllabus. Thereby providing
us with a valuable opportunity to improve our knowledge and experience on doing a project, this will
come very useful when we go out to the industry as Chemical and Process Engineers.
We appreciate the support given by all the non academic staff of the Department of Chemical
and Process Engineering, especially the people who were in charge of the department of CAPD center,
for keeping it open at all hours so we could continue our work without interruption.
Then we would like to thank the staff of the Ceylon Glass Limited and the Holcim Lanka
limited for giving us permission to visit the glass plant and provide us necessary experience and
relevant data regarding this project.
Finally we thank all our colleagues of the department of Chemical and Process Engineering for
their help stimulating suggestions and encouragement.
Thanking You.
Group Members
Danushka D.G.

: 050069L

Gunasekara D.T

: 050137U

Jayakody J.R.U.C

: 050166G

Madurika B.N.

: 050254B

Weerasinghe.D.T.

: 050472P

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COMPREHENSIVEDESIGNPROJECT

CONTENTS
PREFACE

ACKNOWLEDGEMENT

iii

CONTENTS

iv

CHAPTER 1: INTRODUCTION

CHAPTER 2: LITERATURE SURVEY


2.1. General Information

4
5

2.1.1. Other Names for Sodium Carbonate

2.1.2. Physical Properties of Sodium Carbonate

2.1.3. Hydrates of Sodium Carbonate

2.1.4. Chemical Properties of Sodium Carbonate

2.1.5. Grades and Specification of the Soda Ash

2.2. Uses of Na 2 CO 3 in Industrial Sectors

2.2.1. Glass Industry

2.2.2. Detergent Industry

2.2.3. Metals and Mining

2.2.4. Steel Industry

2.2.5. Paper and Pulp

2.2.6. Textiles

2.2.7. Non-ferrous metallurgy industry

2.2.8. Chemical industry

2.2.9. Other Applications

2.3. Uses of NaHCO3 in Industrial Sectors

10

2.4. History of the Production

10

2.5. Overview about Type of Production

12

2.5.1. Le Blanc process

12

2.5.2. Solvay Process

14

2.5.3. Hou's Process

15

2.5.4. Dual process

15

2.6. Sodium Carbonate Minerals

15

2.6.1. Trona Based Process

16

2.6.1.1.

Trona Products

17

2.6.1.2.

Monohydrate Process

18

2.6.1.3.

Sesquicarbonate Process

19

2.6.1.4.

Alkali Extraction Process

20

2.6.2. Nahcolite based process

22
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COMPREHENSIVEDESIGNPROJECT

2.7. International Scenario

22

2.8. Structure and Status of Indian Industry

23

CHAPTER 3: FEASIBILITY STUDY


3.1. Preliminary Study

24
25

3.2. Economical Feasibility

27

3.3. Market Feasibility

30

3.4. Technical Feasibility

31

3.5. Social Feasibility

33

CHAPTER 4: PROCESS SELECTION


4.1. Introduction
4.2. Comparison of Solvay process with Others Methods of Production
4.3. Process Selection Conclusions

35
36
37
40

CHAPTER 5: PROCESS DESCRIPTION

41

5.1. Main Chemical Reactions in Solvay process

42

5.2. Process Steps

44

5.2.1. Brine purification

44

5.2.2. Calcinations of limestone in kilns and the production of CO2 and milk of lime

45

5.2.3. Absorption of ammonia into purified brine

46

5.2.4. Carbonation of the ammoniated brine with CO2 to produce sodium bicarbonate

46

5.2.5. Separation of Sodium Bicarbonate from Mother Liquid

47

5.2.6. Recovery of the Ammonia using Milk of Lime

48

5.2.7. Calcinations of Sodium Bicarbonate to form Sodium Carbonate (light ash)

49

5.2.8. Densification of Sodium Carbonate to form Dense ash

49

5.3. Product (Soda Ash) Storage and Handling

50

5.4. Raw Materials

50

5.4.1. Brine

50

5.4.2. Limestone

51

5.4.3. Carbon for the Lime Kiln

51

5.4.4. Ammonia

52

5.4.5. Various additives

52

5.5. Utilities

53

5.5.1. Steam

53

5.5.2. Process water

53

5.5.3. Cooling waters

53

5.5.4. Electricity

54

5.6. Energy saving in the process

54
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COMPREHENSIVEDESIGNPROJECT

5.6.1. Heat recovery

55

5.6.2. Energy Minimization

55

5.7. Process Flow Diagram

57

5.8. P & I Diagram

58

CHAPTER 6: SITE SELECTION & PLANT LAYOUT


6.1. Introduction
6.2. Site Selection Considerations

60

6.3. Plant layout

65

CHAPTER 7: ENVIRONMENTAL IMPACT ASSESSMENT


7.1. Gaseous Effluents

66
67

7.1.1. Particulate Dust

67

7.1.2. Carbon dioxide and monoxide

67

7.1.3. Nitrogen oxides

68

7.1.4. Sulfur oxides

68

7.1.5. Ammonia

68

7.1.6. Hydrogen sulfide

69

7.2. Gaseous Effluents Management

69

7.2.1. Calcinations of Limestone

69

7.2.2. Precipitation of Crude Sodium Bicarbonate

70

7.2.3. Filtration of the Bicarbonate

70

7.2.4. Conveying and Storage of Soda Ash

70

7.3. Liquid Effluents

71

7.3.1. Wastewater from Distillation

71

7.3.2. Wastewater from Brine Purification

72

7.4. Liquid Effluent Management

73

7.4.1. Liquid Effluent Treatments

73

7.4.1.1.

Total Dispersion

74

7.4.1.2.

Separation of the Suspended Solids and Liquid Dispersion

74

7.4.2. Liquid Effluent Discharge Management

75

7.5. Solid Effluents

76

7.6. Solid Materials Management

76

7.6.1. Limestone Fines

76

7.6.2. Grits from slaker

76

7.7. By-Products Recovery and Reuse

59
60

77
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COMPREHENSIVEDESIGNPROJECT

7.7.1. Calcium Chloride

77

CHAPTER 8: SAFETY MEASURES

78

8.1. Plant Safety

79

8.2. General Plant Safety

79

8.3. Personal Safety

80

8.4. Safety Aspects of Equipments

81

8.4.1. Lime Kiln

81

8.4.2. NH3 Absorbing Unit

82

8.4.3. Carbonator Unit

82

8.4.4. NH3 Recovery Unit

82

8.4.5. Drier

83

8.4.6. Storage Vessels

84

8.4.6.1.

Ammonia

84

8.4.6.2.

Soda ash

84

8.4.6.3.

Baking soda

84

8.4.6.4.

Calcium Carbonate and Calcium Oxide

84

8.4.7. Pipelines

85

8.5. Safety Aspects of Chemical

85

8.5.1. Carbon Dioxide (CO 2 )

85

8.5.2. Ammonia (NH 3 )

86

8.5.3. Sodium Carbonate (Na 2 CO 3 )

88

CHAPTER 9: MATERIAL BALANCE

91

9.1. Product specification

92

9.2. Components in Purified brine

92

9.3. Calculations for NH 3 Absorption Unit

93

9.4. Air Mixture

95

9.5. Gas Washing Tower with Purified Brine

96

9.6. Carbonator Unit

97

9.7. Filter

99

9.7.1. Calculation for residue solid

100

9.7.2. Calculation for permeate

100

9.8. Lime Kiln

101

9.9. Slaker of lime

103

9.10.

104

Ammonia Recovery Unit

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COMPREHENSIVEDESIGNPROJECT

9.11.

Gas Cooler

107

9.12.

Air Mixture (Before the Gas Cooler)

108

9.13.

Dryer

109

9.14.

Material Flow Sheet

111

CHAPTER 10:

ENERGY BALANCE

112

10.1.

Kiln Energy Balance

113

10.2.

Energy Balance for Air Preheated

115

10.3.

Calcinations of Crude Bicarbonate

116

10.4.

CaCO3 Preheated

119

10.5.

Air Mixer Energy Balance

120

10.6.

Heat Balance for Gas Cooler

122

10.7.

Slaking of Lime

123

10.8.

Recovery of Ammonia Column Energy Balance

126

10.8.1. Find Outlet Temperature of the Cool Gas

127

10.8.2. Fine Quantity of Steam Consumption

128

10.9.

Carbonation of Ammoniated Brine Column

CHAPTER 11:

CONCLUSION

133

REFERENCE

135

CD CONTENTS
Excel Spreadsheets
Soft Copy Of Report

130

viii

COMPREHENSIVEDESIGNPROJECT

Table & Figure


Table2.1: Market specifications of dense soda ash

Table2.2 : Worldwide capacity of soda ash manufacture

11

Table 2.3: Natural soda minerals occurred worldwide

16

Table 2.4: products of Trona

17

Table 4.1 a comparison of the Solvey and dual processes

40

Table5.1: Raw and purified brines (typical composition ranges)

51

Table 5.2: Typical compositions for coke to the lime kiln

52

Table 5.3: Soda ash process major Input/output levels

56

Table 7.1: Rough concentrations of the waste water from the distillation column

71

Table 7.2: Typical concentration wastewater from brine purification

72

Table 9.1- Soda ash specification

92

Table 9.2- Purified brine specification

92

Table 9.3- Residue solid composition

99

Table 10.1- a,b,c constant

113

Table 10.2- kiln inlet enthalpy

114

Table 10.3- kiln outlet enthalpy

114

Table 10.4- Air enthalpy change

115

Table 10.5- CaO enthalpy change

116

Table 10.6- flue gas enthalpy change

119

Table 10.7- Soda ash specification

123

Table 10.8- a, b, c constant for CaO

124

Figure 2.1: Distribution of soda ash by end use

Figure 2.2: Flow diagram of monohydrate process

18

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COMPREHENSIVEDESIGNPROJECT

Figure2.3: Flow diagram of sesquicarbonate process

19

Figure 2.4: Flow diagram of alkali extraction process

21

Figure 3.1: Soda ash imports (2006)

25

Figure 3.2: Variation in soda ash imports

26

Figure5.1: Block diagram of the soda ash production plant

42

Figure5.2: Vertical shaft kiln for lime stone

46

Figure5.3: Process flow diagram

57

Figure5.4: P&I diagram


Figure 6.1- Mineral Map of Sri Lanka

63

Figure 6.2- Geographical map of proposed land

64

Figure 6.3- Plant layout

65

Figure 9.1- NH 3 Absorption Unit

93

Figure 9.2- Air mixture before NH3 Absorption Unit

95

Figure 9.3- Gas washing tower with purified brine

96

Figure 9.4- Carbonator Unit

97

Figure 9.5- Filter

99

Figure 9.6- Lime Kiln

101

Figure 9.7- Slaker of lime

103

Figure 9.8- Ammonia Recovery Unit

104

Figure 9.9- Gas Cooler

107

Figure 9.10- Air mixture before gas cooler

108

Figure 9.11- Dryer

109

Figure 10.1- kiln

113

Figure 10.2- Air preheated

115

Figure 10.3- Dryer

117

Figure 10.4- Cyclone

119

Figure 10.5- Air mixture before gas cooler

120

COMPREHENSIVEDESIGNPROJECT

Figure 10.6- Gas cooler

122

Figure 10.7- Slaker

124

Figure 10.8- NH3 Recovery column

126

Figure 10.9- Carbonation column

130

xi

Chapter1

INTRODUCTION

CHAPTER 01

INTRODUCTION

Sodium carbonate or soda ash is used in many


process
industries
such
as
in
glass
manufacturing, Detergents & soaps, Metals and
mining, Paper and pulp and Textiles industries.
Raw materials for the manufacturing of sodium
carbonate are readily available and inexpensive.
Raw materials for the Sodium carbonate can be
obtained from sea water and lime stone mines
exist in number of places in the country

Chapter1

INTRODUCTION

In developed areas of the world mainly in the western European countries and in North
America the annual dollar value of industrial mineral production has surpassed that for metals and
continues to grow rapidly. This is due to the fact of high income levels per capita consumption of
industrial mineral products in developed Countries exceeds that in developing countries. While in
developed countries industrial minerals and rocks provide inputs in many industrial processes, in some
developing countries with little industrial infrastructure significant portions of their foreign exchange
derive from exports of industrial minerals like Sri Lanka. Thus, industrial minerals are of great
economic value to developed and developing economies alike.
When we consider the Sri Lankan perspective as one of the developing countries the scenario
mentioned above applies without much deviation. Sri Lanka is a country which is rich in minerals and
natural resources, but these have not been utilized to an extent where they will contribute to the
country production and hence to its development. Sri Lanka as a county can capitalize on its exports if
it were to manufacture value added products from the existing resources instead of an economy based
on export of raw materials to industries in other countries.
Soda ash, the common name for sodium carbonate (Na 2 CO 3 ), has significant economic
importance because of its applications in manufacturing glass, chemicals, detergents metals and
mining, paper and pulp, textiles industries and many other products. There are many evidences to show
that people have been using soda ash extracted from earth in crude form, in glass manufacturing
industries since ancient times. But the production of soda ash as an industry itself, emerged only
during the late 18th century.
Raw materials for the manufacturing of sodium carbonate are readily available and
inexpensive. Main raw materials can be obtained from sea water and lime stone mines exist in number
of places in Sri Lanka. So the purpose of our final year comprehensive design project is production of
sodium carbonate from brine and lime stone. The comprehensive design project is done as per the
requirement for the award of the B.Sc. (Honors) Engineering degree.
The literature survey that was conducted as part of the project included a thorough study on
several soda ash consuming and lime stone consuming industries in Sri Lanka. Since the Holcim
Cement plant in Palavi will have a considerable amount of relation to the proposed plant, as explained
in later chapters a brief study on its operations was also carried out.
The results of the design project for the commercial production of soda ash are presented. The
project has been performed in two stages. The first part concerns the feasibility of the project, literature
survey and the second part presents the detailed material and energy balances.

Chapter1

INTRODUCTION

From the investigation into project feasibility, it is proposed to construct a plant using the
Solvay process for the production of soda ash and will deliver 50 tons per day of 99.5(wt) Na 2 CO 3 . It
is envisaged that this soda ash production facility will be located in Karadipuval near Puttalam. The
process has been tailor-made and designed to utilize limestone available locally at the North-Western
area of the country. Saturated brine from the adjacent lagoon is the other raw material utilized for the
proposed soda ash plant. Coke for the combustion of limestone in order to produce CO 2 for the process
will have to be imported. It is hoped that this project makes a contribution to further the cause of
national development by provision of a viable, cost-effective, and environmental friendly solution.

Chapter2

LITRETURESURVEY

CHAPTER 02

LITRETURE SURVEY

Soda ash has a number of diversified uses that touch


our lives every day. Glass manufacturing is the
largest application for soda ash whether it is in the
production of containers, fiberglass insulation, or flat
glass for the housing, commercial building etc.
As environmental concerns grow, demand increases
for soda ash used in the removal of sulfur dioxide and
hydrochloric acid from stack gases. Chemical
producers use soda ash as an intermediate to
manufacture products that sweeten soft drinks,
relieve physical discomfort and improve foods and
toiletries, Household detergents and paper products
are a few other common examples of readily
identifiable products using soda ash

Chapter2

LITRETURESURVEY

2.1 General Information


2.1.1 Other Names for Sodium Carbonate

Soda ash

Carbonate acid.

Disodium salt

Dry alkali

Molecular formula:

Na 2 CO 3

2.1.2 Physical Properties of Sodium Carbonate

Specific Gravity

: 2.53

Solubility in water(22C) : 22g/100ml

Melting Point

: 851.0C

Boiling Point

: Decomposes before melting

pH (1% aq. solution.)

: 11.5

Sodium carbonate is an odorless, opaque white, crystalline or granular solid. It is soluble in


water and insoluble in alcohol, acetone, and ether. Sodium carbonate reacts exothermically with strong
acids evolving carbon dioxide. It corrodes aluminium, lead and iron.

2.1.3 Hydrates of Sodium Carbonate


The three known hydrates exist in addition to anhydrous sodium carbonate.
Sodium carbonate monohydrate ( Na 2 CO 3 .H 2 O )

This contains 85.48 % Na 2 CO 3 and 14.52 % water of crystallization. It separates as small


crystals from saturated aqueous solutions above 35.4 C, or it may be formed simply by wetting soda
ash with the calculated quantity of water at or above this temperature. It loses water on heating, and its
solubility decreases slightly with increasing temperature. In contact with its saturated solution it is
converted to Na 2 CO 3 at 109 C.

Chapter2

LITRETURESURVEY

Sodium carbonate heptahydrate ( Na 2 CO 3 .7H 2 O ),

This contains 45.7 % Na 2 CO 3 and 54.3 % water of crystallization. It is of no commercial


interest because of its narrow range of stability, which extends from 32 C to 35.4 C.

Sodium carbonate decahydrate ( Na 2 CO 3 .10H 2 O ),

Commonly called sal soda or washing soda which usually forms large transparent crystals
containing 37.06 % Na 2 CO 3 and 62.94 % water. It may be crystallized from saturated aqueous
solutions below 32.0 C and above -2.1C or by wetting soda ash with the calculated quantity of water
in this temperature range. The crystals readily effloresce in dry air, forming a residue of lower
hydrates, principally the monohydrate.

2.1.4 Chemical Properties of Sodium Carbonate


Sodium carbonate is hygroscopic. In air at 96 % R.H. (relative humidity) its weight can
increase by 1.5 % within 30 minutes. If sodium carbonate is stored under moist conditions, its
alkalinity decreases due to absorption of moisture and carbon dioxide from the atmosphere. Water
vapor reacts with sodium carbonate above 400 C to form sodium hydroxide and carbon dioxide.
Sodium carbonate is readily soluble in water and the resulting solutions are alkaline, as expected a salt
formed from a strong base and weak acid. At 25 C the pH of 1, 5 and 10 wt % solutions are 11.37,
11.58 and 11.70 respectively. Sodium carbonate reacts exothermically with chlorine above 150 C to
form NaCl, CO2, O2 and NaClO4.
2.1.5 Grades and Specification of the Soda Ash
Soda ash is produced in two principal grades, known as light soda ash and dense soda ash.
These grades differ only in physical characteristics such as bulk density and size and shape of
particles, which influence flow characteristics and angle of repose. Dense soda ash has a bulk density
of 950 to 1100 kg/m3, may command a slightly higher price than the light variety, and is preferred for
glass manufacture because the lighter variety leads to frothing in the glass melt. Light soda ash having
a bulk density at 520 to 600 kg/m3, is the normal production item direct from the calcining furnace and
is preferred by the chemical and detergent industries. Other physical properties, as well as chemical
properties and properties of solutions, are common to both grades of soda ash.
All commercial grades are chemically similar. As density differences are the main distinguishing
feature, Table 2.1 shows the typical market specifications of dense soda ash.

Chapter2

LITRETURESURVEY

Chemical composition
Sodium Carbonate (Na2CO3)

99.8 %

Sodium Oxide (Na2O)

58.4 %

Sodium Sulfate (Na2SO4)

0.10 %

Sodium Chlorite (NaCl)

0.03 %

Iron (Fe)

0.0005% ( 5 ppm)

Bulk density

(0.96-1.04 g/cm3)

Particle size

75 micron - 850 micron


Table2.1: Market specifications of dense soda ash

2.2 Uses of Na 2 CO 3 in Industrial Sectors

Figure 2.1: Distribution of soda ash by end use

The distribution of soda ash by end use in 2007 was glass, 49%; chemicals, 27%; soap and
detergents, 10%; distributors, 5%; miscellaneous uses, 4%; flue gas desulfurization and pulp and
paper, 2% each; and water treatment, 1%.
2.2.1 Glass Industry
Soda ash is used in the manufacturing of flat and container glass. When mixed in proportion
with sand and calcium carbonate, heated to the right temperature and then cooled quickly, the end
result will be a glass that has an excellent level of durability and clarity. Na2CO3 as a network
modifier or fluxing agent, it allows lowering the melting temperature of sand and therefore reduces the
energy consumption.

Chapter2

LITRETURESURVEY

Soda ash reduces the viscosity and acts as a fluxing agent in glass melting [soda-lime glass (flat
and container glass), fiber-glass, specialty glass (e.g. borosilicate glass)].

2.2.2 Detergent Industry


Soda ash is used in a large number of prepared domestic products: soaps, scouring powders,
soaking and washing powders containing varying proportions of sodium carbonate, where the soda ash
acts primarily as a builder or water softener. The addition of the soda ash prevents hard water from
bonding with the detergent, allowing for a more even distribution of the cleaning agent during the
washing cycle. In addition, soda ash has demonstrated an ability to help remove alcohol and grease
stains from clothing.
Sodium carbonate is a major raw material in the manufacture of sodium phosphates and sodium
silicates which are important components of domestic and industrial cleaners. Sodium carbonate is also
added to these detergents to produce formulations for heavy duty laundering and other specialized
detergents manufacture. Sodium carbonate may also be used for neutralizing fatty acids in the
production of soap.

2.2.3 Metals and Mining


Sodium carbonate is used for the production of metals in both the refining and smelting stages.
It is often used for producing a metal carbonate which can later be converted to the oxide prior to
smelting.

2.2.4 Steel Industry


Soda ash is used as a flux, a desulfurizer, dephosphorizer and denitrider. Aqueous soda ash
solutions are used to remove sulfur dioxide from combustion gases in steel desulfurization, flue gas
desulfurization (FGD) systems, forming sodium sulfite and sodium bicarbonate.
Na 2 CO 3 + SO 2

Na 2 SO 3 + CO 2

CO 2 + Na 2 CO 3 + H 2 O

2NaHCO 3

2Na 2 CO 3 + SO 2 + H 2 O

Na 2 SO 3 + 2NaHCO 3

Chapter2

LITRETURESURVEY

2.2.5 Paper and Pulp


Sodium carbonate solution is used for the production of sodium sulphite or bisulphite for the
manufacture of paper pulp by various sulphite processes.
2.2.6 Textiles
Sodium carbonate is widely used in the preparation of fibers and textiles. In wool processing it
is used during scouring and carbonizing to remove grease and dirt from wool. It is also used as a
neutralizer after treatment with acids.
2.2.7 Non-ferrous metallurgy industry

Treatment of uranium ores.

Oxidizing calcination of chrome ore.

Lead recycling from discarded batteries.

Recycling of zinc, aluminium.

2.2.8 Chemical industry


Soda ash is used in a large number of chemical reactions to produce organic or inorganic
compounds used in very different applications. It is used to manufacture many sodium-base inorganic
chemicals, including sodium bicarbonate, sodium chromates, sodium phosphates, and sodium silicates.

2.2.9 Other Applications

Production of various chemical fertilizers

Production of artificial sodium bentonites or activated bentonites

Manufacture of synthetic detergents

Organic and inorganic coloring industry

enameling industry

Petroleum industry

Fats, glue and gelatine industry, etc.

Chapter2

LITRETURESURVEY

2.3 Uses of NaHCO 3 in Industrial Sectors


Sodium bicarbonate can also be manufactured by Solvay process.

Animal feeds to balance their diets to compensate for seasonal variations and meet specific
biological and rearing needs

Paper industry for paper sizing

Plastic foaming

Water treatment

Leather treatment

Flue gas treatment, especially in incinerators

Detergent and cleaning products such as washing powders and liquids, dishwashing products,
etc

Drilling mud to improve fluidity

Fire extinguisher powder

Human food products and domestic uses: baking soda, effervescent drinks, toothpaste, fruit
cleaning, personal hygiene, etc.

Pharmaceutical applications: effervescent tablets, etc.

2.4 History of the Production


Before the advent of industrial processes, sodium carbonate, often-called soda ash, came
from natural sources, either vegetable or mineral. Soda made from ashes of certain plants or seaweed
has been known since antiquity.
At the end of the 18th century, available production was far below the growing demand due to
the soap and glass market. The French Academy of Science offered an award for the invention of a
practical process to manufacture soda ash. Nicolas Leblanc proposed a process starting from
common salt and obtained a patent in 1791.
The so-called Leblanc or black ash process was developed in the period 1825 till 1890. The
major drawback of this process was its environmental impact with the emission of large quantities of
HCl gas and the production of calcium sulfide solid waste which not only lost valuable sulfur but also
produced poisonous gases. In 1861, Ernest Solvay rediscovered and perfected the process based
on common salt, limestone and ammonia.

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Competition between both processes lasted many years, but relative simplicity, reduced
operating costs and, above all, reduced environmental impact of the Solvay process ensured its
success. From 1885 on, Leblanc production took a downward curve as did soda ash price and by the
First World War, Leblanc soda ash production practically disappeared. Since then, the only production
process used in Western Europe as well as in main part of the world is the Solvay process.
In the meantime and mainly since the twenties, several deposits of minerals containing
sodium carbonate or bicarbonate have been discovered. Nevertheless the ore purity and the location of
these deposits, as well as the mining conditions of these minerals, have limited the effective number of
plants put into operation.
Worldwide capacity of soda ash manufacture

Table2.2 Worldwide capacity of soda ash manufacture

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2.5 Overview about Type of Production


Geographical location and site characteristics such as environmental matters, specific energy
resources, distribution methods, and trade barriers are key elements in a selection of processing
method. Soda ash is readily produced from either natural deposits or trona or by synthetic pathways.
Soda ash production methods are given below in historical sequence.

Le Blanc Process (synthetic soda ash)

Solvey Process (synthetic soda ash)

Dual and NA Processes (synthetic soda ash)

Monohydrate Process

Sesquicarbonate Process

Carbonation Process

Alkali Extraction Process

2.5.1 Le Blanc process


This process was invented by Nicolas Le Blanc, a French man, who in 1775, among several
others submitted an outline of a process for making soda ash from common salt, in response to an offer
of reward by the French academy in Paris. Le Blanc proposal was accepted and workable on a
commercial scale.
Reactions
2NaCl + H 2 SO
4C

NaSO 4

Na 2 S + CaCO 3

Na2SO4 + 2HCL
NaS + 4CO
Na 2 CO 3 + CaS

A mixture of equivalent quantities of salt and concentrated sulphuric acid is heated in cast iron
salt cake furnance. Hydrochloric acid gas is given off and sodium hydrogen sulphate is formed. The
gas is dissolved in water and the mixture is raked and transferred to the muffle bed reverbratory
furnance where it is subjected to stronger heat. Here sodium sulphate called salt cake is formed.
The cake is broken, mixed with coke and limestone and charged into black ash furnace. The
mass is heated and a porous grey mass know as black ash is withdrawn.

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The black ash is cursed and leached with water in the absence of air in a series of tanks. The
extract containing sodium carbonate, sodium hydroxide and many other impurities, is sprayed from the
top of a tower counter current to the flow of hot gases from the black-ash furnace.
This converts sodium hydroxide, aluminate, silicate, cyanate to sodium carbonate. The liquor is
concentrated in open pans until the solution is concentrated in open pans until the solution is
concentrated enough to precipitate sodium carbonate on cooling.
The product is calcined to get crude soda ash which is purified by recrystallisation. The liquor
remaining after removal of first crop of soda crystals is purified to remove iron and causticised with
lime to produce caustic soda. The mud remaining in the leaching tanks containing calcium sulphide is
suspended in water and lime kiln gas is passed through it. The following reaction occurs.
CaS + H 2 O + CO 2

CaCO 3 + H 2 S

The lean gas containing hydrogen sulphide is passed through another tank containing
suspension of calcium sulphide.
CaS + H 2 S

Ca(SH) 2

This solution is again treated with lime kiln gas liberating a gas rich in hydrogen sulphide.
Ca(SH) 2 + CO 2 + H 2 O

CaCO 3 + 2H 2 S

The hydrogen sulphide is burnt in limited supply of air in a special furnace in presence of
hydrated iron oxide as a catalyst to obtain sulphur.
H 2 S + 1/2O 2

H2O + S

This sulphur is sublimed and collected.The hydrochloric acid produced by the Leblanc process
was a major source of air pollution, and the calcium sulfide byproduct also presented waste disposal
issues. However, it remained the major production method for sodium carbonate until the late 1880s.

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2.5.2 Solvay Process


In 1861, the Belgian industrial chemist Ernest Solvay developed a method to convert sodium
chloride to sodium carbonate using ammonia. The Solvay process centered on a large hollow tower. At
the bottom, calcium carbonate (limestone) was heated to release carbon dioxide:
CaCO 3 CaO + CO 2
At the top, a concentrated solution of sodium chloride and ammonia entered the tower. As the
carbon dioxide bubbled up through it, sodium bicarbonate precipitated:
NaCl + NH 3 + CO 2 + H 2 O NaHCO 3 + NH 4 Cl
The sodium bicarbonate was then converted to sodium carbonate by heating it, releasing water
and carbon dioxide:
2 NaHCO 3 Na 2 CO 3 + H 2 O + CO 2
Meanwhile, the ammonia was regenerated from the ammonium chloride byproduct by treating
it with the lime (calcium hydroxide) left over from carbon dioxide generation:
CaO + H 2 O Ca(OH) 2
Ca(OH) 2 + 2 NH 4 Cl CaCl 2 + 2 NH 3 + 2 H 2 O
Because the Solvay process recycled its ammonia, it consumed only brine and limestone, and
had calcium chloride as its only waste product. This made it substantially more economical than the
Leblanc process, and it soon came to dominate world sodium carbonate production.

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2.5.3 Hou's Process


This process is developed by a Chinese chemist Hou Debang in 1930s. It is the same as the
Solvay process in the first few steps. But, instead of treating the remaining solution with lime, carbon
dioxide and ammonia is pumped into the solution, and sodium chloride is added until it is saturated at
40 C. Then the solution is cooled down to 10 C. Ammonium chloride precipitates and is removed by
filtration, the solution is recycled to produce more sodium bicarbonate. Hou's Process eliminates the
production of calcium chloride and the byproduct ammonium chloride can be used as a fertilizer.

2.5.4 Dual process


In this process ammonium chloride is produced as a co product in equivalent quantities and
differs from conventional, Solvay process and it does not recycle ammonia.
The mother liquor from the carbonating system, containing ammonium chloride, unreacted salt
and traces of carbonate is ammoniated in ammonia absorber. The ammoniated mother liquor is passed
through a bed of salt in a salt dissolver. Exit liquor from the dissolver, saturated with salt, is gradually
0

cooled from 40 C to 10 C by evaporation under vacuum to separate ammonium chloride. The slurry
containing ammonium chloride is centrifuged and dried. The product is 98% pure and is marked as
ammonium chloride fertilizer with nitrogen content of 25%.
The mother liquor obtained after the separation of ammonium chloride crystals is recycled to
the carbonation vessels placed in series. Carbon dioxide obtained from ammonia plant and the calciner
section of soda ash plant is injected in the carbonation vessels. There is provision of cooling coils in
the lower carbonation vessels. Sodium bicarbonate is formed. The growth of crystals, of sodium
bicarbonate is controlled by the supply of cooling water to cooling water to cooling coils in
carbonation vessels. Sodium bicarbonate is thickened in a thickener and centrifuged. The sodium bi
carbonate is calcined to soda ash.

2.6 Sodium Carbonate Minerals


Whereas the production of sodium carbonate from the ashes of plants in salty soil near the sea
is only of historical interest, extraction from soda-containing minerals, especially trona, is of
increasing importance. The natural soda minerals occurred in the world is given in the following table.

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Types of Natural soda minerals occurred worldwide


Mineral

Chemical Name

Chemical Composition

Trona

Na 2 CO 3 .NaHCO 3 .2H 2 O

Nahcolite
Bredeyit

Natural sodium
sesquicarbonate
Natural sodium bicarbonate
Natural sodium bicarbonate

Gaylusitte

% Na 2 CO 3
content
70.3

NaHCO 3

63.1
47.1

Natural sodium bicarbonate

Na 2 CO 3 .CaCO 3 .5H 2 O

35.8

Pirrsonite

Natural sodium bicarbonate

Na 2 CO 3 .CaCO 3 .2H 2 O

43.8

Thermonatrite

Na 2 CO 3 .H 2 O

85.5

Na 2 CO 3 .10H 2 O

37.1

Burkeit

Sodium carbonate
monohydrate
Sodium carbonate
decahydrate
-

Na 2 CO 3 .2Na 2 SO 4

27.2

Dawsonit

NaAl(CO 3 )(OH)

35.8

Hankcite

Na 2 CO 3 .9Na 2 SO 4 .KCl

13.5

Sortite

Na 2 CO 3 .2CaCO 3

34.6

Natron

Table 2.3: Natural soda minerals occurred worldwide

Only Trona and Nahcolite are the minerals those commercial interest. These Na 2 CO 3
containing minerals were formed from the original rock by the erosive action of, air, water, heat, and
pressure, followed by chemical changes caused by the action of atmospheric carbon dioxide. The
carbonate containing salts formed were leached by water and then concentrated and crystallized by
evaporation.

2.6.1 Trona Based Process


The production of sodium carbonate from the ashes of plants in salty soil near the sea is only of
historical interest, extraction from soda-containing minerals, is of increasing importance. Trona,
hydrated sodium bicarbonate carbonate (Na 2 CO 3 .NaHCO 3 .2H 2 O), is mined in several areas of the
world.

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This underground dry Trona processing consists in several steps:

First Trona has to be mined by the room and pillar or long wall method mechanically.

As Trona is an impure sodium sesquicarbonate mineral (Na 2 CO 3 NaHCO 3 2H 2 O), it has to be


calcined to produce a soda ash still containing all the impurities from the ore.

Next, calcined Trona is dissolved, the solution is settled and filtered to remove impurities
(insoluble and organics), and the purified liquor is sent to evaporators where sodium monohydrate
crystals precipitate.

The monohydrate slurry is concentrated in centrifuges before drying and transformation into dense
soda ash.

Deposits from Trona lakes and solution mined Trona are processed as follows:

Dissolving Trona in wells

Carbonation of the solution in order to precipitate sodium bicarbonate filtration of the slurry and
Calcination of the bicarbonate to get light soda ash , recycling of the carbon dioxide to the
carbonation

Light soda ash transformation into dense by the monohydrate method

Carbon dioxide make-up produced by burner off-gas enrichment

2.6.1.1 Trona Products


Various Forms of Sodium

Formula

Carbonate
Anhydrous sodium carbonate

Na2CO3

Sodium carbonate monohydrate

Na2CO3. H2O

Sodium carbonate heptahydrate

Na2CO3 .7H2O

Sodium carbonate decahydrate

Na2CO3 .10H2O

Caustic Soda

( NaOH )

Sodium Bicarbonate

( NaHCO3)

Sodium Derivatives

Table 2.4: products of Trona

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2.6.1.2 Monohydrate Process


Soda ash is generally produced from trona by monohydrate process that produces only dense
soda ash. The first FMC Wyoming Corporation plant using this process went into operation in late
1972. In this process, the trona ore is first converted to crude soda ash by calcination and all
subsequent operations are performed on the resulting carbonate solution, as given in following figure.

Figure 2.2: Flow diagram of monohydrate process

Crushed Trona is calcined in a rotary kiln to dissociate the ore and drive off the carbon dioxide
and water by the following reaction:
2 (Na 2 CO 3. NaHCO 3 .2H 2 O) (s) .

3 Na 2 CO 3 (s) + 5 H 2 O + CO 2

The calcined material is combined with water to dissolve the soda ash and to allow separating
and discarding of the insoluble material such as shale or shortite by settling and /or filtration. The
resulting clear liquid is concentrated as necessary by triple-effect evaporators, and the dissolved soda
ash precipitates as crystals of sodium carbonate monohydrate, Na 2 CO 3 .H 2 O. Other dissolved
impurities, such as sodium chloride or sodium sulfate, remain in solution.
The crystals and liquor are separated by centrifugation. The sodium carbonate monohydrate
crystals are calcined a second time to remove water of crystallization. The resultant finished product is
cooled, screened.

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2.6.1.3 Sesquicarbonate Process


An alternate method of soda ash production from trona is the sesquicarbonate process. This is
the original process, developed by FMC Wyoming Corporation and put in operation in 1953, for
producing pure soda ash from Wyoming trona.
Trona ore is leached in recycled mother liquor at as high a temperature as possible to maximize
the amount dissolved. The solution is then clarified, filtered and sent to a series of evaporative cooling
crystallizers where sodium sesquicarbonate (Na 2 CO 3 .NaHCO 3 .2H 2 O) is crystallized. Carbon is added
to the filters to control any crystal modifying organics. The purified sesquicarbonate crystals may be
calcined to produce a light soda ash product. Simplified flow diagram of sesquicarbonate process is
shown in following figure.
The mother liquor is recycled to the dissolvers. In a variation of the process, trona ore is
dissolved in hot water and the centrate is returned to the evaporator crystallizer (Haynes, 1997). This
produced soda is the light soda ash. Densities similar to the monohydrate soda ash may be achieved by
subsequently heating the material to about 350 C. Alternatively, soda ash can be converted to the
monohydrate and then calcined.

Figure2.3: Flow diagram of sesquicarbonate process

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2.6.1.4 Alkali Extraction Process


Alkali extraction process is mainly to dissolve crude trona in an aqueous sodium hydroxide
solution. In this process, trona is dissolved in an aqueous sodium hydroxide to obtain pregnant sodium
carbonate solution. This method is generally used for bicarbonate content that dissolves to be an
incongruent consisted in trona. The diluted solution has a composition of 2-7 % caustic soda.
Dissolution reaction is given as follows:
Na 2 CO 3 .NaHCO 3 .2H 2 O + NaOH

2 Na 2 CO 3 + 3 H 2 O

The solution at 30 C was filtered and the pregnant carbonate solution is heated, sufficient
water is evaporated to form slurry of sodium carbonate monohydrate crystals and aqueous sodium
carbonate. The slurry was filtered and the mother liquor was recycled to dissolve raw mineral. The
regeneration was done by adding sodium hydroxide to the mother liquor.

The monohydrate crystals were dried and calcined. The most important parameters in alkaline
extraction process are; the dissolution temperature, concentration of sodium hydroxide and evaporative
crystallization temperature. The appropriate temperatures for the dissolution and evaporative
crystallization are 30 C and 100 C respectively. The flow diagram of alkali extraction process is
shown in following figure.

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Figure 2.4: Flow diagram of alkali extraction process

In a trona bed, the effect of water on the solubility of sodium carbonate will decrease due to the
precipitated bicarbonate. In the conventional mining technique, bicarbonate can be converted to
carbonate with a pre-calcination stage. The problem associated with the presence of sodium
bicarbonate in trona deposits can be solved by applying of sodium hydroxide solution. The required
amount of sodium hydroxide is the stochiometric amount that is necessary to convert all of the
bicarbonate to carbonate. The aqueous sodium hydroxide solvent preferably contains 1-15 wt% NaOH.
Using an excess of sodium hydroxide causes unreacted NaOH to remain in the solution and this effect
decreases the solubility of sodium carbonate.

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2.6.2 Nahcolite based process


A Nahcolite deposit has been found in several places in the world.
Nahcolite is processed as follows:

By solution mining (wells, with injection of hot mother liquor returned from the surface facilities),
Nahcolite is separated.

As nahcolite is an impure sodium bicarbonate mineral (NaHCO 3 ), it must be treated.

The hot solution is decarbonated by heating. Then the solution is sent to settling and filtration.

Next, the purified liquor is sent to evaporators where sodium monohydrate precipitates.

The slurry is concentrated by centrifugation and the monohydrate crystals transformed to soda ash
by drying. The mother liquor is sent back to the solution mining

2.7 International Scenario


The present global capacity of soda ash is 37.0 million tones per annum and the long term
growth rate is 1.5-2%.
The major technology suppliers for the soda ash plant are:

Solvay and Cie SA, Belgium

AKZO-ZOUT Chemie BV, Netherlands

Asahi Chemical Industry, Japan

Polimex Cheepok, Poland

Technology Exports Divn, DSTA, China

The basic process for the manufacturer of soda ash has not undergone much change since last
130 years. Developments however are taking place in the following areas:

Process technology

Operation technology

Improvement of quality

New product from waste

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2.8 Structure and Status of Indian Industry


The manufacture of soda ash in India started in 1932 at in Gujarat with an installed capacity of
50 tons per day.
This was followed by the entry of another Chemicals manufacturing plant at Mithapur in
Gujarat in 1894 with an installed capacity of 100 tons per day. In a span of 50 years it has grown to be
the biggest soda ash unit in the country with daily capacity of 2000 tones.
In the same region in Gujarat, two more soda ash plants came up after-wards. First one was
commissioned in 1959 with a capacity of 200 tons per day which has been expanded to 800 tons per
day. Second one was commissioned in 1988 with a capacity of 1200 tons per day. All these four units
in Saurashtra in Gujarat are based on Solvay process.
Three units are operating on the modified Solvay process (Dual Process) in which ammonium
chloride is the co-product. The first plant based on this technology was set up in 1959 at Varansai, with
an installed capacity of 120 tons per day. The two other units operating on Dual process are at a
capacity of 200 tons per day. The present installed capacity of six soda ash manufacturing units is
17.09 lakh tones.

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CHAPTER 03

FEASIBILITY STUDY

The feasibility analysis is a preliminary study


undertaken to determine a project's viability or
the discipline of planning, organizing, and
managing resources to bring about the
successful completion of specific project goals
and objectives. The results of this study are used
to make a decision whether or not to proceed
with the project. In the case of the soda ash plant
an analysis of possible alternative solutions and
scenarios that has an impact on the proposed
was done and recommendations have been made
on the best alternative.

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3.1 Preliminary Study


As a preliminary study of the prospective soda ash plant a simple feasibility analysis has been
summarized in this chapter. The main objective of this feasibility is to explore the economical aspects
of the process and other concerns like environmental, technical, social issues that may arise as a result.
It can be said that the necessity of the plant is primarily based on final out come of the plant
and the market availability for its products. The bulk of the soda ash imported into the country is
primarily for the consumption of the glass industry. The main player in the present glass industry in Sri
Lanka is Ceylon Glass with a daily consumption of almost 20 Metric Tones per day. A considerable
growth in the consumption of Soda ash can be seen within this single entity itself.
SODA ASH IMPORTS (2006)
Quantity
Kg

Country
Bulgaria
China
India
India
Iran
Japan
Kenya
Malaysia
Pakistan
Romania
Singapore
Taiwan
Turkey
U.K.
Ukraine
Total
Avg price of 1kg of imported Na 2 CO 3
(Rs)
Average consumption per day

Value Rs.

619000
975407
4089598
83284
1
792000
1
100000
440000
725350
78
36000
469
175000
8,036,188

17120020
28721920
9342
101802615
2643973
4282
15948728
9510
3496878
13901583
19914608
26244
960489
824657
3573407
208958256

26.00
22016.95342
22.01695342

kg
MT

Figure 3.1: Soda ash imports (2006)

When we consider the total soda consumption based on the amount imported to the country it can be
clearly seen from the above graph (figure 3.1)that an average of almost 40 MT (2008)is consumed
daily. Also a considerable increase in the amount demanded per year is depicted in the figure 3.2.
Therefore a daily production capacity of 50 MT on a continuous basis is justifiable.

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Variation of Soda ash imports


45
40
35
MT/day

30
25
20
15
10
5
0
2004

2005

2006

2007

2008

year

Figure 3.2: Variation in soda ash imports

The present average imported price per kg of soda ash is `23`1. The cost incurred for the
production of a single kg based on the raw material costs, maintenance and operation costs and other
overheads will be far less than the importing price because of the availability of CaCO3 deposits in Sri
Lanka at a considerable degree of purity, availability of skilled workers at considerably lower wage
rates and mainly due to the avoidance of cost for freight services. But the lower price in itself doesnt
justify the high capital cost that has to be incurred for the implementation and construction of soda ash
plant based on the Solvay process. A further in-depth analysis with considerations of strength of export
market, pay back period, etc has to be taken into account.
When we consider the importing scenario there are considerable fluctuations in the demand for
soda ash and related products. It was noted that most of the soda ash imported to the country is in the
form of high dense soda ash. This is because high dense soda ash is one of the main raw materials of
the glass industry and most of the soda ash imported to the country is consumed by the same industry.
A main factor for the increased price of the imported soda ash in to the country is because of the fact
that different local companies import soda separately in small amounts and because of the cost
incurred for the freight services. Also as mentioned above the unstructured importing from various
suppliers and the unavailability of an agent to handle the soda import has led to higher prices. Another
factor that would lead to higher prices when importing is because of levies and taxes that has been
imposed on imported products and charges at the customs. Since soda is being imported to the country
at a higher price the related industries face restrictions in implementation and expansion because they
have a huge problem ofthe market share because of the high final cost.

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The main raw materials for the production of soda ash from the Solvay process are Brine and
Calcium Carbonate. When we consider the availability of these raw materials in Sri Lanka, brine is
present in the form of sea water all around the country and Calcium Carbonate can be obtained from
sand stone or Dolomite reserves present throughout the country. Pure Miocene sand stone can be found
in the land strip stretching from Puttalam to the Jaffna peninsula. Dolomite reserves are present to the
middle of the country. Areas well known in this aspect is present in the Matale district. Also Calcium
Carbonate can be found in the form of coral reefs in various parts of the costal belt in Sri Lanka though
this is not an environmental friendly and feasible option. Also sea shells that is present in the costal
areas is a good form of Calcium Carbonate but this is not a viable and secure raw material source for a
soda ash production facility of the proposed scale. Therefore it can be concluded with confidence that
a local soda ash production plant will be able to get the essential raw materials easily. Therefore based
on this preliminary feasibility analysis it can be said that building a soda ash plant in Sri Lanka would
be profitable.
In addition to the facts highlighted and discussed above, the feasibility has been further divided
and analyzed as economical, legal and administrative; market feasibility as part of the initial
evaluations and technical, social and environmental feasibilities have been analyzed as a measure of
viability when work is in progress.

3.2 Economical Feasibility

Impact on local industry- Soda ash is one of the most important raw materials for the
manufacturing as well as process industry. It can be used as a raw material for the production
of glass, polymers, etc. Also it is extensively used in the process industry as a raw material in
the production of various chemicals, fertilizers, etc. When soda ash is available locally at a
lower price and most importantly in form of a continuous, secure supply there would be a
considerable boom in the above mentioned industries. Also since the there would be
developments in industries that are in parallel with this industry. For example saturated brine is
required as a raw material in the Solvay process. Hence a salt production facility in the area can
be utilized to provide saturated brine.

Impact on economy of area- As studied and evaluated under chapter 5 the location of the soda
ash plant is designated as Karadipuval site in Puttalam. The Holcim Lanka cement plant and its
quarry is located in the puttalam district. The Aruwakkaru Limestone Quarry site of Holcim
Lanka Ltd is used to extract limestone to produce cement in Palavi plant of Holcim Lanka (pvt)

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ltd. This is the only quarry

in operation to extract limestone which is 150 km away from

capital city Colombo of Sri Lanka. Other than few industries the area presently can be
considered as remote or rural. With the establishment of the soda ash plant and the completion
of Norochcholai coal power plant the area will comprise of 3 main industries and would be
similar to an industrial zone. The Norochcholai coal power plant already has many
infrastructure developments which include the development of a port. The development of such
industries will lead to considerable development of the facilities, economy and availability of
jobs in the area.

Reduction of Imports- When we consider in a macro scale there will be considerable amount
of savings when the production of Sri Lanka is increased. This in tern will benefit the country
as a whole because of increase in GDP, reduction of unemployment, drop of inflation, increase
of local currency.

Opportunity for export- There are several industries that consumes soda ash as a raw
material. Also there is a high demand for soda ash in neighboring India and other south Asian
countries. Though India is one of the major producers of soda ash in the world it utilizes the
Dual purpose method to cater the fertilizer demand in the country and most of the plants are
sited north of the country. Also the dual purpose method leads to higher cost for the soda ash
because NH3 used in the process is of high cost. Therefore there would be considerable market
for soda ash produced in Sri Lanka in the south Indian region. Also there would be
considerable demand for end products like glass that is made from soda ash throughout the
south Asian region.

Increase of production- The availability of locally produced soda ash will lead to a boom in
the soda related industries. This would lead to the possibility of expanding local industries and
emerging of new ones. Such an increase of production, production capacity and availability of
raw materials would make Sri Lanka attractive to investors.

Production costs- As mentioned earlier the availability of raw materials locally for the
production of soda ash in Sri Lanka itself will lead to reduction production cost. Also the
availability of skilled workers and manpower at a relatively lower wage rates comparative to
that of other soda ash producing European counterparts will lead to reduced cost. But it needs

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to be noted that the other overhead costs in Sri Lanka would be somewhat higher because of
high electricity tariffs and condition of infrastructure.

Incentives and levies imposed on the industry- Presently there are various levies and taxes
imposed on imported goods. But Ceylon glass which is involved with importing most of the
soda ash into the country for its production activities has a considerable concession as part of
the agreement with the government when it was taken over by an Indian company. Even
though this is the case if soda ash is produced locally the government would impose taxes on
imported soda ash to promote the local producer.

Government support- Since a soda ash production plant is a huge production facility and it
would be involved with providing jobs for considerable amount of people the government is
likely to act in favor of the local soda ash producer. Government support at a considerable
degree would be required because purchasing of land in the proposed area under Chapter 6,
establishment of infrastructure support, environmental impact mitigations, obtaining quarrying
rights for limestone, provision of security from terrorist threats etc would require government
intervention and support.

Security- As discussed later in Chapter 5 the most suitable location for the proposed soda ash
plant is at Karadipuval in Puttalam. Though more pure Miocene Limestone deposits are
available in the Jaffna Peninsula, it will not be a likely option because of the terrorist activities
present in the area and the on-going war effort. When we consider the site at Puttalam a secure
security situation has been prevailing for several years. Also a tight security parameter
presently has been set in the area which would be further strengthened once the Norochcholai
coal power plant has been commissioned. Therefore it can be said that the security threat or
risk is minimum.

Inflation and its impact- The present inflation rate of the country is very high. Therefore this
would negatively impact on the project at the construction and maintenance phases because
most of the equipment would have to be imported. But once the plant is running the soda
produced and sold locally would not be severely affected. But the competitive edge of soda ash
that is to be exported would be lost.

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Regional impact- A major administrative and management issue that would affect the
functioning of the plant is the environmental concerns and waste management. When the plant
has necessary control measure in-place, which is used successfully in other parts of the world,
this threat can be avoided.

Impact from other main industries in the area (Holcim) - An administrative issue that the
company involved will have to face is when obtaining quarrying rights to the limestone quarry.
At present Holcim Lanka is involved with quarrying activities at Aruwakkaru. Since this site
has already been reserved by the cement company obtaining quarrying rights and reserving of
limestone deposits would be necessary.

When we consider the economical evaluation as a whole after considering lagal and
administrative issues the implications are positive. But since this is a preliminary feasibility
analysis of the project in-depth cost and benefit analysis are not possible. But when viewing the
above facts and considering the economical parameters, it can be said with certainty that the
expected outcome would be positive.

3.3 Market Feasibility

Market trends Presently there is considerable market trend towards the development of soda
and salt related industries in Sri Lanka. This will result in a huge demand for soda ash which is
being used as raw material. Also there is tremendous potential for the development of the glass
industry. For instance Ceylon Glass moved from their conventional plant at Ratmalana and
built a new one at Horana to cater the increasing demand. Therefore it can be said with
confidence that there would be considerable demand for locally produced soda ash with the
expected boost in industry.

Allowance for expansion- As mentioned in the economic feasibility and later on in the site
layout selection there is considerable potential for expansion. The present demand for soda ash
is about 40 MT/day. The proposed plant has a capacity of 50MT/day with an allowance of 10
MT/day. In the event of a huge increase in the market a new plant or an expansion of the plant
itself would be required. The land selected under the latter chapter of site selection has
allowance for such an expansion.

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Sales generation- As highlighted above the current market price for soda ash is around Rs 25.
According to the present economic evaluation it can be said that a kg of soda ash can be
produced from a cost of around Rs 8 which means that the gross profit is considerably high.

Pay back- As mentioned above the gross profit per kg of soda ash sold is high. Therefore it can
be said that the payback would be less event though a thorough evaluation with a detailed
financial statements would be required for in order to estimate the payback accurately.

Sales and marketing concerns- At present there wont be any marketing concerns because
there are no other players in this industry. The only competitor would be soda ash importers.
But there are no big importers that have specialized in this business, currently in Sri Lanka.
Also since the government is biased towards the development of the local industry there would
be restrictions on imports once the plant has commenced production. Also since the no of
consumers if Soda ash is less a highly costly marketing campaign would be meaningless.

Distribution network As mentioned above since the consumers of soda ash is less the ideal
distribution network would be a one-to-one system. For example when soda ash for the glass
company can be sold to the Ceylon glass (pvt) ltd directly without the involvement of
intermediates and complex sales networks. This would benefit the producer as well as the
consumer because of simplicity and high profitability.

3.4 Technical Feasibility

Infrastructure requirement- The proposed plant with a capacity of 50 MT/day would require
considerable amount of infrastructure and utility processes. Normally Solvay process plants are
considered to be some of the biggest plants in the world. The plant would require a road
network, railroad or durable road to transport limestone from the quarry, uninterrupted
electricity, basic water supply and process water, etc. The producers would have to build the
internal road network as required. In the event of building a rail network for the transportation
of limestone from the quarry the company would require the assistance of the governments.
The case would-be the same if the plan to transport limestone from the quarry to the plant in
Lorries and vehicles because a road with reinforced layer would be required. The plant could
fulfill its power requirement by means of electricity from the National grid and power
generated from steam/cogeneration at the plant. The plant can fulfill its domestic water

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requirement from the National water supply lines. But the process would require extensive
amounts of process water. Since the use of treated and purified salt water for this purpose
would not be feasible the need will have to be met by water from dug wells or stream/river.

Geological aspects- A process plant of this scale would require a strong foundation. Therefore
the stability of the bedrock on which the plant is sited, is of importance. The land of Puttalam
area consists of hard, moisture free soil. It has already been proved that the bedrock in the
Puttalam area is one of the best to locate process plants by the survey done for the
Norochcholai coal power plant. This is a positive aspect. But the soil in the area, especially in
places near the lagoon and the salt production plants the soil consist of salts which might be
harmful to the plant. By adopting necessary coatings on surfaces and having corrosion
allowances this problem can be solved.

Availability of skilled workers and professionals for maintenance of plant- At present the
district of Puttalm doesnt comprise of a considerable skilled and professional workforce.
Hence the human force requirement will have to be met by resident workers from other areas of
the country. But it is possible to obtain unskilled laborers from the area for the plant
construction activities and maintenance when the plant has been commissioned.

Availability of construction companies- At present Sri Lankan Process development


companies doesnt have the experience and capacity for the construction of a Solvay plant with
a daily capacity of 50MT. Hence the assistance of process plant construction companies abroad
with experience in similar construction activities will be required.

Availability of expert consultancy firms- At present there are companies that have extensive
amounts of technical expertise regarding the Solvay process. Some of them are given below.
Solvay and Cie SA, Belgium
AKZO-ZOUT Chemie BV, Netherlands
Asahi Chemical Industry, Japan
Polimex Cheepok, Poland
The technical assistance of such a consultancy provider will be required to oversee the
construction activities and provide process consultancy when the plant has been commissioned.

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Fabrication concerns- Presently Sri Lanka has the capacity for fabricating most of the process
vessels required for the plant. Other equipment that cannot be produced locally will have to be
imported or fabricated and shipped to Sri Lanka.

Imported equipment transportation- The port that has been built at Norochcholai is to be
used as a transportation channel for the imported equipment of the Norochcholai Coal Power
Plant. The same port can be used when bringing Heavy process equipment or vessels for the
proposed soda ash plant.

3.5 Social Feasibility

Social condition of people- The living standard of an average resident in the area is low. Most
of the population is farmers. The proposed plant will not have a huge impact on the residents of
the area since not much farming is done or vegetation is present in the chosen area. It cannot be
said that the plant will be involved to a great extent in uplifting the living standards of these
people, but there are certain direct and indirect means related to the activities of the plant
through which the local population can thrive and earn an extra income.

Resettlement and rehabilitation- This will not be a problem because the land chosen is a
piece of bare land. Therefore no concern of this matter would be required. But in the event of
placing rail lines from the existing one from the Holcim factory to the quarry, acquiring of
certain land plots from the residents will be required. But even in this case resettlement or
rehabilitation will not be a concern because this project will not need land from a process of
nationalization.

Social resistance- The construction of the plant will definitely have to face public pressure and
cultural resistance, as quite evident from other projects of this sort. The pressure would mainly
be based on environmental issues, pollution and waste disposal. These resistances can be
subdued to a certain degree by implementation of the best available pollution control
techniques and waste management principles and increasing public awareness regarding them.
This scenario as whole will not affect the decision of implementation of the plant.

Health and safety concerns- As mentioned above with the implementation of the best
available practices and by designing process vessels according to standards the risk of a

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disaster occurring due to failure can be avoided. By having a good training programme in-place
and by recruiting skilled and experienced workers there would not be a risk of health and
safety. Then it would not be a concern in the feasibility concern.

Employment- One of the positive implications of the plant on the surrounding community is
the increase in job opportunities. These jobs can be in the form direct or indirect means. For
instance with the start of construction activities of the plant many laborers (both skilled and
unskilled), will be recruited from the area. Once the plant is complete and has been
commissioned people across a diverse range will get job opportunities. In recruiting of
recruiting such people the priority will be given to the locals in the area because the company
will then not have to bear accommodation and transport costs. Also with the establishment of a
new plant various businesses would come into being, whose activities are not directly related to
the operation of the plant. For example many new shops and stores would be established by
external people to cater the needs of the employees, suppliers, etc. This would result in the
provision of employment as well as flow of money into the area. But on the plants perspective
relying on employees from the adjacent areas alone, will not be sufficient because the lack of
skilled workers and professionals in the area will affect the operations of the plant. Therefore
the company will have to provide transport and accommodation to a certain degree to attract
employees with the necessary traits from other parts of the country.

Local industry- At present in the Puttalam district, there are industries and commercial entities
that will directly benefit from the proposed soda ash plant at Karadipuval. For instance the
heavily spread saltern industries in the area discharge the Mother Liquor from the tanks after
salt has crystallized. But since this mother liquor with saturated Sodium Chloride is a raw
material for the soda ash industry the salterns can earn an income from their effluent. Also the
Holcim cement factory can benefit immensely by leasing out their assets like the quarry, rail
carriages, kiln for hazardous waste disposal, etc. Also the jetty/port that is being built in the
area can benefit from the activities of the plant. Other than these industries small commercial
entities like suppliers, caterers, transporters, etc also will get a new market onto which they can
expand their business.

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CHAPTER 04

PROCESS SELECTION

The selection of an appropriate process is an


important decision, all the subsequent work
depends upon this choice. Although the selection
can be changed or modified at a latter stage, at
least before the plant is built, such a decision
results in a serious waste of time and
money.

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4.1 Introduction
The stepping stone for the chemical revolution begun in Europe with the introduction of the
Leblanc process for the production of Soda by Leblanc in 1790. This industry used as raw materials,
salt, sulfur, limestone, saltpeter, coal, air, and water; its products were the alkalis, sodium carbonate
and sodium hydroxide. Cheap alkalis brought to the ordinary citizen those luxuries which had formerly
been enjoyed only by the rich and powerful: glass for bringing light into dark places, paper for
bringing the printed word into proletarian homes, and soap for bringing sanitation into cities oppressed
by filth and disease.
A highlight of the developments in the soda ash industry was witnessed when the Belgian
industrial chemist Ernest Solvay (in 1861), developed a method to convert sodium chloride to sodium
carbonate using ammonia. Other than the Leblanc and Solvay process there have been various
developments in the soda ash industry during the last 100 years. The processes that are present used for
the production of soda ash are given below.

Leblanc Process

Solvay Process

Dual Process

Akzo Dry Lime Process

New Ashai ( NA) Process

Akzo Zoul Chemie Method

Nepheline syenite process

Carbonation of caustic soda

Also Trona and nahcolite based process are used in different countries but this is not an option
in the Sri Lankan context because the island does not have soda ash reserves which can be mined and
processed under these methods to yield soda ash for consumption. In other words Trona and Nahcolite
processes are used for processing soda ash reserves to remove impurities within them. Also there are
some plants operating under the Nepheline syenite process and Carbonation of caustic soda
method. But it is not possible to obtain soda ash of good quality from the Nepheline syenite process
and this would lead to additional cost for purification processes as demanded by soda ash consuming
industries. Also carbonization of caustic soda is not feasible for Sri Lanka at present because it is
dependent on imports to fulfill caustic soda requirements.

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4.2 Comparison of Solvay process with Others Methods of Production


As mentioned above in the introduction, Leblanc process was the industrial process for the
production of soda ash used throughout the 19th century. It involved two stages: Production of sodium
sulfate from sodium chloride, followed by reaction of the sodium sulfate with coal and calcium
carbonate to produce sodium carbonate. The Leblanc process was a batch process in which sodium
chloride was subjected to a series of treatments, eventually producing sodium carbonate.It is also
noteworthy that in addition to valuable alkalis, the Leblanc process produced two waste products,
hydrogen chloride and calcium sulfide. Acidic hydrogen chloride gas was sent up the chimney, after
which it decimated vegetation in the vicinity of an alkali works. Insoluble calcium sulfide was
conveniently disposed of in heaps where the vegetation used to be. Unfortunately, when calcium
sulfide reacts with rain water it farts out noxious hydrogen sulfide.
Hence alkali manufacturers based on Leblanc process became popular targets for lawsuits and
government regulations. The British Alkali Act of 1863, for example, required the absorption of 95%
of the hydrogen chloride produced by the salt cake furnace. This was easily accomplished, hydrogen
chloride being quite soluble in water; the waste gas was sent up through a stone tower filled with coke;
water dribbling down through the tower absorbed the hydrogen chloride, producing aqueous
hydrochloric acid.
In addition to hydrogen chloride which can be presently considered as valuable product own its
own account and after Henry Deacon in1868 introduced a process for turning waste hydrogen chloride
into bleaching powder, which could be utilized in paper and textiles industry, calcium sulfide produced
is a problem for soda manufacturers using the Leblanc process. This (calcium sulfide produced)
became a persistent problem owing to the twin problems of stinking heaps of tank waste, and the loss
of valuable sulfur. It is noteworthy at this point that pure source of Sulfur is not present in Sri Lanka.
An alternative to sulfur is sulfur dioxide which was obtained during the latter stages of the soda
industry from roasted from pyrites, which alternatively would have to be imported to Sri Lanka. Also
whatever the source may be, it will eventually end up as calcium sulfide waste. The only positive
solution for the disposal of calcium sulfide lies in the fact that it could be converted into sodium
thiosulfate, used by photographers to fix photographs but this cannot be considered as a feasible
option. Also at present there is a method of recovering sulfur from tank waste owing to the discoveries
of Alexander Chance in 1887. But these slight improvements would adversely affect the efficiency of
the overall process.

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While the construction of a Solvay plant would be more expensive than a comparable Leblanc
plant, it would require fewer raw materials; thus capital investment is higher but operating costs will
be less. With lower operating costs, the Solvay process will be able to drop the price of soda produced.
It can be said that the Solvay process is cleaner and more efficient where else Leblanc process is
crippled by pollution and waste. Also the Solvay process has a distinct advantage over its Leblanc
counterpart because of the continuous developments being carried on it, in other parts of the world
where else soda production from Leblanc process is one of the diminishing technologies. It is evident
from the fact that world production of soda in 1863 had been 150,000 tons, all produced in Leblanc
plants. By 1902 world production of soda was at 1,760,000 tons, where over 90% of the amount was
be produced using Solvay plants.
A very recent development in the soda ash industry has enabled the co production of vinyl
chloride monomer (for production of Poly Vinyl Chloride) and soda ash. Akzo Zoul Chemie
Nederland has succeeded in producing (on a small scale) vinyl chloride with soda ash as a co-product.
The process uses medium pressure steam and carbon-dioxide instead of more expensive electrical
energy (for the electrolytic production of production of chlorine). The overall energy consumption of
the new process is about one half that of the conventional method when caustic soda is the co-product.
Here soda ash is produced from the reaction of salt with a concentrated aqueous trimethylamminecarbon doxide solution obtained downstream in the vinyl chloride process.
Even though the advantages of the Akzo Zoul Chemie process are attractive, as evident from
the above process description soda ash would be a by-product in this process. This would mean that
the amount of soda- ash produced would be dependent on the demand for vinyl chloride monomer.
That would imply that the soda ash output would be governed by the demand for PVC in the market.
Also the capital cost that needs to be incurred for a plant involved with the cogeneration of both soda
ash and PVC would be relatively higher than that for a plant involved with only the production of soda
ash only. Also this is a relatively new technology which is still being developed and the rights for this
plant are restricted by the patent company. Therefore additional administrative charges and royalty
from the revenue needs to be bared.
The Dual purpose plant came into being because of the concerns associated with the discharge
of solid waste. The dual purpose is a modification of the existing Solvay process. It was developed by
a Chinese chemist Hou Debang in 1930s. It is the same as the Solvay process in the first few steps.
But, instead of treating the remaining solution with lime, carbon dioxide and ammonia is pumped into
the solution, and sodium chloride is added until it is saturated at 40 C. Then the solution is cooled
down to 10 C. Ammonium chloride precipitates and is removed by filtration, the solution is recycled

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to produce more sodium bicarbonate. Hou's Process eliminates the production of calcium chloride and
the byproduct ammonium chloride can be used as a fertilizer. The constraints of Dual process are facts
that it has to depend on the availability of carbon dioxide gas and ammonia from fertilizer unit and the
production of soda ash will be restricted depending on the demand for ammonium chloride in the
market.
The New Asahi process in a relatively new modification of the Dual purpose process. This
process came into being owing to the developments in the Japanese soda ash industry. The Japanese
soda ash industry was based on high cost imported salt. Therefore this new NA process was developed
which is essentially dual purpose process on a large scale. Many new modifications were made to
incorporate a more efficient and less raw material utilizing process. These modifications include
changes in the Carbonation section, cooling system used for cooling the mother liquor from
centrifuges, adoption of Ammonium chloride distillation unit, system of raw salt crushing, etc. It also
bears the same constraints of the conventional dual purpose process. In addition the initial investment
is very high for New Asahi (NA) process. This is because the New Asahi process requires more
investment to be made in the lime burning/lime slaking, ammonia recovery and ammonium chloride
crystallization sections.
It can be said that the effluent generation from Solvay plants is more compared to other process
plants. Owing to the requirement of placing Solvay plants with proximity to the sea, the effluent from
process are discharged into sea after some minor treatment which does not affect the ecological
balance because the composition of effluent compares favorably with sea-body composition.
Generally, a costal soda ash plant should go for the Solvay process whereas inland plant should opt for
Dual process near a fertilizer unit.
As discussed above the most likely option for the soda ash production plant is the conventional
Solvay process and the Dual purpose method. A comparison of the two processes is given below.
Solvay Process
Uses Brine, limestone and coke as raw
materials
Uses small amounts of ammonia and carbon
dioxide as makeup gases, while the bulk of the
gases are recycled
Soda ash is obtained as product

Dual Purpose Process


Uses brine, ammonia, limestone and coke.
Uses small amounts of and carbon dioxide as
makeup gases, while the bulk of the gase is
recycled
Soda ash and Ammonium chloride(fertilizer) is
obtained as co-products

Calcium chloride is obtained as a by


product/waste. Therefore has a waste disposal No effluent disposal problem
problem
Ammonia has to be imported as a raw material
Recovers most of the valuable ammonia
if the process is stand alone plant (Not adjacent
to a fertilizer production facility)
Depend on availability of carbon dioxide and
Production is not constrained
ammonia from a fertilizer unit. But presently in
Sri Lanka there is no such production facility

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Completely close process when fertilizer unit is


also present
The production is solely dependent on the soda Production of soda ash is restricted by the
ash demand in the market
demand for ammonium chloride
Efficiency is comparatively low
Yield is slightly higher
Investment and maintenance costs are
Investment and maintenance costs are low
comparatively high
Many factors influence the placement of the
plant. For example fertilizers produced is in
Since the raw materials are present at the same
demand at the agricultural zones near the
location at Puttalam the plant can be easily
Mahaweli, saturated brine is obtainable from
sited there
salterns, imported ammonia can be stored at a
low cost near a port, etc.
The technology of the Solvay process has
This is relatively a new technology used mainly
undergone several developments and is at a
in China and India
mature state
Table 4.1 a comparison of the Solvey and dual processes
Not a completely closed process

4. 3 Process Selection Conclusions


The conventional solvay process appears to be preferred for a plant producing 50 tonne/day of
light soda ash. The capital cost advantage of this process and the ability function independently
surpasses the benefits of the high efficiency dual purpose process. Furthermore, the higher temperature
(because of the availability of a kiln) and the favorable effect of pressure enable a greater recovery of
energy from the process. This choice, made on both economic and operational grounds, can be said as
being consistent when we consider the production capacity of soda ash, in the world throughout, from
Solvay process over the Dual purpose method.

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CHAPTER 05

PROCESS DESCRIPTION

Chemical and process Engineers are the leading


characters in the process design and
optimization. They put the desired target into a
real world application by putting some unit
processes together and interchange the possible
unit operations along the process streams where
it gives the best economic value.
Under this section a thorough evaluation of the
process selected is carried out. The process
description of a particular process is expected to
yield the parameters and restrictions that bind
the process. Also an special emphasis on the
process unit operations are considered under the
process description

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5.1 Main Chemical Reactions in Solvay process

Figure5.1: Block diagram of the soda ash production plant

The Solvay process relative to the production of soda ash could be summarized by this
equation involving the two main components: sodium chloride and calcium carbonate.
2 NaCl + CaCO 3 Na 2 CO 3 + CaCl 2
In practice this direct way is not possible and it needs the participation of other substances and
many different process steps to get the final product, soda ash.
First reactions occur in salt solution (brine). First of all, ammonia is absorbed (equation 1) and
then, the ammoniated brine is reacted with carbon dioxide to form successive intermediate compounds:
ammonium carbonate (Equation 2) then ammonium bicarbonate (Equation 3). By continuing carbon
dioxide injection and cooling the solution, precipitation of sodium bicarbonate is achieved and
ammonium chloride is formed (equation 4).

Chemical reactions relative to different steps of the process.


NaCl + H 2 O + NH 3 NaCl + NH 4 OH

---------------(1)

2 NH 4 OH + CO 2 (NH 4 ) 2 CO 3 + H 2 O

--------------- (2)

(NH 4 ) 2 CO 3 + CO 2 + H 2 O 2 NH 4 HCO 3

--------------- (3)

2 NH 4 HCO 3 + 2 NaCl 2 NaHCO 3 + 2 NH 4 Cl

--------------- (4)

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Sodium bicarbonate crystals are separated from the mother liquor by filtration, then sodium
bicarbonate is decomposed thermally into sodium carbonate, water and carbon dioxide (Equation 5).
2 NaHCO 3 Na 2 CO 3 + H 2 O + CO 2

--------------- (5)

CO 2 is recovered in the carbonation step (Equations 2 and 3). Mother liquor is treated to
recover ammonia. The ammonium chloride filtrate (Equation 4) is reacted with alkali, generally milk
of lime (Equation 6), followed by steam stripping to recover free gaseous ammonia.
2 NH 4 Cl + Ca(OH) 2 CaCl 2 + 2 NH 3 + 2 H 2 O

--------------- (6)

NH 3 is recycled to the absorption step (Equation 1). Carbon dioxide and calcium hydroxide
originate from limestone calcination (Equation 7) followed by calcium oxide hydration (Equation 8).
CaCO 3 CaO + CO 2

--------------- (7)

CaO + H 2 O Ca(OH) 2

--------------- (8)

Brine (NaCl) has to be treated before the input in the process to remove impurities like calcium
and magnesium. If not removed they would react with alkali and carbon dioxide to produce insoluble
salts contributing to scale formation inside equipment. Brine purification reactions are described in the
following equations.
2+

2-

Ca + CO 3 CaCO 3
2+

--------------- (9)

Mg + 2 OH Mg(OH) 2

--------------- (10)

Sodium carbonate formed (Equation 5) is called light soda ash because its bulk density is
approximately 0.5 t/m3. A subsequent operation called densification enables this value to be doubled
by crystallization into sodium monohydrate, by adding water (Equation 11) then followed by drying
(equation 12). Final product is dense soda.
Na 2 CO 3 + H 2 O Na 2 CO 3 .H 2 O

--------------- (11)

Na 2 CO 3 .H 2 O Na 2 CO 3 + H 2 O

--------------- (12)

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5.2 Process Steps


The manufacturing process consists of several discrete operations, each comprising a plant area:

Brine purification

Calcination of limestone in kilns and the production of CO 2 and milk of lime

Absorption of ammonia into purified brine

Carbonation of the ammoniated brine with CO 2 to produce sodium bicarbonate

Separation of sodium bicarbonate from mother liquid

Recovery of the ammonia using milk of lime

Calcination of sodium bicarbonate to form sodium carbonate (light ash)

Densification of sodium carbonate to form dense ash

5.2.1 Brine purification


Crude brine received from the salt fields is treated to remove any impurities. Impurities such as
calcium and magnesium have to be removed from brine. This operation is achieved in the brine
purification area.
Magnesium ions, are precipitated as insoluble magnesium hydroxide, Mg(OH) 2 , by the
addition of an alkaline reagent. The most commonly used reagent is milk of lime as this is already
produced in large quantity for ammonia recovery; another possibility consists of using sodium
hydroxide (NaOH).
Calcium ions are precipitated as insoluble calcium carbonate, CaCO 3 , by reaction with sodium
carbonate. Depending upon the purification process used and to sulfate and magnesium contents, a
certain amount of calcium can be precipitated as gypsum (CaSO 4 .2H 2 O).
Addition of these two reagents is regulated in such a way as to reach the necessary reagent
excesses for adequate purification. A sufficient reaction time of the suspension that contains suspended
CaCO 3 and Mg(OH) 2 ensures a correct crystallization of the two components. Thereafter the
separation of Mg(OH) 2 and CaCO 3 from the purified brine is usually achieved in a decanter or brine
settler. The decanter has to be purged frequently. The purge can be treated or sent back to salt wells or
cavities after treatment.
A certain amount of CO 2 gas is sent in to the absorber at the same time with NH 3 but not
enough to form (NH4) 2 CO 3 ,the calcium and the most of the Magnesium and all the iron salt
precipitate and collect in the cone of the NH 3 absorber.

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5.2.2 Calcination of limestone in kilns and the production of CO 2 and milk of lime
Theoretically, in the soda ash process, the CO 2 balance is stoichiometrically neutral. However,
a CO 2 excess is needed to compensate the non complete absorption of CO 2 in the carbonation stage, in
the different washers and losses in the treatment of the mother liquid in the distillation. This excess is
generated by combustion of normally coke which provides an energy source used for limestone
decomposition, as well as the additional CO 2.
Burning of the limestone (natural form of CaCO 3 ) is carried out in a temperature range of 950
to 1100C. The operating conditions for a lime kiln fitted to soda ash production are critically different
from those used for lime production, because of the need to produce a gas with the maximum
concentration of carbon dioxide for its subsequent use in the process. This is done to the detriment of
produced lime purity, which will be less than that necessary in the lime industry. To improve particle
sizing of limestone loaded in lime kiln, screening is carried out prior to kiln charging.
In the case of soda ash plants, considering the quantities of limestone to be burned and the
necessary CO 2 concentration, the energy contribution is generally provided by means of solid high
carbon fuels such as coke, coal or lignite. Use of gaseous fuel leads to too low a CO 2 concentration in
the gas produced making its subsequent use impossible without an expensive reconcentration unit.
Raw burnt lime produced by lime kilns associated with a soda ash plant contains approximately
75 to 90% of CaO. Its direct use in the solid form is uncommon because of the difficulty in controlling
an adequate feed rate of a material in which the active constituent, CaO, is not constant. By hydrating
the CaO to milk of lime a better control of the alkali addition is achieved during the ammonia recovery
step.
Hydration of the raw lime is carried out in slakers (dissolvers) where raw lime and water flows
are regulated to ensure that the alkali content of milk of lime produced is as constant as possible. This
reaction is a highly exothermic. A part of the heat generated vaporizes some water which is released
from the slaker vent. During the hydration, fine inert materials contained in limestone (sulfates, silica,
clay, silico-alumina compounds, unburned limestone and others) can mainly be found in milk of lime.
Larger particles are separated by screening, then washed and recycled or released out of the process.
The unburned pieces of limestone are recycled.

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Figure5.2: Vertical shaft kiln for lime stone

5.2.3. Absorption of ammonia into purified brine


Ammonia is recovered by recycling the outlet gas from the distillation plant to the absorption
stage where it is absorbed in purified brine. This flow mainly contains recovered NH 3 and a quantity of
CO 2 . This chemical operation is achieved in equipment that allows close gas liquid contact.
Because this is an exothermic reaction, cooling of the liquid is necessary during the operation
to maintain efficiency. The outlet solution, with a controlled ammonia concentration, is called
ammoniacal brine. Any gas that is not absorbed is sent to washer contacted with purified brine to
remove traces of ammonia before it is recycled or released to the atmosphere.

5.2.4 Carbonation of the ammoniated brine with CO 2 to produce sodium bicarbonate


Ammoniacal brine is progressively CO 2 enriched (carbonated) with recycled carbon dioxide
from sodium bicarbonate calcination and carbon dioxide originating from lime kilns. To ensure
adequate CO 2 absorption and sodium bicarbonate precipitation, the ammoniacal brine is cooled with
water. Suspension of crystals exiting from columns or carbonators is sent to the filters.
Outlet gas from the carbonation towers is sent to a final washer, contacted with purified brine
to absorb NH 3 traces still present in the gas before release to the atmosphere.

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There two sources of CO 2 . One is the lime stone kiln which furnishes gas containing 35 to 40
percent CO 2 the rest mainly Nitrogen, and other source is the furnace in which the sodium bicarbonate
is calcined. it gets may be as high as 95 percent of CO 2 .This second portion of the gas maybe
considered as circulating. In some plants these two gases are combined to in the pump house and no
distinction is made.
When separate flows are used at the first stage absorbs 40 vol% CO 2 gas from the kilns into the
ammoniated brine stream from the absorbers, and proceeds to the point where most of the CO 2 in the
solution exists as carbonate ions. Sodium Carbonate at the second stage of carbonation occurs in the
Solvay towers. More kiln gas, and a recycled stream of up to 90 vol% CO 2 , are used to convert
carbonate ions to bicarbonate ions. More heat is liberated, and cooling of the tower contents is
necessary to assist absorption and to control crystallization of sodium bicarbonate. At the bottom of the
Solvay towers, where the stronger CO2 stream enters, the pressure is approximately three atmospheres,
giving maximum CO2 absorption.

5.2.5 Separation of Sodium Bicarbonate from Mother Liquid


Separation of sodium bicarbonate crystals from mother liquor is achieved by means of
centrifuges or vacuum filters. After washing of the cake to eliminate mother liquor chloride, it is sent
to calcination. The liquid phase mother liquor is sent to the distillation sector for ammonia recovery.
Where filters are used, air is pulled through the cake by means of vacuum pumps. Thereafter,
this gas carrying ammonia and some CO 2 is cleaned by a washer fed with purified brine before
exhausting to atmosphere.
Crude sodium bicarbonate manufactured by the carbonation process is the primary output of
the Solvay ammonia soda process. The bicarbonate produced in this way is the feed to the calcination
stage for the conversion to the finished product solid soda ash. In some cases a small part of this crude
bicarbonate, which although predominantly sodium bicarbonate also contains a mixture of different
salts (ammonium bicarbonate, sodium carbonate and sodium chloride), may be extracted from the
Solvay process cycle to be dried as crude bicarbonate product made without purification, by simple
drying process. This crude product may find applications in some commercial outlets.

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5.2.6 Recovery of the Ammonia using Milk of Lime


The filter liquor contains unreacted sodium chloride and substantially all the ammonia with
which the brine was originally saturated, present as fixed and free ammonia. The fixed ammonia or
ammonium chloride corresponds stoichiometrically to the sodium bicarbonate that had been
precipitated. Free ammonia includes ammonium hydroxide, bicarbonate, carbonate, and the several
possible carbon compounds of ammonia that decompose at moderate temperatures.
Before preheating, sulfide solution may be added for corrosion protection. The sulfide is
distilled for eventual absorption by the brine in the absorber. The filter liquor is preheated by indirect
contact with the gases leaving the distiller. The warmed feed liquor then enters the main coke, or
bubble cap filled sections of the distiller where heat decomposes free ammonium compounds and
steam strips almost all of the free ammonia and carbon dioxide. The carbon dioxide free solution is
usually treated with milk of lime in an external well agitated limiting tank called a prelimer. Here the
ammonium chloride reacts with the milk of lime and evolved ammonia gas is vented back to the
distiller.
The resulting hot calcium chloride solution, containing residual ammonia in the form of
ammonium hydroxide, flows back to a lower section of the distiller. Low pressure steam sweeps
practically all of the ammonia out of the limed solution. The final solution, known as distiller waste,
contains calcium chloride, unreacted sodium chloride, and the excess lime, and is diluted by the
condensed steam and the water in which the lime was conveyed to the reaction. Distiller waste also
contains the inert of this solution.
However, the waste liquors are usually pumped to settling basins where the suspended solids
are deposited. The clear over flow contains dissolved salts, which are objectionable contaminants are
locations where the quality of the receiving waters is materially affected.

Close control of the

distillation is required to thoroughly strip carbon dioxide to avoid waste o flame and achieve nearly
0

complete ammonia recovery. The hot (56 C) mixture of wet ammonia and carbon dioxide leaving the
top of the distiller is cooled to remove water vapor before being sent to the absorber.
One of the major achievements of the Solvay process is the high efficiency of the ammonia
recycle loop. This loop circulates roughly 500 to 550 kg NH 3 /t soda ash from which the ammonia loss
is less than 0.5 % of this flow rate. The purpose of this important process distillation is to recover
ammonia from the ammonium chloride containing mother liquors recovered from the bicarbonate
filters , centrifuges.
After pre heating with outlet gas from the distiller, supported by the injection of steam at the
bottom of the NH 3 stripping column, the mother liquor releases almost all its CO 2 content. Addition of

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alkali normally in the form of milk of lime decomposes NH 4 Cl into NH 3 which is stripped from the
solution by injected low pressure steam at the bottom of the distillation column. The outlet solution
contains calcium chloride together with all the residual solid materials. Ammonia recovery yield is
controlled according to the permitted ammonia concentration in the released liquid. The lower the
permitted value, the higher the quantity of stripping steam and therefore the global energy
consumption, and the higher the cost of the ammonia recovery. This control can only be applied to a
theoretical minimum ammonia level.
After cooling and condensation of steam, the gaseous phase containing recovered CO 2 and NH 3
is returned to the absorption area for reuse.

5.2.7 Calcinations of Sodium Bicarbonate to form Sodium Carbonate (light ash)


Sodium bicarbonate cake is heated (160 to 230C) to achieve calcination into a solid phase
light soda and a gaseous phase containing CO 2 , NH 3 and H 2 O.
This gas is cooled to condense water and the condensates formed are sent to distillation for
NH 3 recovery, either directly or via filter wash water. After cleaning, the gas (high CO 2 concentration)
is compressed and sent back to the carbonation columns.
Normally, energy needed for sodium bicarbonate calcination is provided by steam that
condenses in a tubular heat exchanger which rotates through the sodium bicarbonate. The method
consisting of heating externally by gas or fuel oil combustion in a rotating drum containing sodium
bicarbonate is occasionally encountered. The kiln flue gas is also can be used.

5.2.8 Densification of Sodium Carbonate to form dense ash


Sodium carbonate formed first is called light soda ash because its bulk density is approximately
0.5Mg/m3. A subsequent operation called densification enables this value to be doubled by
crystallizations into sodium monohydrate, by first reacted with water and then gives sodium carbonate
monohydrate crystals. These are then dehydrated by heating in a rotary drier or fluid bed drier.

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5.3 Product (Soda Ash) Storage and Handling


Soda ash has to be stored in a dry place to avoid hydration, crusts formation or hardening.
Precautions are taken to prevent contamination by other nearby stored products, and to prevent the
release of soda ash dust during handling.
Most of the time, sodium carbonate is stored in large capacity metallic or concrete silos.
Because of high daily production in large production units ,the available total storage volume is
normally less than a week production.
Bulk handling of dense soda ash is easily achieved, for example, by belt conveyor. Necessary
precautions have to be taken to avoid and control dust release. Handling methods are selected to
minimize any particle size reduction of the product.

5.4 Raw Materials


Because the production of sodium carbonate is a large-tonnage low cost operation, the plants
have been historically situated close to some or all of the critical raw materials (limestone, brine,
water) to reduce the transport cost.

5.4.1 Brine
Sodium chloride (common salt) is extracted by evaporation of sea water. In several cases
mother liquor from salt production process can be used as raw material to partially replace brine when
the mother liquor has a suitable composition for the soda ash.
So for our plant, we decided to brought brine or mother liquor from Puttalama soltern. In the
Solvay process, the sodium chloride reacts in liquid phase (brine) which contains as much sodium
chloride as possible (around 300 g NaCl/l) and is virtually saturated. This brine also contains
impurities, mainly magnesium, calcium and sulfate.

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The raw and purified brine can be stored in open tanks made of mild steel, polymers, or in open lined
reservoirs.

Table5.1: Raw and purified brines (typical composition ranges)

5.4.2 Limestone
Basically, a high content of CaCO 3 in the limestone is an important parameter to avoid
difficulties related to the limestone calcination and improves production efficiency. The cost to
transport the inert part of the limestone from the quarry to the plant is also minimized. A limestone
rich in CaCO 3 will not only reduce solid matters in the effluent of the distillation unit but will also, for
those soda ash plants that have settling, reduce the volume of solids to be treated.
Particle size distribution of the limestone from quarries is generally between 40 and 200 mm.
The more homogeneous it is, the better the lime kiln will work but the greater the amount of limestone
fine by-product produced at the quarry. We decided to take lime stone from Puttalam, Aruwakkalu,
Eluwamkulam quarry.
5.4.3 Carbon for the Lime Kiln
Coke, and rarely coal, is used in lime kilns for soda ash production due to the necessity to
obtain the highest CO 2 concentration. Other type of fuels, natural gas or fuel oil, would result in a too
low CO 2 concentration in the kiln gas. This is important because the kiln gas is used further in the

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process for its CO 2 contents. Higher CO 2 concentration enables reduction of the equipment size and
ammonia losses.
The particle size distribution of the solid fuel has to be appropriate in order to get a
homogeneous distribution within the kiln.
Constituents
H 2 O [kg/t]
Volatiles [kg/t]
Fix carbon [kg/t]
Ashes [kg/t]
Net calorific value [GJ/t]

Coke
40 - 70
0 - 30
800 - 890
60 - 110
26.6 - 29.6

Table 5.2: Typical compositions for coke to the lime kiln

For the storage of coke requires no specific precaution other than normally adopted, that is
open ground storage.
5.4.4 Ammonia
The Solvay process for soda ash requires an input of ammonia to compensate for the inherent
losses from the process. The input is generally carried out as aqueous ammonia solution (10 to 35%),
or direct injection of anhydrous gaseous ammonia or by the use of an aqueous solution of ammonium
bisulfide. Ammonia addition may also be achieved by the use of ammoniacal liquor from coal gas
plants.
Storage of the aqueous ammonia solution in achieved in steel tanks. Specific precautions have
to be taken during works on the equipment, because some mixtures of air and NH3 are explosive when
in contact with a heat source or flame. When liquefied NH3 is stored, additional specific preventive
measures are required for safety.
5.4.5 Various additives
In addition to the major raw materials there are a number of miscellaneous raw materials which
may be added to the process for their various physical attributes: compounds to aid gas absorption,
compounds to avoid scaling, corrosion inhibitors, settling aids. These all may have minor potential
environmental

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5.5 Utilities
5.5.1 Steam
Steam is an important energy vector in the manufacture of soda ash by the Solvay process both
because of its mechanical capability (to drive a range of machinery including turbo generators, gas
compressors, vacuum machines,etc) and as a thermal energy carrier for distillation and drying. A
range of pressures and temperatures are therefore required to meet the process needs and to maximize
the energy efficiency of the process. LP steam is primarily used for ammonia distillation. The steam
process consumptions lie in the range of: 1300 to 2400 kg/t soda ash for recovery of ammonia
(depending of the applied process): The correctness of those values can be checked by material
balance calculations.

5.5.2 Process water


Basically, the main consumer of water (apart from brine) is the slaker where the lime coming
from the lime kilns reacts with water to produce milk of lime. The quantity is in the range of 1.9 to 2.4
m3/t soda ash. The quality requirement for this water is not high. It is normally taken at the outlet of
the cooling water system (warm water).
Soda Ash Process other water needs, soda ash require higher purity (absence of Ca and Mg
salts) for different uses as additional wash water to wash the sodium bicarbonate cake at the filter
outlet. The above quoted process water needs exclude the water entering the process in the form of
brine and steam condensate mainly partially condensing in the distillation tower.

5.5.3 Cooling waters


Many unit operations of the soda ash process are exothermic. The cooling agent is normally
cooling water in open or closed loop. The closed loop requires a cooling tower with special water
treatment. The open loop is the once-trough system using for example river water.
The total flow of cooling water required for,

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Lime kiln gas treatment

Carbonation towers

CO2 compression

Distillation

Absorption

Calcination

5.5.4 Electricity
The gas compressors can be driven by either electrical motors or steam turbines, leading to a
range of electrical consumption between 50 and 130 kWh/t soda ash. The necessary consumption for
compression is also linked to CO2 concentration. Cooling water consumption is minimized by
managing different cross flow heat exchangers.

5.6 Energy saving in the process


Within the plant itself, reductions of energy losses are obtained by favouring energy transfer
between flows at different thermal levels by the installation of heat exchangers and flash vessels for
hot fluids, several possibilities to reduce the energy consumptions are possible as far as the technology
and the economics allow.
At the level of the use of primary energy, the initial design stages have to verify the interest of
combined heat and power generation to improve the generation efficiency of electricity since the soda
ash plant acts as the final stage condenser. Primary energy efficiency is outside the scope of this
document.
Energy savings are achieved at two levels, namely,

Heat recovery

Minimization of consumption.

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5.6.1 Heat recovery


The recovery of heat has been gradually improved throughout the history of the process by
optimizing energy fluxes of different thermal levels contained in gas and liquids flowing through the
process.
Heat generated from the system is used to preheat different streams such as,

Pre heat the air before enter in to the kiln by using the heated CaO to reduce the coke
consumption.

Use kiln flue gas for calcinations of Sodium bicarbonate in the dryer, further the CaCO3 feed
also pre heated by using this remaining heat flow.

The inlet stream in to the kiln is heated by using exit stream from the striping column.

The heat absorbed cooling water is used for the shaking of the lime.

Mother liquor from the filtration to the recovery of ammonia by the distillation off gas.

5.6.2 Energy Minimization


The following techniques may be used to minimize energy consumption.

Careful control of the burning of limestone and a good choice of the raw materials allow a
reduction of the primary energy necessary for the operation.

Improvement of process control by the installation of distributed control systems.

Reduction of water content of the crude bicarbonate by centrifugation before calcination to


minimize energy need for its decomposition.

Back-pressure evaporation for calcium chloride liquors.

Equipment lagging, steam trap control and elimination of energy losses.

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Soda ash process major Input/output levels

Table 5.3: Soda ash process major Input/output levels

56

5.7 Process Flow Diagram

Compressor

Purified brine

Waste gas
CO2 from dissociation

Water

Flue gas

Gas Cooler
Waste gas

C
on
d
w en
at s
er ed

Recovered gas

Drier

Gas washing with


purified brine
Recovered gas

CaCO3

Cyclone

Brine

Preheated CaCO3

Ammonia
recovery unit
Makeup NH3

NH3 Absorption
Unit

Lime Kiln

Coke

Carbonator
Unit

End Product

Preheated Air

Air preheater

NaHCO3 Solution

Hot Air
Cool Air

Pump
Cooled CaO

Centrifugal fan

Waste water

Filter
Ammoniated brine water
Filtrate

pump

shaking of lime
Vaporizes water

Figure 5.3: Process Flow Diagram

Excess water

5.8 P & I Diagram

Figure 5.4: Pipe and Instrumentation

Chapter6

SITESELECTION&PLANTLAYOUT

CHAPTER 06

SITE SELECTION & PLANT


LAYOUT

Selecting a suitable site is the immediate step


after process is selected. Its a matter of mainly
the raw materials, market, infra structure, water
resources and impact on an adjacent ecologic
systems.
Process plants are complex facilities consisting
of equipment, piping systems, instruments,
electrical systems and control systems. The
design, engineering and construction of process
plants involve multidisciplinary team effort. Plant
layout and design of piping systems constitute a
major part of the design and engineering effort.
The objective is to design safe and dependable
processing facilities in a cost effective
manner.

Chapter6

SITESELECTION&PLANTLAYOUT

6.1 Introduction
The basis for the site of the proposed soda ash plant, according to the feasibility study of
Chapter 2 can be taken as availability of raw materials, geology, market, infrastructure, water
resources, cultural /social impact, ease of waste discharge and the impact on the adjacent ecological
systems. Also the process selected plays a major role in the location of the plant. The suitable location
for the proposed plant has been selected as a piece of bare land in Karadipuval near Puttalam (Figure
6.2). The facts that had led to the selection of this particular site for the proposed soda ash plant are
considered in the next section.
6.2 Site Selection Considerations

The process has been selected as Solvay process which uses concentrated brine and limestone
to produce soda ash. Therefore the availability of these raw materials is important in the site
selection. Brine is present all around the country. Since saturated brine is required the ideal
option is to place the plant close to a saltern. Presently salterns are present at Puttalam,
Muturagawela and Hambantota. Makeup ammonia for the plant will have to be imported. CO2
can be generated onsite by burning limestone. Limestone is available in Sri Lanka in 4 forms.
Miocene limestone is present in the land strip stretching from Puttalam to the Jaffna peninsula.
Dolomite reserves are present to the middle of the country. Areas well known in this aspect is
present in the Matale district. Also Calcium Carbonate can be found in the form of coral reefs
in various parts of the costal belt in Sri Lanka though this is not an environmental friendly and
feasible option. Also sea shells that is present in the coastal areas is a good form of Calcium
Carbonate but this is not a viable and secure raw material source for a soda ash production
facility of the proposed scale. The distribution of the limestone resources in Sri Lanka can be
seen in Figure 6.1. Therefore according to the availability of raw materials placing the plant at
Puttalam or Mutragawela is suitable. But Mutragawela is not an option because of the present
security threat.

When we consider the market availability in the Puttalam area no huge demand exists for soda
ash. But there is considerable potential that many industries will be built in the near future in
this area because of land availability and climate.

The population density of the area is very low. This has its advantages as well as
disadvantages. There amount of people affected by the plant would be less because of less
population while there would be difficulties in finding manpower for the construction phase
and the maintenance of the plant. But this problem can be dealt with by recruiting workforce
from other areas and developing a residential workforce.

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SITESELECTION&PLANTLAYOUT

The dry and sunny condition that is present throughout the year in this area is extremely
suitable for a process plant because loss of heat by cooling of process due to rain is avoided.
This also saves energy and makes it possible to obtain consistent product quality.

The geology and topology of the area has been assessed as being suitable for process plants
because of the solid soil condition. From the feasibility study done to assess the feasibility of
Norchcholai coal power plant it has shown that the area around Puttalam is one of the ideal
areas to construct huge plants and factories.

The possibility of a natural disaster like an earthquake, flood, etc occurring in this area is very
low. This is great advantage because the consequences of such an event will be very disastrous
for the plant.

When we consider the site at Puttalam a secure security situation has been prevailing for
several years. Also a tight security parameter presently has been set in the area because of the
presence of the Palavi air force base, and the security would be further strengthened once the
Norochcholai coal power plant has been commissioned. Therefore it can be said that the
security threat or risk is minimum.

There is a considerable amount of infrastructure development in the area. The port that is been
developed to assist the Norchcholai power plant will be of assistance in the process of
constructing the soda ash plant at the proposed site.

There is a sound network of roads in the area. These roads have withstood the constant
movement of container loads of cement and raw materials to and from the Holcim Cement
plant, salt laden trucks and food containers moving to the North.

The Puttalam lagoon has been naturally sited to assist a network of salt water canals. Most of
these canals lead to the salterns in the area. The white salt piles can be seen in close proximity
to the proposed land in figure 6.2. Also a canal network has been highlighted in light blue in
the diagram. The tanks with the mother liquor is just south of the proposed area.

Other infrastructure requirements like municipal water for general activities are available in the
area. Once the Norochcholai coal power plant is complete high tension lines from the plant will

Chapter6

SITESELECTION&PLANTLAYOUT

pass near these areas and connect to the National grid. Hence the capital cost that has to be
incurred in the event of power line erection in the construction phase will be less.

The plant will require a constant supply of limestone from a quarry at the North. The most
viable option would be to transport limestone via rail. Limestone for the Holcim cement factory
is brought through by rail carriages through a network of railroads from its quarry at
Aruwakkaru. Since the cement factory is present farther to the south of the proposed land as
seen the figure 6.2, the rail line from the quarry can be used to transport limestone to the soda
ash plant from a quarry at the north.

As mentioned in the technical feasibility the plant will require a source of process water. There
are several water streams flowing through the area which can be utilized. But the proposed site
has the option of using on-site water from the water pond that has been highlighted in figure
6.2 by a red circle.

Another great advantage of the selected site at Karadipuval is the availability of land for
expansion. There are several pieces of bare land across the main road to the west and adjacent
to the North and eastern boundaries of the proposed land. Also the availability of land can be
used to aid in the establishment of an effective waste disposal system.

Because the area is gradually transforming into an industrial area rather than an attractive
residential area the cost of land is low. Therefore the initial investment and cost for land in the
event of an expansion is low.

The proposed land has a main road on the western perimeter while it has remote roads on the
northern and the eastern boundaries. This is of great advantage because the access to the plant
will not be restricted.

A positive aspect of the proposed site is that it is not situated close to vegetation or agricultural
land. This is important because the impact on environment in the event of an unforeseen
incident is low.

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SITESELECTION&PLANTLAYOUT

Figure 6.1- Mineral Map of Sri Lanka

Chapter6

SITESELECTION&PLANTLAYOUT

Figure 6.2- Geographical map of proposed land

Chapter6

SITESELECTION&PLANTLAYOUT

6.3 Plant layout

Security Post

Office Area

Security Post
NH4 Recovery Unit

NH4 Absorption Unit

Gas Cooler

Gas washing
with brine

NH4 Storage

Brine purifying unit

Brine storage area


Control Room

Filter

Carbonator Unit

Cooling Tower

Na2CO3 Storage
Slaker of CaO

Product packing

Product Storage

Dryer

Boiler Room

CaCO3 Miller

Kiln
CaCO3 Crusher
Water Source

Crushed CaCO3 storage area

Security Post

Figure 6.3- Plant layout

CaCO3 Unload

Chapter7

ENVIRONMENTALIMPACTASSESSMENT

CHAPTER 07

ENVIRONMENTAL IMPACT
ASSESSMENT

Environmental impact assessment is the process


of identifying, predicting, evaluating and
mitigating the biophysical, social, and other
relevant effects of development proposals prior
to major decisions being taken and commitments
made.
This may include an assessment of both the
short and long term effects on the physical
environment, such as air, water and noise
pollution; as well as effects on local services,
living and health standards, and aesthetics.....

Chapter7

ENVIRONMENTALIMPACTASSESSMENT

7.1 Gaseous Effluents


7.1.1 Particulate Dust
Dust is emitted from the soda ash production in limited quantities, arising from the following steps:

handling of mineral raw materials (coke, limestone) as diffuse sources

limestone conversion in kilns, but in limited quantities or during abnormal operation since
all the gas is collected to a washing cooling step and thereafter is used in the carbonation
stage in a liquid solution

handling of soda ash and densification of light ash (hydration and dehydration) to produce
dense ash

during the handling of these products

It is common to use bag filters or wet scrubbers which significantly reduce the levels of dust
emitted to atmosphere. Roughly the dust emitted is around 0.10-0.15 kg of dust/t soda ash, and
represents a typical quantity of 50-75 t/year.
The composition of the dust reflects the composition of material handled, those are,

C from coke

CaCO 3 , Al 2 O 3 and SiO 2 from limestone, sand and clays

CaO from burnt lime

Na 2 CO 3 and NaHCO 3 from soda ash and sodium bicarbonate production and transport

The most stringent environmental regulations in western countries require limit values of 40
or 50 mg/Nm3 for atmospheric emission of dust.

7.1.2 Carbon dioxide and monoxide


During the burning of CaCO3 to CaO inside the limekilns, CO and CO2 are produced from the
combustion of coke and from the decomposition of limestone. A normal Solvay process needs an
excess of CO2 above that which is stoichiometrically required. Some of the excess is required to
compensate for non ideal absorption of CO2 in the carbonation towers.
Carbonating towers also have an outlet for the discharge of gases that have not reacted in the
process. This gas is cleaned with brine in a washer to recover NH3 and possibly H2S, if present, and to

Chapter7

ENVIRONMENTALIMPACTASSESSMENT

reintroduce these components back into the process, while CO2, CO and other inert gases pass out to
atmosphere.
7.1.3 Nitrogen oxides
NOx are produced inside the kiln by oxidation of nitrogen during the combustion. Since the
temperature inside the kiln are moderate (up to 1100C), the formation of NO x is rather limited.
Measurements in some plants indicate concentration after washing less than 500 mg NOx/m3.
7.1.4 Sulfur oxides
SOx are produced by the oxidation of sulfur containing compounds in the limestone and coke.
7.1.5 Ammonia
The soda ash production emissions of NH 3 represent only 0.2- 0.4 % of all emissions. The
main atmospheric emissions containing ammonia originate from the bicarbonate precipitation and
filtration stages of the process.

From precipitation of bicarbonate in carbonation tower after cleaning in a tower washers

From filtration of bicarbonate, after cleaning in filter washers

In addition they are a number of diffuse losses of ammonia from filters, bicarbonate
conveyors and from the handling and processing of the distillation effluent.

The emissions fluctuate due to,

Performance of the stripping columns and operating parameters control (height, steam
injection, temperature control, monitoring of outlet concentrations)

Disturbances in the mother liquor feed (flow rate, composition)

Normally the emitted gaseous load is on average of 0.55kg NH 3 /t soda ash but the spread can
be very large, from 0.09 up to a typical range of 0.6 to 1.5 kgNH 3 /t soda ash from the production unit,
representing a release into the environment of 30 to 750 t/year for a 500 kt/year soda ash unit.
Considering the turnover in the process, the loss rate of ammonia in the process is therefore very low.

Chapter7

ENVIRONMENTALIMPACTASSESSMENT

7.1.6 Hydrogen sulfide


In some plants H 2 S may be added as a corrosion inhibitor, in the form of sodium hydrogen
sulfide. Emission sources are from the tower gas washers and H 2 S is typically controlled at maximal
emission levels of 5 to 15 mg/Nm3.

7.2 Gaseous Effluents Management


7.2.1 Calcinations of Limestone
The calcination of limestone produces CaO and CO 2 and is designed to maximize the CO 2
content by minimizing the presence of oxygen in the outlet gas. A conventional ammonia soda process
produces about 30 % more CO 2 than theoretically needed and it is necessary to purge some of the CO 2
produced to the atmosphere.

Further excess CO 2 may be beneficially used in sodium bicarbonate production. Any


surplus CO 2 is vented as kiln gas to atmosphere. If there is an associated sodium
bicarbonate plant then this gas wasting can be reduced or avoided. But we havent such
plant. So by optimizing the process we should reduce the amount of excess CO 2 .

CO gas is virtually inert through the process. All CO produced must therefore be vented to
the atmosphere either at the kilns or through the carbonation tower after gas scrubbers.

Furthermore, provided the dispersion of CO and CO 2 is adequate and the stack construct
according to the standard conditions, no local impact on the environment or health are
expected or experienced.

Atmospheric emissions of SO 2 from the lime kilns are low. Because the concentration of
sulfur in the fuel (coke) and the limestone employed is very low.

The formations of SO x are limited due to low sulfur content of fuels used and some auto
purification reactions in the lime kilns. The small amount of SO 2 produced tends to be
fixed by CaO and CaCO 3 as CaSO 4 furthermore ,SO x in the kiln gas sent to the process
are absorbed.

Before discharge to the atmosphere, kiln gas may be cleaned and generally cooled at the
same time by washing towers.

Considering the type of release the very low persistence of ammonia into the atmosphere
due to its high solubility in rainwater and its rapid turnover into the ecosystems by
biological nitrification/ denitrification mechanisms, the local or regional environmental
impact trouble is to be considered as very low

Chapter7

ENVIRONMENTALIMPACTASSESSMENT

Alternatively, gas cleaning systems (normally bag filters) can also be used to collect the
dust as dry material. If dry cleaning is used, residual material is made of fine particulates
containing limestone, lime, coke. This can be collected separately and may be disposed
without further treatment. However this type of gas cleaning is difficult to operate because
the lime kiln gas may be too hot for the filtering media.

7.2.2 Precipitation of Crude Sodium Bicarbonate


Outlet gas from the carbonation columns is subjected to a cleaning process with brine in a
packed or plate washer to recover NH 3 and possibly H 2 S and recycle them into the process via the
feed brine.
Washers may have an optional final water washing section to minimize emissions. This type of
equipment has been designed to meet the specific needs of the process and to allow efficient recycle of
valuable raw materials. Other way round the emissions to the atmosphere also is reduced.

7.2.3 Filtration of the Bicarbonate


Air containing ammonia from the filtration step of crude sodium bicarbonate undergoes a
cleaning process with brine in a washing tower to recover NH 3 and reintroduce it to the process.

7.2.4 Conveying and Storage of Soda Ash


Storage of light and dense soda ash is achieved in large silos equipped with dedusting systems,
which keep the products dry and isolated and prevent dust emission to the atmosphere.
Because of the nature of conveyers, elevators, air lock valves, etc. the soda ash process
typically uses a range of high efficiency bag filters to separate dust from vent gas streams.

Chapter7

ENVIRONMENTALIMPACTASSESSMENT

7.3 Liquid Effluents


The sources of liquid effluent from the soda ash process are typically,

Wastewater from the distillation (after treatment).

Wastewater from the brine purification.

Cooling waters from lime kiln gas washers.

Cooling water in the CO 2 compression loop.

Cooling water of the absorption and distillation towers and calcinations.

7.3.1 Wastewater from Distillation


Flow rates and concentrations for the major components present in the liquid outlet of
distillation. These indicative ranges represent distiller effluent prior to any form of treatment and
should not necessarily be considered as levels or concentrations emitted to the environment.

Table 7.1: Rough concentrations of the waste water from the distillation column

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ENVIRONMENTALIMPACTASSESSMENT

Some additional low quantities of calcium sulfate (CaSO4), calcium hydroxide (Ca(OH)2) and
trace elements are also present. Traces of heavy metal originating naturally from raw materials are
related to limestone, coke and salt composition; the process in itself does not add heavy metals. Given
the alkaline nature of wastewater emissions, metals are in major part insoluble and are included as part
of suspended solids. According to its composition, the suspended solids are classified as nonhazardous.

7.3.2 Wastewater from Brine Purification


Brine purification wastewater is basically brine with suspended precipitated CaCO3 and
Mg(OH)2 in variable proportions according to the nature of the salt deposits (calcium and magnesium
ions coming naturally from the original sea water).
These solids can be treated separately or can be disposed together with liquid effluent from the
distillation unit for solid removal and treatment.

Table 7.2: Typical concentration wastewater from brine purification

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ENVIRONMENTALIMPACTASSESSMENT

7.4 Liquid Effluent Management


Wastewater discharge treatment is the environmental aspect in which significant differences
arise from one production plant to another. Apart from cooling water, aqueous emissions of soda ash
production plants are characterized by a high concentration of suspended solids and dissolved salts.
These solids and salts are unreacted lime stones and salts of natural origin.
Suspended solids and dissolved salts originate from three different steps of the process.

Brine purification

Ammonia recovery

Cleaning of CO2 originating from calcination of limestone

In most soda ash production plants, brine purification effluent is discharged jointly with
effluent originating from the distillation unit. The typical composition varies according to raw
materials quality.
However different treatment schemes have been developed according to geographical location
of the production plants and the requirements of the local regulatory authorities.

Options available for treatment of these effluents are:

Direct discharge of raw effluent, with or without partial removal of some fraction of the
solids, and with or without preliminary pH adjustment

Indirect discharge of waste water after removal of suspended solids and with or without
preliminary pH adjustment

Further treatment to produce by-product such as CaCl 2

7.4.1 Liquid Effluent Treatments


According to production plants location and raw materials deposits, two basic lines are
established for the suspended solid treatment.

Total dispersion

Separation of the suspended solids and liquid dispersion.

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ENVIRONMENTALIMPACTASSESSMENT

7.4.1.1 Total Dispersion


Total dispersion is employed when production plant is close to the sea or high flow rivers. We
decided to establish our plant close to the sea and we can use this method.
This technique ensures that the solid material is incorporated with the natural sediments of similar
composition. Chlorides and other soluble salts present in the liquid fraction are dispersed in a medium
(in the sea). The environmental impact is minimal due to the similarity between the chemicals present
in the receptor medium and in the discharged material (chloride, sodium, calcium as ions).

7.4.1.2 Separation of the Suspended Solids and Liquid Dispersion


Separation of the suspended solids and liquid dispersion has generally been used where there is
no suitable environmental medium to allow for total dispersion. This method involves the physical
separation of liquid and solid phases. The liquid phase is then discharged to a local watercourse with or
without pH adjustment as appropriate and solids are used to build up the settling basin itself. The
underground deposition of the solids is carried out when salt deposits are found near production plants
and when deposit characteristics and the salt extraction system enables it.

Settling ponds
The clarification by liquid/solid separation large quantities of suspended solids in aqueous
effluents is usually achieved in settling ponds. Fines of lime stones or solid particles settled in the
basin can be used to build up the walls as the deposit in the basin accumulates
The aqueous outfall is collected at several points through separators and drainage pipes to a
secondary channel collecting all outfalls of drainage.

The location of settling ponds depends on several factors.

Area available for permanent long term land occupation

Distance between factory and final discharge point

Underground geological and hydro geological characteristics

Landscape impact.

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ENVIRONMENTALIMPACTASSESSMENT

7.4.2 Liquid Effluent Discharge Management


The impact of direct discharge of the liquid phase containing soluble salts in rivers is linked to
the flow rate of the receiving rivers, the fluctuations of it and the inherent qualities of the water
including its natural salinity.

Management of equalization basins


The management of buffer equalization basins can be optimized by continuous monitoring of
flow rate and chloride concentration in the receiving water, after complete mixing, controlling the
daily discharge to be allowed.

Adjustment of pH
The typical value of pH of raw effluent is higher than 11.5 due to the alkalinity of OH ions
from Ca(OH)2. Theoretically the pH adjustment of such an effluent can be achieved by,

Mixing, in open channels or basins, with natural or raw waters containing dissolved
bicarbonate.

Reacting with gas containing CO2 in pH adjustment columns.

Other pH adjustment mechanisms if acid solutions or acids wastewaters are available.

In practice, the pH adjustment of soda ash wastewater is usually achieved by mixing with
natural water according to the following mechanism:
Ca(OH) 2 + Ca(HCO3) 2

2 CaCO 3 .+ 2 H 2 O

Wastewater is mixed with available natural water (cooling waters after use or surface waters:
river, channel, lake, sea or underground water,) in a typical ratio natural water/wastewater at 5 to 10:1.
The formed CaCO3 particles are discharged or settled in ponds.
Appropriate hydraulic retention time for settling in quiescent waters is usually 6 to 8 hours.
Periodic removal of settled particles is achieved. This method offers numerous advantages: pH
adjustment mechanism is efficient and reliable; no consumption of supplementary reactants is needed.
The settled particles are inert.

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ENVIRONMENTALIMPACTASSESSMENT

7.5 Solid Effluents


The typical solid wastes produced by the soda ash process

Fines of limestone

None recycled stone grits at slaker

7.6 Solid Materials Management


7.6.1 Limestone Fines
After crushing, the limestone is passed through a sieve in order to remove the fine gravel
fraction which could be a cause of plugging and bad distribution of combustion air in the lime kiln.
The fines composition is 85% to 97% CaCO 3 with impurities of sand, clays ( SiO 2 , Al 2 O 3 )
depending on the limestone composition in the deposit
Since the composition of the limestone fines is the same as or close to raw limestone, this
material can be used without any restriction for civil engineering works and filler material for roads,
highway, and for cement manufacturing. Within the selected area of our plant the cement
manufacturing plant (Holcim) has located and we can sell it to them.
In some existing soda ash factories it is mainly used for internal purposes (walls of the dikes,
roads in quarry operation). Higher specification would require a further separation of gravel and clay
material by water washing.

7.6.2 Grits from slaker


Some under burned stone, due to imperfect conversion reaction inside the kiln, are drawn with
the lime to the slaker. The coarser unburned stone can be separated at the slaker and is sent back to the
kiln.
The smaller sizes of unburned stone are rejected and the very fine material is suspended in the
milk of lime and simply passes through the distiller and out in the distiller waste liquid. The unburned
stone contains most of the impurities and pieces of silica present in the limestone feeding the kiln.
The composition of grits from slaking operation enables recycling of this product to the lime
kiln, reuse of it as soil conditioner for pH correction or as filler for concrete. A milling step is required
to adjust the particle size distribution, as fine as possible for soil conditioning or as regular as possible
for concrete incorporation.

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ENVIRONMENTALIMPACTASSESSMENT

7.7 By-Products Recovery and Reuse


By-products recovery and reuse can be done as an alternative of the total discharge method.
The manufacturing of soda ash by the Solvay process enables two main co-products.

Calcium chloride

Sodium bicarbonate

7.7.1 Calcium Chloride


Outlet liquor from the distillation unit contains primarily CaCl 2 in solution in quantity
corresponding to sodium carbonate production. By treating this liquid by removing suspended solids
and dissolved sodium chloride, a pure solution of calcium chloride can be obtained.
By successive concentration steps in evaporators, the solution is concentrated from 11% to
40% and by further concentration up to around 78% CaCl 2 , to produce a white solid hydrated flake,
which has to be dried, stored and it can be used for several applications.
The recovery of CaCl 2 dissolved in wastewater from distillation requires a large amount of
energy mainly in the form of steam to concentrate the diluted solution to solid CaCl 2 . Moreover, the
market for CaCl 2 is also limited. So the CaCl 2 recovery units operating in soda ash plants has
progressively decreased.

Chapter8

SAFETYMEASURES

CHAPTER 08

SAFETY MEASURES

Safety first is a common set of words that you


can see any where around. As far as the
production industries are concerned, physical,
chemical and operational safety are some the
major issues which should be analyzed and
monitored thoroughly for the whole plant and
equipment wise well.....

Chapter8

SAFETYMEASURES

8.1 Plant Safety


Industrial processing plant may lead to accidents that unexpectedly interrupt the work process
carry the potential for damage, injury - or even death. Hazardous conditions also can cause loss of
material or property or decrease a company's production capability. But many of those accidents can
be avoided all together by implementing proper safety program in the plant and following through with
it.
Safety program of our caustic soda plant should include general safety practices which are
common to all kind of plants and unique safety practices due to its process, equipments and materials.
Also safety program should include plans to fight accidents when it occurs.

8.2 General Plant Safety


Plant location is important in safety point of view when considering the impact of the
environment to the plant and its activities. Plant should be located at a place where inhabitants are
interested in its success, the product can be sold profitably and production is in minimum cost.
Selecting the location and reasons for the selection is described in detail in Chapter 6.
Plant layout is a fundamental of every plant which strongly linked to safety aspects. Layout
planning plays a key role in the inherent safety performance of process plants since this design feature
controls the possibility of accidental chain-events and the magnitude of possible consequences. In
order to obtain safe layout to the plant following points should be considered. Plant layout is described
in detail in Chapter 6.

Considering safety practices spaces between different areas and equipments need to be taken in
to account when deciding the layout.

Proper interconnecting paths should be included in the layout.

Access points, walking ways and emergency exits need to be clearly indicated.

There should not be hard to access areas in the plant.

As lime kiln handle a temperature around 1000C it should be positioned away from the other
equipments.
Common safety measures for the plant are as following.
Visual indicators should be used in appropriate places in order to express information,
directions and warnings. Each equipment including vessels, pumps, heat exchangers, distillation
columns, furnaces, valves ect. And sub components of those) should be labeled and coded in order to
identify easily. There should be isolation valves for equipments in order to use in maintenance or

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SAFETYMEASURES

emergency and safety valves should be used so that accidents due to pressure increment can be
avoided. Identified risky areas and hazarders areas should be isolated and indicated through standard
indicators (warning signs). If any maintenance is going on or if there any special tests going on (ex: Xray test) those areas also need to be indicated with warning signs. In maintenance standard safety
procedures should be followed. Rotating equipments and sharp edges should be covered appropriately
in order to prevent accidents. Hot surfaces should be labeled with warning signs.
All the parameters which related to safety (vibrations, noise, efficiency of equipment, and
compositions of air, pressures in pipelines & vessels ect.) of the plant should be recorded as practical
and analyzed to identify trends. Measuring instruments should be standardized time to time in order to
maintain the accuracy. Measuring equipments should have proper positioning and lighting in order to
get the reading easily and accurately. Rotating equipments and moving parts should get a special care.
Those should be lubricated and tested regularly to make sure the long life of the equipment and safety.
Inspections should be done time to time in order to identify material and energy leaks and should take
corrective actions. Electrical wires should have a proper and full insulation.
Automated alarm system should be implemented in the plant which activate out of the given
safe region, so that it announce hazards situations when they occur, that may help to reduce the
damage. Automated alarm system can be integrated with isolation valves and safety valves to assure
more safety in the plant. Those equipments should be standardized time to time in order to keep the
accuracy.
Proper drainage system is important for safety in disposing materials. To avoid static electricity
all electrical equipment and metal components should be earthed. Buildings, structures, supporters and
equipments should have a proper strength to barer its load at work. High platforms, staircases and
ladders should be in the standards and should be properly maintained. Highly toxic or flammable or
radioactive materials should be stored in special areas. Special areas inside the plant should be
separated by appropriate arrangement, if those areas need special authentication to enter, doors/gates
and fences can be used. Whole plant or the land should be protected by appropriate fences and security
system.
Emergency showers and eye wash bottles should be provided. Instructions about personal
protective equipments should be worn in each area should be displayed. Mobile phones, lighters and
smoking will be prohibited in the plant area to reduce the risk of accident.

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SAFETYMEASURES

8.3 Personal Safety


There employees should be trained and audited continuously about the proper use of personal
safety equipments and safety practices. Employees should be promoted to behave safely. Commitment
of top management and employees to the safety program is vital to its success.
Personal Protective equipment (Safety glasses, safety helmet, Earplugs, gloves, overall, boots,
safety shoes, safety belts) must be worn in the plant according to the job the employee involve and the
area he/she work. Loose clothing or jewelry should not be worn when operating machinery. All guards
provided must be in place before machine operation. Always machine should be turn off before
adjusting, cleaning, lubricating or repairs. Aisles, doors, fire extinguishers or electrical power panels
should not be blocked. Given instructions should be followed in disposing materials. No food or drink
is permitted in the plant. Employee should not be drunk during the work hours. Seat belts must be
worn by the driver and all passengers of company owned or leased vehicles.

8.4 Safety Aspects of Equipments


8.4.1

Lime Kiln

The Kiln handles high temperature and high amount of heat in its operation. Because of the
high temperatures, firing a kiln also does release volatiles into the air, many of which are toxic. The
kiln should have a proper insulation system which reduces heat transfer to the environment. It may
help to improve the kiln efficiency and reduce the adverse effect on environment. Even when the kiln
has more than adequate insulation, its outer surface can become hot enough to seriously burn someone
if touched or brushed against with bare skin.

Kiln mitts or gloves should be worn when handling any part of a kiln (other than a control
panel) while it is firing or cooling. Even after power or fuel has been turned off, kilns will
remain hot for hours. Do not open or touch until fully cooled.

Dark glasses from a safety supply house are recommended when looking into kiln spy holes.
These protect your eyes from the radiant heat. (Please note that regular sunglasses are
inadequate for this purpose and may actually melt.) Protective glasses may also allow you to
see your cone packs more clearly.
The kiln should properly vent to the outside. Every firing releases gases which will be irritating

to the body; they may also be toxic or even lethal if safety measures are not followed.

Follow the kiln manufacturer's instructions and use a licensed heating, ventilation and airconditioning (HAC) contractor for proper installation.

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SAFETYMEASURES

HAC contractors have equipment to accurately test the adequacy of the systems ventilation.
Light a match in front of the kiln's hood. If the system is working properly, the hood draw
should blow the match out.

Always turn on your kiln hood or vent prior to loading to prevent ceramic glaze dust exposure.
Gases given off by kilns when firing can cause respiration problems. This is possibility is

heightened if it is a reduction or salt firing. Specific gases to be aware of are:

Carbon dioxide is given off during any fuel-burning firing. Overexposure leads to blood
oxygen levels falling, a decrease in hearing and pulse rate, and a rise in blood pressure.

Carbon monoxide is released during reduction firing. Exposure can lead to headache, dizziness,
fatigue, and drowsiness. Carbon monoxide can be lethal.

Sulfur dioxide can be released when firing soluble metal salts; it is a strong lung irritant.

8.4.2

NH3 Absorbing Unit

As the ammonia absorbing tower handles brine ammonia and carbon dioxide, which create
favorable condition to corrosion, the contact surfaces should have the property of corrosion resistant.
Sprinklers and the tower should be able to withstand the load and safety valves should be fixed in
order the act in pressure increment. There should be a proper drainage system to remove the liquid in
order to empty the column. Column should be washed and purged with steam before entering for
inspection or repair.
Ammonia reacts corrosively with all body tissues so it is dangerous to allow contaminate air
with ammonia. Even liquid output of the Ammonia absorption unit can release ammonia to the air
when in expose to the environment.

Before entering to the area gas tight chemical goggles or full-face piece respirator, gloves made
of any suitable material should be worn.

Level C respiratory protection with full face piece or self-contained breathing apparatus should
be available for emergency use. Air purifying respirators must be equipped with suitable
cartridges.
As ammonia has a flammable property the tower should be separated from high temperature

(especially kiln) to reduce fire risk.

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SAFETYMEASURES

8.4.3

Carbonator Unit

A safety aspect for the carbonator unit is much similar to the NH 3 absorbing unit because both
units handle similar chemicals and similar operations.
Carbonator unit has a cooling system which improves the efficiency of absorption. If the
cooling water fails to supply the operation in the carbonator should be stopped in order to prevent over
heating due to exothermic carbonization reaction.
8.4.4

NH3 Recovery Unit

Same as the NH 4 absorption unit and carbonator unit, the NH 4 recovery unit handles similar set
of chemicals. Unlike absorption in NH 4 absorption unit desorption occur here. So the safety aspects for
the units are also similar.
NH 4 recovery unit has a heating unit which directly injects steam in to the column to provide
required temperature to carry its operation. Safety steps should be followed in handling steam.

8.4.5

Drier

Dryer handles high temperature level (around 200C) in its operation which can lead to instant
fire if supply oxygen level goes up. So oxygen level should be monitored and CO 2 purging should be
fixed to use in an emergency. It will be very helpful if CO 2 purging is automated with oxygen set
level.
Air streams flow in the dryer is in high temperature and very low (theoretically zero) in oxygen
so it is dangerous to directly contact the flow. Appropriate actions should be taken to prevent such
situations. Workers should be trained to deal with dryer. Dryer room should have proper ventilation.
Pressure protections should be there to withstand pressure fluctuations inside the dryer.
As the dryer handles high temperature in its inside, so there should be a proper insulation
system. But although there is insulation the outer surface will be hot, workers should be informed not
to contact outer surface of dryer and bare skin.

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SAFETYMEASURES

8.4.6

Storage Vessels

8.4.6.1

Ammonia

If Ammonia store in insulated tanks those should be refrigerated and stored in low-pressure
tanks. Generally structure should be fire resistant, separated from work areas. It is important to keep
storage area dry and cool and away from steam pipes, heating devices, and tanks containing flammable
liquids.
If Ammonia stored outside in an uninsulated tank must be painted with reflective paint, which
controls rust or corrosion, and helps keep the temperature and internal pressure lower during hot
weather.
8.4.6.2

Soda ash

Bag Storage Soda ash tends to cake when exposed to moisture or the atmosphere for a long
time. Dense soda ash does not cake as readily as lighter density products. Typically, the soda ash layer
at the bag surface will begin to dissolve in a bag exposed to adverse conditions. Caking occurs because
not enough water is present to dissolve the soda ash completely. Because caked soda ash has less
surface area than the powdered product, the caked product does dissolve readily.
Normal warehouse storage of soda ash seldom presents caking problems, especially if the
oldest stock is used first. For best results, soda ash should not store in a damp or humid place or where
there is excessive air circulation.
Warehouse floors should be dry, smooth, free of breaks and able to support concentrated loads,
especially when bags are tiered or handled with forklift trucks (nearly the entire weight of a loaded
forklift falls on the two front wheels). Table 6-1 lists approximate floor areas, space requirements and
floor loadings for warehousing soda ash in bags.
8.4.6.3

Baking soda

In between Carbonator and filter there is a NaHCO 3 storage tank. NaHCO 3 is in sludge state in
the storage. When baking soda is stored as slurry, it may be convenient to store it in a tank.
8.4.6.4

Calcium Carbonate and Calcium Oxide

Calcium Carbonate and Calcium Oxide can be stored in dry sheltered open yards. But material
should not be subjected to humidity or rain, especially Calcium Oxide (it react with water). if there is a
risk of contaminating with water it is better to store I store rooms.

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SAFETYMEASURES

8.4.7

Pipelines

All the pipelines should be inspected continuously for leaks, damages ect. If any of these
failures noticed proper actions should be taken to correct it. There should be a proper insulation to
reduce energy loss to environment and avoid hot and cold surfaces. Dangerous surfaces should be
indicated with slandered sign.

8.5 Safety Aspects of Chemical


Similar to any processing plant this plant also involve with number of chemicals in its process
and tastings. Those chemicals should be clearly labeled and details of the chemicals should be kept in
order to refer any time. All the chemical should be stored according to their safety regulations. And
safety regulations also should follow in transportation and usage. If there any spillage or contamination
occurs recommended procedures should be followed in order to remove the adverse effect on health
and environment. Employees should be trained to handle each chemical.
8.5.1

Carbon Dioxide (CO 2 )

Hazard Identification

High concentrations may cause asphyxiation.

Slightly corrosive in the presence of moisture.

Solid carbon dioxide is white and when in direct contact with the skin will cause acute cold
damage to skin cold burn.

Health Effects &First Aid Measures


Inhalation:

Symptoms may include loss of mobility/consciousness. Victim may not be aware of


asphyxiation. Low concentrations of CO2 cause increased respiration and headache. Remove
victim to uncontaminated area wearing self-contained breathing apparatus. Keep victim warm
and rested. Call a doctor. Apply artificial respiration if breathing stopped.

Skin/eye contact:

Ingestion is not considered a potential route of exposure.

Ingestion:

Ingestion is not considered a potential route of exposure.

Handling And Storage

Below 30C only use low temperature carbon steel, austenitic stainless steels, aluminum,
copper and their alloys.

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SAFETYMEASURES

If carbon dioxide is dissolved in water, particularly at elevated pressures and in the presence of
oxygen, use materials resistant to carbonic acid, e.g. stainless steel or Monel.

Keep container below 50C in a well ventilated place.

Stability And Reactivity

Stable under normal conditions.

Disposal Considerations

Do not discharge into any place where its accumulation could be dangerous. Discharge to
atmosphere in large quantities should be avoided.

Toxicological Information

High concentrations cause rapid circulatory insufficiency.

Symptoms are headache, nausea and vomiting, which may lead to unconsciousness.

Carbon dioxide is mildly toxic, with no cumulative effects.

Permeable Exposure Limit

TLV-ACGIH-5000 ppm TWA

TLV-ACGIH-30,000 ppm STEL

Personal Protective Equipments

Safety goggles or glasses as appropriate for the job.

Protective gloves of any material appropriate for the job.

Positive pressure air line with full-face mask and escape bottle or self-contained breathing
apparatus should be available for emergency use.

8.5.2

Ammonia (NH 3 )

Hazard Identification

Irritating or corrosive to exposed tissues.

Inhalation of vapors may result in pulmonary edema and chemical pneumonitis.

Slightly flammable.

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SAFETYMEASURES

Health Effects &First Aid Measures


Inhalation:

Corrosive and irritating to the upper respiratory system and all mucous type tissue. Depending
on the concentration inhaled, it may cause burning sensations, coughing, wheezing, shortness
of breath, headache, nausea, with eventual collapse.

Inhalation of excessive amounts affects the upper airway (larynx and bronchi) by causing
caustic-like burning resulting in edema and chemical pneumonitis. If it enters the deep lung,
pulmonary edema will result. Pulmonary edema and chemical pneumonitis are potentially fatal
conditions.

Conscious persons should be assisted to an uncontaminated area and inhale fresh air. Quick
removal from the contaminated area is most important. Unconscious persons should be moved
to an uncontaminated area, given mouth-to-mouth resuscitation and supplemental oxygen.
Keep victim warm and quiet. Assure that mucus or vomited material does not obstruct the
airway by positional drainage.

Skin/eye contact:

Mild concentrations of product will cause conjunctivitis. Contact with higher concentrations of
product will cause swelling of the eyes and lesions with a possible loss of vision.

Mild concentrations of product will cause dermatitis or conjunctivitis. Contact with higher
concentrations of product will cause caustic-like dermal burns and inflammation. Toxic level
exposure may cause skin lesions resulting in early necrosis and scarring.

If contact eye(s) flush contaminated eye(s) with copious quantities of water. Part eyelids to
assure complete flushing. Continue for a minimum of 15 minutes.

Remove contaminated clothing as rapidly as possible. Flush affected area with copious
quantities of water. In cases of frostbite or cryogenic "burns" flush area with lukewarm water.

Ingestion:

Ingestion is not considered a potential route of exposure.

Handling And Storage

Use only in well-ventilated areas.

Do not drag, slide or roll cylinders. Use a suitable hand truck for cylinder movement.

Use a pressure regulator when connecting cylinder to lower pressure (<500 psig) piping or
systems. Do not heat cylinder by any means to increase the discharge rate of product from the
cylinder.

Store in cool, dry, well-ventilated area away from heavily trafficked areas and emergency exits.

Do not exceed temperature 125oF (52oC).

Chapter8

SAFETYMEASURES

Stability And Reactivity

Unstable

Disposal Considerations

Do not attempt to dispose of residual waste or unused quantities.

Toxicological Information

Genetic mutations observed in bacterial and mammalian test systems.

Toxic effects to the respiratory system, senses, liver, kidneys and bladder observed in
mammalian species from prolonged inhalation exposures at above 100 ppm.

Permeable Exposure Limit

TLV-ACGIH-25 ppm TWA

TLV-ACGIH- 35 ppm STEL

Personal Protective Equipments

Gas tight chemical goggles or full-face piece respirator.

Protective gloves made of any suitable material.

Level C respiratory protection with full face piece or self-contained breathing apparatus should
be available for emergency use. Air purifying respirators must be equipped with suitable
cartridges.

8.5.3

Sodium Carbonate (Na 2 CO 3 )

Hazard Identification

Hazardous in case of skin contact (irritant), of eye contact (irritant), of ingestion, of inhalation
(lung irritant).

Health Effects &First Aid Measures


Inhalation:

Inhalation of excessive amounts affects the upper airway (larynx and bronchi) by causing
caustic-like burning resulting in edema and chemical pneumonitis. If it enters the deep lung,
pulmonary edema will result. Pulmonary edema and chemical pneumonitis are potentially fatal
conditions.

Conscious persons should be assisted to an uncontaminated area and inhale fresh air. Quick
removal from the contaminated area is most important. Unconscious persons should be moved

Chapter8

SAFETYMEASURES

to an uncontaminated area, given mouth-to-mouth resuscitation and supplemental oxygen.


Keep victim warm and quiet. Assure that mucus or vomited material does not obstruct the
airway by positional drainage.
Skin/eye contact:

Skin contact cause irritant.

In case of contact, immediately flush skin with plenty of water. Cover the irritated skin with an
emollient. Remove contaminated clothing and shoes. Cold water may be used. Wash clothing
before reuse. Thoroughly clean shoes before reuse. Get medical attention.

Eye(s) contact cause irritant.

Check for and remove any contact lenses. In case of contact, immediately flush eyes with
plenty of water for at least 15 minutes. Cold water may be used.

Ingestion:

Do NOT induce vomiting unless directed to do so by medical personnel. Never give anything
by mouth to an unconscious person. Loosen tight clothing such as a collar, tie, belt or
waistband. Get medical attention if symptoms appear.

Handling And Storage

Do not ingest. Do not breathe dust. Wear suitable protective clothing. In case of insufficient
ventilation, wear suitable respiratory equipment. If ingested, seek medical advice immediately
and show the container or the label. Avoid contact with skin and eyes. Keep away from
incompatibles such as acids.

Hygroscopic. Keep container tightly closed. Keep container in a cool, well-ventilated area. Do
not store above 24C (75.2F). Hygroscopic

Stability And Reactivity

The product is stable.

Disposal Considerations

Waste must be disposed of in accordance with federal, state and local environmental control
regulations.

Toxicological Information

Routes of Entry: Inhalation. Ingestion.

Acute oral toxicity (LD50): 4090 mg/kg [Rat].

Acute toxicity of the dust (LC50): 1200 mg/m3 2 hours [Mouse].

Effects on Humans: May cause damage to the following organs: upper respiratory tract, skin,
eyes.
Hazardous in case of skin contact (irritant), of ingestion, of inhalation (lung irritant).

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SAFETYMEASURES

Permeable Exposure Limit

LDL (Lowest Published Lethal Dose) [Man] - Route: Oral; Dose: 714 mg/kg

Personal Protective Equipments

Splash goggles. Lab coat. Dust respirator. Be sure to use an approved/certified respirator or
equivalent. Gloves.

Personal Protection in Case of a Large Spill: Splash goggles. Full suit. Dust respirator.
Boots. Gloves. A self contained breathing apparatus should be used to avoid inhalation of the
product. Suggested protective clothing might not be sufficient; consult a specialist BEFORE
handling this product.

Chapter9

MATERIALBALANCE

CHAPTER 09

MATERIAL BALANCE

Material balances are based on the fundamental


law of conservation of mass. In particular,
chemical engineers are concerned with doing
mass balances around chemical processes.
Doing a mass balance is similar in principle to
accounting. In accounting, accountants do
balances of what happens to a Companys
money. Chemical engineers do a mass balance to
account for what happens to each of the
chemicals that is used in a chemical process.....

Chapter9

MATERIALBALANCE

This chapter contains the material balance for the process we designed. There are number of
assumptions and those are described in appropriate places. Some values are extracted from literature
and those are mentioned in reference.
This calculation based on 50Mg (tons) of product (Na 2 CO 3 ) output per day. All the rates are given in
daily basis and havent mention in calculations. Most of the flow rates are calculated in mole.
9.1 Product Specification
Ingredients
Na 2 CO 3
Na 2 SO 3
Moisture and impurities

Percentage
99.5%
0.004%
0.495%

Table 9.1- Soda ash specification

Average molar weight of product

= (10630.995) + (1830.005) + (14230.000042)


= 105.566 g/mol

Production rate

= 50000kg/day

Production rate in kmol

/
.

= 473.6375kmol/day
Note: We used Microsoft Excel in our calculation and its goal seek function was used to do the calculation
targeting above calculated flow rate by varying total NH 3 input to the NH 3 Absorption Unit. Microsoft Excel
worksheet was attached at the end of the chapter.
9.2 Components in Purified Brine
NaCl
Na 2 SO 4
Other Na/Ca/Mg salts
H2O
Salt (Total)

5.07
0.05
0.009
45.42
50.549

kmol/m3
kmol/m3
kmol/m3
kmol/m3
kmol/m3

Table 9.2- Purified brine specification

Density of brine

= 1122 kg/m3

By calculating we found that amount of NaCl we need for our process is 1477.31kmol. Using above
concentrations the Flow rate of purified brine was calculated.
Flow rate of purified brine

.
.

= 291.38m3
Flow rate of purified brine (mole)

= 291.38 m3 50.549 kmol/m3


= 14729.05kmol

Chapter9

MATERIALBALANCE

Now using the flow rate and above compositions of brine,


= 291.38m3 0.05 kmol/m3

Flow rate of Na 2 SO 4 (mole)

= 14.57kmol
Flow rate of Other Na/Ca/Mg salts (mole)

= 291.38m3 0.009kmol/m3
= 2.62kmol
= 291.38m3 45.42kmol/m3

Flow rate of H 2 O (mole)

= 13234.56kmol

9.3 NH 3 Absorption Unit

NaCl
Na 2 SO 4
Other Na/Ca/Mg salts
H2O
NH 3 OH

Brine

1477.31
14.57
2.62
13057.79
176.77

Waste gas

126.2654
29.67

kmole
kmole

NH3 Absorption
Unit

NH 3
CO 2

Makeup ammonia
+
Gas from ammonia
recovery unit

H2O
NH 3 OH
NaCl
Na 2 SO 4

13055.16
1136.389
1477.305
14.56909

kmole
kmole
kmole
kmole

CO 2
NH 3

Ammoniated brine water

Figure 9.1- NH 3 Absorption Unit

32.28992
1085.883

kmol
kmol

kmol
kmol
kmol
kmol
kmol

Chapter9

MATERIALBALANCE

Possible reactions inside the NH 3 Absorption Unit,


NaCl (aq) + H 2 O (l) + NH 3(g) NaCl (aq) + NH 4 OH (aq)
CO 2 (aq) + H 2 O (l) CO 3
Ca

2+
(aq)
2+

Mg

+ CO 3

2(aq)

2(aq)

+ 2H

----------- (2)

(aq)

CaCO 3 (s)

----------- (3)

(aq)

----------- (1)

+ 2 OH (aq) Mg(OH) 2 (s)

----------- (4)

Gaseous streams at output of NH 3 Absorption Unit,


NH 3
Total NH 3 (as ammonia gas and ammonium hydroxide) input to the NH 3 adsorption unit is
1262.654kmol. Gas stream of the output of NH3 Absorption Unit is assumed to have gas NH 3 . And the
amount is equal to 10% of total NH 3 enter to the unit.
NH 3 output of NH 3 Absorption Unit

= 1262.654 kmol 10%


= 126.25kmol

CO 2
Assume reacted amount of carbon dioxide with salt is equal (mostly salt contains Ca2+, Mg2+ which
react 1:1 with CO 3 2+) to the salt amount (mole).
Carbon dioxide output

= Input Reacted with salt


= 32.28992 kmol - 2.62kmol
= 29.67kmol

Liquid streams at output of NH 3 Absorption Unit,


NH 3
Ammonia exits as ammonium hydroxide in liquid stream from the system. As mentioned above input
of total NH 3 is 1262.654kmol.
Ammonium Hydroxide amount

= 1262.654 - 126.25 kmol


= 1136.389 kmol

NaCl
No reaction on NaCl, So Input is equal to output.
Output

= 1477.31 kmol

Chapter9

MATERIALBALANCE

Na 2 SO 4
No reaction on Na 2 SO 4 , So Input is equal to output.
Output

= 14.57 kmol

Other Na/Ca/Mg salts


Here we assume 100% precipitation of salts of Na, Ca and Mg except Na 2 CO 3 and CaCO 3 . And equal
amount of moles of water removes with the salt solid from the NH 3 Absorption Unit. This salt and
water removes from the system at this unit. And it is assume that Na 2 SO 4 is 100% soluble in this
condition.
Salt precipitation

= 2.62kmol

H 2 O (Water)
Water removed with the salt

= 2.62kmol (See Other Na/Ca/Mg salts)

Amount of water enter to the unit

= 13051.47kmol

Amount of water exit from the unit = Water enter to the unit - Water removed with the salt
= 13048.85kmol

9.4 Air Mixture

Makeup Ammonia

NH 3

6.410432

CO 2
NH 3

CO 2
NH 3

kmol
kmol

Air mixture
To NH3 absorption unit

kmole

32.28992
1079.472

32.28992
1085.883

kmole
kmole

Gas from ammonia


recovery unit

Figure 9.2- Air mixture before NH 3 Absorption Unit

Air mixture has two input streams; both get mixed and go to the NH 3 Absorption Unit.
CO 2
No two inputs of carbon dioxide and output stream equal to the input. 32.28992kmol.
NH 4
Output Ammonia Amount

= From Ammonia recovery unit + Ammonia Makeup


= 1079.472 + 6.410432
= 1085.883kmol

Chapter9

MATERIALBALANCE

9.5 Gas Washing Tower with Purified Brine

Purified brine

Waste gas

CO 2
N2
NH 3
NaCl
Na2SO4
Other Na/Ca/Mg salts
H2O

1477.31
14.57
2.62
13234.56

kmole
kmole
kmole
kmole

423.78
1604.452
6.313271

kmole
kmole
kmole

NH 3
CO 2

56.81944
394.1129

kmole
kmole

Waste gas from


Carbonator unit

Gas washing with


purified brine
Brine

NaCl
Na 2 SO 4
Other Na/Ca/Mg salts
H2O
NH 3 OH

1477.31
14.57
2.62
13057.79
176.77

Waste gas from NH3


adsorption unit

kmol
kmol
kmol
kmol
kmol

NH 3
CO 2

126.2654
29.67

Figure 9.3- Gas washing tower with purified brine

Output gas stream,


CO 2
Assume carbon dioxide does not dissolve in brine.
Output carbon dioxide amount

= From carbonator + From NH 3 Absorption Unit


= 394.1129 + 29.67
= 423.78kmol

N2
Assume Nitrogen does not dissolve in brine.
Output Nitrogen amount

= From carbonator + From NH 3 Absorption Unit


= 1604.452 + 0
= 1604.452kmol

kmole
kmole

Chapter9

MATERIALBALANCE

9.6 Carbonator Unit

NH 3
CO 2
N2

NH3 , CO2, N2 Mixture

57
394
1,604

kmole
kmole
kmole

Ammoniated brine

H2O
NH 4 OH
NaCl
Na 2 SO 4

13054
1136
1477
15

kmole
kmole
kmole
kmole

Carbonation tower

CO2, N2 mixture

Cooling System

H2O
NaHCO 3
NaCl
NH 4 Cl
NH 4 HCO 3
Na 2 SO 4

13,359
1,047
430
1,047
32

15

1,604
1,474
305

N2
CO 2
H2O

kmole
kmole
kmole
kmole
kmole
kmole

kmole
kmole
kmole

NaHCO3 Solution

Figure 9.4- Carbonator Unit

Possible reactions inside the Carbonator Unit,


NH 4 OH (aq) NH 3(g) + H 2 O (l)

----------- (5)

2 NH 4 OH (aq) + CO 2(g) (NH 4 ) 2 CO 3(aq) + H 2 O (l)

----------- (6)

(NH 4 ) 2 CO 3(aq) + CO 2(g) + H 2 O (l) 2 NH 4 HCO 3(aq)

----------- (7)

2 NH 4 HCO 3(aq) + 2 NaCl (aq) 2 NaHCO 3(aq)

----------- (8)

+ 2 NH 4 Cl (aq)

Gaseous streams at output of Carbonator Unit,


NH 3
Ammonia occurs from decomposes of NH 4 OH in the carbonator column. We assumed the
decomposed amount is equal to 5% of total NH 4 OH input to the Carbonator.
NH 3 output of carbonator Unit

= NH 4 OH input 5%
= 1136 5%
= 126.25kmol

Chapter9

MATERIALBALANCE

CO 2
Reacted amount (mole) of carbon dioxide in the column is equal to NaHCO 3 , NH 4 HCO 3 amount
produce. Carbone dioxide enters only from the gas stream from the gas cooler.
Carbon dioxide output

= Input Reacted for NaHCO 3 - Reacted for NH 4 HCO 3


= 1473.68 kmol - 1047.182 kmol - 32.387kmol
= 394.1129 kmol

Liquid streams at output of NH 3 Absorption Unit,


NaHCO 3
The efficiency of the carbonator column was taken as 97% (generation of NaHCO 3 as a percentage to
effective NH 4 OH input).
Effective NH 4 OH amount (mole)

= NH 4 OH input decomposes to NH 3
= 1136.388 kmol - 56.819 kmol
= 1079.569kmol

Generation of NaHCO 3 amount (mole)

= Effective NH 4 OH amount 97%


= 1079.569kmol 97%
= 1047.182kmol

NH 4 HCO 3
This is an intermediate product in reaction chain and amount is inversely proportional to the efficiency.
Generation of NaHCO 3 amount (mole)

= Effective NH 4 OH amount 3%
= 1079.569kmol 3%
= 32.387kmol

NaCl
Sodium spent to generate NaHCO 3 .
Sodium Chloride output from the carbonator

= Sodium Chloride input - NaHCO 3 output


= 1477.305kmol - 1047.182kmol
= 430.1231kmol

Chapter9

MATERIALBALANCE

NH 4 Cl
Ammonium chloride generated in the reaction is equal to NaHCO 3 generated in the reaction.
Ammonium chloride output

= 1047.182kmol

Na 2 SO 4
No reaction on Na 2 SO 4 , So Input is equal to output.
Na 2 SO 4 output

= 14.57kmol

H 2 O (Water)
Water amount exits from the unit is equal to the water enters to the system.
= Water from NH 3 Adsorption unit + Gas Cooler

Water exits from the unit

= 13054.34kmol + 304.9075kmol
= 13359.25kmol

9.7 Filter
13,359
1,047
430
1,047
32
15

kmole
kmole
kmole
kmole
kmole
kmole

From Carbonator Unit

H2O
NaHCO 3
NaCl
NH 4 Cl
NH 4 HCO 3
Na 2 SO 4

Residue solid

Filter

H2O
NaCl
NH 4 Cl
NaHCO 3
NH 4 HCO 3
Na 2 SO 4

13,123.9
430.1
1,047.2
104.7
32.4
14.5

kmole
kmole
kmole
kmole
kmole
kmole

Permeate

NaHCO 3
H2O
Na 2 SO 4

942.464
235.3804
0.02

kmole
kmole
kmole

Figure 9.5- Filter

Product composition after the filter as follows,


Component
NaHCO 3
H2O
Na 2 SO 4

Percentage
80%
19.98%
0.02%

Table 9.3- Residue solid composition

And the filter assumed to have 90% efficiency (based on NaHCO 3 ). As NaHCO 3 is our main product
this calculation is based on NaHCO 3 .

Chapter9

MATERIALBALANCE

9.7.1.

Calculation for residue solid

NaHCO 3
NaHCO 3 in residue solid

= Input to the filter 90%


= 1047.182kmol 90%
= 942.464kmol

Other components are calculated according to the above composition.


H2O
Water in the residue solid (wet)

= 235.38kmol
Na 2 SO 4
Although Na 2 SO 4 is not a solid in this condition, considering End Product composition it assumed
some amount of Na 2 SO 4 remain in the residue solid. So Na 2 SO 4 amount remain in the residue solid
equal to the Na 2 SO 4 in the End Product. Calculations are shown in dryer calculations.
Na 2 SO 4 in the residue solid
9.7.2.

= 0.02kmol

Calculation for permeate

NaHCO 3
NaHCO 3 in permeate

= Input to the filter 10%


= 1047.182kmol 10%
= 104.7kmol

H2O
Water in permeate

= Water input Water in filtered solid


= 13359.25 - 235.38
= 13,123.9kmol

Na 2 SO 4
Na 2 SO 4 in permeate

= 14.5kmol

NaCl
It assumed that total NaCl amount is filtrate through the filter. So amount is equal to input of the filter.
NaCl in permeate

= 430.1kmol

Chapter9

MATERIALBALANCE

NH 4 Cl
It assumed that total NH 4 Cl amount is goes through the filter. So amount is equal to input of the filter.
NH 4 Cl in permeate

= 1,047.2kmol

NH 4 HCO 3
It assumed that total NH 4 HCO 3 amount is goes through the filter. So amount is equal to input of the
filter.
NH 4 HCO 3 in permeate

= 32.4kmol

9.8 Lime Kiln

Hot Flue Gas

N2
CO 2

1604.45
1002.45

kmole
kmole

Heated CaCO3
Coke

Coal

426.50

CaCO 3

kiln

kmole

575.95

kmole

Heated Ari

O2
N2

426.50
1604.45

kmole
kmole

Figure 9.6- Lime Kiln

Calculation for the Lime Kiln has done considering material requirements (CO 2 , CaO) and energy
requirements. Main base for the calculation was the CO 2 output from the Kiln.

Possible reactions inside the Carbonator Unit,


CaCO 3(s) CaO (s) + CO 2 (g)

----------- (9)

C (s) + O 2 (g) CO 2 (g)

----------- (10)

Chapter9

MATERIALBALANCE

Gaseous products at outlet,


CO 2
Considering above (9) and (10) reactions,
Carbon dioxide output

= CaCO 3 reacted + C reacted


= 575.95kmol + 426.50kmol
= 1002.45kmol

N2
Before calculating N 2 , it needs to calculate air consumption for the kiln. In literature we found that the
kiln is supplied no excess air.
C reacted

= 426.50kmol

According to the Stoichiometric relation, amount of O 2 consumed.


O 2 required

= 426.50kmol

Assuming composition of air is O 2 21%, N 2 79%


N 2 comes with O 2

= 1604.45kmol
Air amount

= O 2 required + N 2 comes with O 2


= 2030.95kmol

Solid products at outlet,


It is assume that only solid product at outlet is CaO. Considering real situations it is possible to remain
unreacted CaCO 3 in outlet but considering calculation complexity and effectiveness on the system we
assumed it as 0kmol.
Amount of CaO

= 575.95kmol

Chapter9

MATERIALBALANCE

9.9 Slaker of lime

water coming from cooler


CaO solid

17068 kmole/day

575.95 kmole/day

Hot water from cooler

Cold CaO

Excess water

extra water

Ca(OH)2 Solution

1417.2 kmole/day

Slaker

Ca(OH)2
H2O
weight of solution
Temperature

576kmole/day
13,418 kmole/day
284,135 kg/day
60 0C

Vaporizes water

evaporated water vapors


1657.4kmole/day
Figure 9.7- Slaker of lime

Possible reactions inside the Slaker Unit,


CaO (s) + H 2 O (l) Ca(OH) 2(aq)

----------- (11)

Liquid products at outlet,


Ca(OH) 2
Ca(OH) 2 amount

= Amount of CaO
= 575.95kmol

H2O
Water input amount

= Water from gas cooler - Excess water (remove)


= 17068.07kmol - 1417.21kmol
= 15650.85kmol

Water reacted with Ca(OH) 2

= 575.95kmol

Water vaporized amount

= 1657.4kmol

Excess water

= Water input - Water reacted - Water vaporized

(see energy balance)

= 15650.85kmol - 575.95kmol - 1657.4kmol


= 13417.507kmol

Chapter9

MATERIALBALANCE

9.10

Ammonia Recovery Unit

CO 2
NH 3

Cool gas (NH3)

32.28992 kmole/day
1079.472 kmole/day

Cool NH4Cl Solution


HE

Condensed water

H2O

1061.655 kmole/day

Hot NH3 ,H2O mixture

H2O
NaCl
NH 4 Cl
NaHCO 3
NH 4 HCO 3
Na 2 SO4

H2O
CO 2
NH 3

13,123.9
430.1
1,047.2
104.7
32.4
14.5

kmole/day
kmole/day
kmole/day
kmole/day
kmole/day
kmole/day

1061.655 kmole/day
32.28992 kmole/day
1079.472 kmole/day

Ammonia
recovery unit

shaking of lime

Ca(OH) 2
H2O

575.95 kmole/day
13417.51 kmole/day

Steam

NaCl
CaCl 2
NaHCO 3
NH 4 OH
Ca(OH) 2
Na 2 SO 4
H2O

430.12
523.59
104.72
0.10
52.36
14.55
25,479.72

kmole/day
kmole/day
kmole/day
kmole/day
kmole/day
kmole/day
kmole/day

Waste water

Figure 9.8- Ammonia Recovery Unit

Possible reactions inside the Carbonator Unit,


2NH 4 Cl (aq) + Ca(OH) 2 2NH 3(g) + CaCl 2(aq) + H 2 O (l)
NH 4 HCO 3(aq) NH 3(g) + CO 2(aq) + H 2 O (l)
(13)

----------- (12)
-----------

Chapter9

MATERIALBALANCE

Gaseous products at outlet,


CO 2
Considering 99.7% efficiency for (13) reaction,
Carbon dioxide output

= NH 4 HCO 3 99.7%
= 32.4kmol 99.7%
= 32.289kmol

NH 4
Considering 100% efficiency for (12) reaction and considering 99.7% efficiency for (13) reaction,
Ammonia output

= NH 4 Cl 100% + NH 4 HCO 3 99.7%


= 1,047.2 100% + 32.4 99.7%
= 1079.472kmol

Liquid products at outlet,


NaCl
NaCl involves with no reaction through the Ammonia recovery column.
NaCl output

= 430.1kmol

NaHCO3
NaHCO3 involves with no reaction through the Ammonia recovery column.
NaHCO3 output

= 104.72kmol

NH 4 HCO 3
Considering 99.7% efficiency for (13) reaction,
NH 4 HCO 3 output

= NH 4 HCO 3 0.3%
= 32.4kmol 0.3%
= 0.10kmol

Na 2 SO 4
Na 2 SO 4 involves with no reaction through the Ammonia recovery column.
Na 2 SO 4 output

= 14.55kmol

Chapter9

MATERIALBALANCE

CaCl 2
According to the reaction (12). (Stoichiometric relation is 2:1)
CaCl 2 at outlet

= NH 4 Cl
= 1,047.2
= 523.59 kmol

Ca(OH) 2
Ca(OH) 2 amount is 110% of the actual Ca(OH) 2 requirement CaCO 3 to the kiln is back calculated
from here.
Ca(OH) 2 at the outlet

= Ca(OH) 2 10%
= 523.59 10%
= 52.36kmol

H2O
Water involve no reaction in the Ammonia recovery column and it is assume that no water vapor in
gaseous output.
Water output amount

= Water from slaker + Water from filter


= 13417.5 kmol + 13,123.9 kmol
= 26,541.38 kmol

Chapter9

MATERIALBALANCE

9.11

Gas Cooler

N2
CO 2
H2O

(g)

1604.452381 kmole/day
1473.682222 kmole/day
304.9074568 kmole/day

Gas out

Water In

300 m3/day

H2O

Cooler

16669 Kmole/day

Gas mixer

H 2 O condense

N2
CO 2
H2O

(g)

1604.45238 kmole/day
1473.68222 kmole/day]
704.26438 kmole/day]

Hot Water Out

H2O

17068 Kmole/day

Figure 9.9- Gas Cooler

Gaseous products at outlet,


CO 2
Carbon dioxide output

= Carbon dioxide input


= 1473.68kmol

N2
Nitrogen output

= Nitrogen input
= 1604.45kmol

H2O
The gaseous outlet assumed to be saturated with water at its temperature.
Water in gaseous outlet

= Dry air flow

= {(N2 28) + (CO 2 44)}

= {(1604.45 28) + (1473.68 44)}


= 304.90kmol

399kmole/day

Chapter9

MATERIALBALANCE

Liquid products at outlet,


H2O
Water in liquid outlet

= From air mixture + Additional injection In gaseous outlet


= 1326.26 + 6,623 304.90
= 7644.77kmol

9.12

Air Mixture (Before the Gas Cooler)

N2
CO 2
H2O

1604.452381
1473.682222
704.264384

Kmole/day
Kmole/day
Kmole/day

CO 2
H2O

471.232
704.264384

Kmole/day
Kmole/day

AirMixer

N2
CO 2

1604.452381
1002.450222

Kmole/day
Kmole/day

Figure 9.10- Air mixture before gas cooler

Air mixture has two input streams; both get mixed and go to the Gas Cooler.
CO 2
CO 2 in outlet

= From dryer + From CaCO 3 preheated


= 471.232 + 1002.45
= 1473.68kmol

H2O
Water in outlet

= From dryer + From CaCO 3 preheated


= 704.26 + 0
= 704.26kmol

N2
Nitrogen output

= From dryer + From CaCO 3 preheated


= 0 + 1604.45
= 1604.45kmol

Chapter9

MATERIALBALANCE

9.13

Dryer

CO2
H2O
N2
CO2

1604.452381
1002.450222

Kmole/day
Kmole/day

471.232
704.264384

Kmole/day
Kmole/day

CO2, H2O Vapour

Flue gas out

NaCO3 Product
NaHCO3 Solution

NaHCO3
H2O
Na2SO4
Flow rate

942.464
235.3804
0.02
1177.844

Kmole/day
Kmole/day
Kmole/day
kmole/day

N2
CO2

Calcinations NaHCO3

Flue gas in
1000 C

1604.45
1002.45

Na 2 CO3

471.232

Kmole/day

H2O
Na2SO4
Total

2.348
0.02
473.6

Kmole/day
Kmole/day
Kmole/day

Kmole/day
Kmole/day

Figure 9.11- Dryer

Possible reactions inside the Carbonator Unit,


2NaHCO 3 (s) Na 2 CO 3 (s) + CO 2 (g) + H 2 O (g)

----------- (14)

Gaseous products at out let,


Heat is supplies to the dryer through indirect contact of flue gas from the kiln. So composition of flue
gas does not change by going through the dryer. In this calculation other gas outlet is considered.
CO 2
CO 2 at outlet

= CO 2 generated by the reaction


= NaHCO 3 amount reacted
= 471.232kmol

H2O
H 2 O at outlet

= H 2 O generated by the reaction + H 2 O in inlet - H 2 O in product


= 471.232 + 235.38 - 2.348
= 704.26kmol

Chapter9

MATERIALBALANCE

Solid products at out let,


Na 2 CO 3
Na 2 CO 3 in product

= Na 2 CO 3 generated by the reaction


= NaHCO 3 amount reacted
= 471.232kmol

Na 2 SO 4
Na 2 SO 4 amount in the product assume to be .02kmol.
H2O
H 2 O amount calculated assuming only material in the product is H 2 O except Na 2 CO 3 and Na 2 SO 4 .

Chapter9

9.14

Material Flow Sheet

MATERIALBALANCE

Chapter10

ENERGYBALANCE

CHAPTER 10

ENERGY BALANCE

Energy is fundamental to the quality of our lives.


Nowadays, we are totally dependent on an
abundant and uninterrupted supply of energy for
living and working. It is a key ingredient in all
sectors of modern economies
Energy supply must be sustainable and diverse.
And energy needs to be used more
efficiently........

Chapter10

ENERGYBALANCE

10.1 Kiln Energy Balance


N2
1604.45
CO 2
1002.45
Temperature 1000 C

Coal
426.50
Temperature 30 C

kmole/day
kmole/day

CaCO 3
575.95
Temperature 566 C

kmole/day

O2
426.50
N2
1604.45
Temperature 900 C

kmole/day
kmole/day

Figure 10.1- Kiln

Assumption

Limestone is mixture of several components


CaCO 3 =78%
SiO 2 =18.5%
Al 2 O 3 =3.5% mole Percentage
Mixture Cp is 136 J/moleK

Heat loss from the kiln is considered as 15%

This calculation is down by using trial and error method using excel

Gas phase enthalpy change were calculated using following equation


H R 0 =

C p = Specific heat capacity

C p is changed with Temperature like following equation

C p = a + b T c /T2
Component
Co2
O2
N2
CaO

a
10.34
8.27
6.5
10

b
0.00274
0.000258
0.001
0.05

Table 10.1- a, b, c constant

c
195500
187700
0
108000

kmole/day

Chapter10

ENERGYBALANCE

Object
Fine the coke requirement for the kiln
Energy balance
Enthalpy of inlet material + Heat of combustion = Enthalpy of outlet material + Dissociation enthalpy of CaCO3 + Loss

Enthalpy of inlet material


Component
O2
N2
CaCO 3

Flow rate (kmole/day)


Enthalpy @ 900 C (J/mole)
426.50
45,385.0
1604.45
28,837.0
575.95
136.0
Total Enthalpy of inlet material (kJ/Day)

Enthalpy(kJ/Day)
19,356,702.5
46,267,593.3
78,329.2
65,702,625.0

Table 10.2- kiln inlet enthalpy

Enthalpy of outlet material


Component
CO 2
N2
CaO

Flow rate (kmole/day)


Enthalpy @ 1000 C (J/mole)
1002.45
51,060.0
1604.45
32,231.0
575.95
73.6
Total Enthalpy of outlet material (kJ/Day)

Table 10.3- kiln outlet enthalpy

Dissociation enthalpy of CaCO3


CaCO 3 supply rate per day =575.95 kmole/day
CaCO 3s CaO s + CO 2g

( H) =177 kJ/mole

Heat absorbed for reaction=101,943,189.33 kJ/Day


Heat of combustion
Calorific value of coke=32000 kJ/kg
Assume kiln coke requirement is 426.5 kmole/day
Coke supply rate per day =426.5 kmole/day
Heat released due to combustion of coke=163776000 kJ/Day

Enthalpy(kJ/Day)
51,185,108.3
51,713,104.7
42,380.3
102,940,593.4

Chapter10

ENERGYBALANCE

Heat loss to Environment


15% generated heat is Lost to the environment
Heat loss = heat of combustion

percentage

=24566400 kJ/day

Substituting this value in to the energy balance equation satisfied both side. Coke requirement is
satisfies
10.2 Energy Balance for Air Preheated
CaO

575.95 kmole/day

Hot CaO
1000 C

Hot Air
900 C

Cool air
25 C

Air flow
rate
O2
N2

Cool CaO
TC

2030.95 kmole /day


426.50 kmole/day
1604.45 kmole/day

Figure 10.2- Air preheated

Assumption
Pressure is constant inside unit. Enthalpy change can calculated as follows
H c 0 =

C p = a + b T c /T2

a, b, c constants are gave in upper part of this chapter

This calculation is done by using trial and error method


Heat loss to the surrounding is 11% of the

Air enthalpy change


Air mixture temperature is change from 25 C to 900 C
Components
N2
O2

Enthalpy Change
(kJ/kmole)
26974.06
31969.88
Total Enthalpy

Flow rate
kmole/day
1604.45
426.50

Table 10.4- Air enthalpy change

Enthalpy Change
(kJ/day)
43278598.8
13635151.83
56,913,751

Chapter10

ENERGYBALANCE

Enthalpy Change of CaO


Hot CaO is cooled from 1000 C to 154 C
Component
CaO

Enthalpy Change
(kJ/kmole)
111218.35

mole Flow
rate(kmole/day)
575.95
Total Enthalpy

Enthalpy Change (kJ/day)


64056233.52
64,056,234

Table 10.5- CaO enthalpy change

Heat loss
Heat loss to the environment is 11% of the heat gain by cooling of the CaO
Heat loss to the surrounding

= 7,117,359.28 kJ/day

Enthalpy Change of CaO = Enthalpy Change of CaO + Heat loss

This equation is satisfies. So air is heated up to 900 C before feed to the kiln.

10.3 Calcinations of Crude Bicarbonate


Objective

To determine the flue gas out T from the calcinations.

Assumption
Pressure is constant inside unit. Enthalpy change can calculated as follows
H c 0 =

C p = a + b T c /T2

a, b, c constants are gave in upper part of this chapter

10 % Heat is lost from indirect dryer which is supply from flue gas

Specific heat capacity of pure substance is get from parry hand book

NaHCO3

96kJ/kmole K

H2O

75.6kJ/kmole K

Na2CO3

121.38kJ/kmole K

Kiln internal pressure 1.5bar

Chapter10

ENERGYBALANCE

N2
CO 2
Temperature

1604.452381
1002.450222
622

CO 2
H2O
Temperature

kmole/day
kmole/day
C

471.232
704.264384
200

kmole/day
kmole/day
C

CO2, H2O Vapour

Flue gas out

NaCO3 Product
NaHCO3 Solution

NaHCO 3
H2O
Na 2 SO 4
Flow rate
Temperature

942.464
235.3804
0.02
1177.844
30

Calcinations NaHCO3

kmole/day
kmole/day
kmole/day
kmole/day
C

Flue gas in
1000 C

N2
CO 2
Temparature

Na 2 CO 3
H2O
Na 2 SO 4
Total
Temperature

1604.45
1002.45
1000

471.232
2.348
0.02
473.6
200

kmole/day
kmole/day
kmole/day
kmole/day
C

kmole/day
kmole/day
C

Figure 10.3- Dryer

Inlet Enthalpy of the NaHCO 3 solution


Heat Capacity of mixture of NaHCO 3

= Cp

mole fraction + C p

NaHCO3

fraction

H2O

mole

= 91.9 kJ/kmole
= C p mixture Flow rate

Enthalpy of inlet mixture

= 32,806,204.21kJ/Day
Outlet Enthalpy of the Na 2 CO 3
Enthalpy of Out let Material of Na 2 CO 3 = C p Na2CO3 Flow rate
=27,190,673.66kJ/Day
Outlet CO 2 , H 2 O mixture Enthalpy
During thermal decomposition of the NaHCO 3 , H 2 O & CO 2 mixture is relished .Assume the
temperature is 200 C
H 2 O g enthalpy from steam table
H 2 O g Total energy

= 2876kJ/kg
= 2876 18 704.2
=36,455,025.6 kJ/kmole

Chapter10

ENERGYBALANCE

CO 2 Enthalpy

=45.2kJ/kmole

Total energy CO 2

=45.2

kJ/day

=21,298.24 kJ/day
Total Enthalpy of the Exit mixture

=36,479,658.89kJ/Day

Flue Gas Enthalpy Change


Mixture of flue gas is cooled 1000 C to T C
If Temperature of flue gas out is 622 C
CO 2 enthalpy change =
= 19,457,719.97 kJ/day

N 2 Enthalpy

=
=24,535,963.06kJ/day

Total enthalpy change = 43,993,683.03 kJ/Day


Decomposition NaHCO3 s Enthalpy Change
NaHCO 3 s

Na 2 CO 3 s + H 2 O g + CO 2g

Total energy absorb

= 9.24

kJ/day

= 8,708,367.36kJ/Day
Heat loss
Heat loss from indirect dryer 10 % supply from flue gas =4399368.303kJ/Day
Energy equation
Enthalpy change of flue gas = Hot product out (NaCO 3(s) ) + CO 2 , H 2 O mixture out + Reaction energy
+ heat loss to environment -Enthalpy of NaHCO 3 in
Substituting the all calculated value to this equation is satisfies. This calculation is down by using trial
and error method.
So flue gas exit temperature is 622 C

Chapter10

ENERGYBALANCE

10.4 CaCO 3 Preheated


Objective
To determine the CaCO3 feed T
Assumption

Pressure is constant inside unit. Enthalpy change can calculated as follows

H c 0 =

C p = a + b T c /T2

a, b, c constants are gave in upper part of this chapter

10% heat loss during preheating

No Cp Change in limestone with increasing T @ Cp

136 J/mole

N2
CO 2

N2
CO 2

1604.452 kmole/day
1002.45 kmole/day

1604.452 kmole/day
1002.45 kmole/day

CaCO 3
Temperature

575.95 kmole/day
566 C

Figure 10.4- Cyclone

Energy Equation
Heat IN = Heat Out + Loss
Enthalpy Change of Flue Gas = Enthalpy Change CaCo3 + Losses
Flue Gas Enthalpy Change mixture of flue gas is cooled 622C to 210 C
CO 2 enthalpy
N 2 Enthalpy
Total enthalpy change

20,913,120.69 kJ/Day
26,177,959.30 kJ/Day
47,091,079.98 kJ/Day

Table 10.6- flue gas enthalpy change

Chapter10

ENERGYBALANCE

Enthalpy Change Of CaCO3

42,376,113.55 kJ/Day

Heat loss 10% enthalpy change of the flue gas


Loss of heat

4,709,108.00 kJ/Day

Energy balance equation is satisfied using these values. Using cyclone CaCO 3 is heated up to 566C.
This Calculation is done by using trial and error method.

10.5 Air Mixer Energy Balance


Objective

To fine the gas mixture temperature


Assumption
Pressure is constant inside unit. Enthalpy change can calculated as follows
H c 0 =

C p = a + b T c /T2

a, b, c constants are gave in upper part of this chapter

Nearly 4% of heat is lost to the environment


Kiln internal pressure 1.5bar
Air Mixture pressure is 1bar

N2
CO 2
H2O
Temperature
Stream 3

1604.452381
1473.682222
704.264384
T

kmole/day
kmole/day
kmole/day
C

CO 2
H2O
Temperature
Stream 2

471.232
704.264384
200

AirMixer

N2
CO 2
Temperature
Stream 1

1604.452381
1002.450222
210

kmole/day
kmole/day
C

Figure 10.5- Air mixture before gas cooler

kmole/day
kmole/day
C

Chapter10

ENERGYBALANCE

Stream 2 carrying energy is calculated in the calcinations energy balance section


Stream 2 energy

= 36,479,658.89 kJ/day

Stream 1 energy

= CO 2 energy + N 2 energy

CO 2 energy change =
N 2 energy change =
Temperature of the mixture is 200 C
Steam 1 energy = 92,634.44 kJ/kmole

Heat loss to the surrounding = (92,634.44+36,479,658.89) .4


=1,462,891.73 kJ/day
Steam 3 energy calculation
If out let temperature is 140 C,
Water vapor enthalpy is = 2756.8 kJ/kg
Energy of water vapor

kJ/day

= 34,947,288.97 kJ/day
Gas carrying energy can calculated same as steam 1.if out let temperature is 140 C
Gas carrying energy =110,493.69 kJ/day
Total energy of steam 3 = 36,520,674.39 kJ/day
Energy equation
Stream 1 energy + Stream 2 energy = Stream 3 energy + loss
Substituting values to the energy equation is satisfies so out let temperature is 140 C

Chapter10

ENERGYBALANCE

10.6 Heat Balance for Gas Cooler


Object

To Find the Cooling water demand required for gas cooler.

Assumption

Cooling water system used is ones through system having 30 0C temperature of inlet water.

Efficiency of the gas cooler is 95%.

Out let gas stream is saturated with water vapor and quantity of energy carries with the steam is
neglected.

N2
CO 2
H2O g
Temperature

1604.452381 kmole/day
1473.682222 kmole/day
304.9074568 kmole/day
40 0C

Gas out

H2O
Temperature

N2
CO 2
H2O g
Temperature

1604.45238 kmole/day
1473.68222 kmole/day]
704.26438 kmole/day]
140 0C

300 m3/day
16669 kmole/day
30 0C

Water In
Cooler

Gas mixer

H 2 O condense
Hot Water Out

H2O
Temperature

17068 kmole/day
50 0C

Figure 10.6- Gas cooler

Heat given by the hot stream = Heat taken by the cold stream
Enthalpy change H R 0 =

C p = a + b T c /T2
H R 0 = a T + b T2 c /T

399 kmole/day

Chapter10

ENERGYBALANCE

Component
CO 2
O2
N2

a
b
10.34 0.00274
8.27 0.000258
6.5
0.001

c
195500
187700
0

Table 10.7- Soda ash specification

Total energy of the inlet gas mixture

= 35,057,783 kJ/day

Total energy of the out let gas mixture = 102,867 kJ/day


Enthalpy change due to condensate of the of the water vapor = 9,751,817 kJ/day
Total enthalpy change in gas stream = Total energy of the inlet gas mixture - Total energy of the out let
gas mixture - Enthalpy change due to condensate of the of the water vapor
= (35,057,783-102,867-9,751,817) kJ/day
= 25203099 kJ/day
Cooling water flow rate required = m kg
Total enthalpy change in gas stream = m C water T = 25203099
Cooling water flow rate required = m = 16669 kg/day
= 300m3/day
Condense water and heated cooling water is mixed and then supply hole quantity in to slaker to make
Ca(OH) 2 solution.

10.7 Slaking of Lime


Objective
Find the quantity of evaporated water vapor from the slaker.
Assumption

15% brix, Ca(OH) 2 mixture is required for the process.

Heat loss to the surrounding is 10 %from the energy due to the reaction enthalpy.

Chapter10

ENERGYBALANCE

CaO solid
Temperature

water coming from cooler


Temperature

575.95 kmole/day
154 0C

17068 kmole/day
50 0C

Hot water from cooler


Cold CaO

Excess water

extra water
temperature

Ca(OH)2 Solution

1417.2 kmole/day
50 0C

Slaker

Ca(OH) 2
H2O
weight of solution
Temperature

576
kmole/day
13,418 kmole/day
284,135 kg/day
60 0C

Vaporizes water

evaporated water vapors

1657.4kmole/day

Figure 10.7- Slaker

Energy with the inlet CaO stream

= m Cp T

Component
CaO

a
10

b
0.05

c
108000

Table 10.8- a, b, c constant for CaO

C p = a + b T c /T2

Energy with the inlet CaO stream = (10+0.05 (154+273) 108,000/(154+273) 2) 4.2 575.95
=

74,402.4 kJ/day

Amount of the input energy of the water from the cooler

= m C water T
= 15,650.9184.2 (273+50)
= 382,175,186 kJ/day

Total Heat in = Energy with the inlet CaO stream + Amount of the input energy of the water from the cooler

Total Heat in = 74,402.4 + 382,175,186


= 382,249,589 kJ/day

Chapter10

ENERGYBALANCE

Reaction Enthalpy:
CaO + H 2 O

Ca(OH) 2

H= - 65 kJ/mole

Heat generated due to reaction = 65 1000 576 kJ/day


Loss to surrounding

= 3,743,675 kJ/day

Cp of the Ca(OH) 2 mixture = 3.6183 kJ/kgK


Heat out with Ca(OH) 2

= 3.6183 284135 (273+60)


= 342,353,062 kJ/day

Energy with water vapor = Heat in+ Heat generated due to reaction - Heat out with Ca(OH) 2 - loss.

Energy with water vapor

= 382,249,589 +37,436,750 - 342,353,062 - 3,743,675


= 73,589,615 kJ/day

Water vapor quantity

= 73,589,615/(4.2 (100-50)+2256.7)
= 29,833 kg/day
=1,657.4 kmole/day

Chapter10

ENERGYBALANCE

10.8 Recovery of Ammonia Column Energy Balance

CO 2
NH 3
Temperature

Boundary line

32.28992
1079.472
T

kmole/day
kmole/day
C

Cool gas (NH3)

H2O

1061.655

kmole/day
HE

Condensed water

Cool NH4Cl Solution

H2O
CO 2
NH 3
Temperature

1061.655
32.28992
1079.472
70

kmole/day
kmole/day
kmole/day
C

Hot NH3 ,H2O mixture

H2O
NaCl
NH 4 Cl
NaHCO 3
NH 4 HCO 3
Na 2 SO 4
Temperature
Flow rate
molecular weight

13,123.9
430.1
1,047.2
104.7
32.4
14.5
30
14,752.8
22.42532

kmole/day
kmole/day
kmole/day
kmole/day
kmole/day
kmole/day
C
kmole/day
kg/kmole

Ammonia
recovery unit

shaking of lime

Ca(OH) 2
H2O
Temperature
weight of solution
Cp

575.95
13417.51
60
284135.4
3.6183

kmole/day
kmole/day
C
Kg/day
kJ/kgK

Steam

Bottom T
low pressure steam

Waste water

NaCl
CaCl 2
NaHCO 3
NH 4 OH
Ca(OH) 2
Na 2 SO 4
H2O
T
Total Flow rate
molecular weight

430.12
523.59
104.72
0.10
52.36
14.55
25,479.72
105
26,605.16
20.84993

kmole/day
kmole/day
kmole/day
kmole/day
kmole/day
kmole/day
kmole/day
C
kmole/day
kg/kmole

Figure 10.8- NH3 Recovery column

Objective

To fine Quantity of steam consumption


Fine out let temperature of the cool gas

105
2

C
bar

Chapter10

ENERGYBALANCE

10.8.1 Find Outlet Temperature of the Cool Gas


Assumption
20 % Heat is lost to surrounding from HE
NH 4 Cl Solution is heated from 30C to 50C
Pressure is constant inside unit. Enthalpy change can calculated as follows
H c 0 =

C p = a + b T c /T2

a, b, c constants are gave in upper part of this chapter


Column Bottom And top Temperatures are got from literature
Top Temperature 70 C
Bottom Temperature 105C
Energy equation
Enthalpy change of cool steam + loss = Enthalpy change of hot stream
Enthalpy change of hot stream
Hot gas mixture is cooled up to T. Assume T is 40 C
NH 3 & CO 2 mixture is cool from 70 C to 40 C this energy relies is = mole flow rate
NH 3 & CO 2 mixture Energy = 1,837,568 kJ/day
Steam Condense energy

= 1,061.55 2257 18 kJ/day


= 43,130,800 kJ/day

Total Energy

= 44,968,368 kJ/day

Enthalpy change of cool steam


Assume heat capacity of the NH 4 Cl mixture is same as water heat capacity because larger portion of
mixture is include H 2 O.
Energy grip by cool stream
=

=
=34,737,885 kJ/day

Chapter10

ENERGYBALANCE

Heat loss to the surrounding

= total energy relies hot stream

0.2

= 8,993,674 kJ/day
Substituting this value to the energy equation it satisfies. So assume temperature is Correct

10.8.2 Fine Quantity of Steam Consumption


Assumption
Fully insulated the column no heat losses
NH4Cl solution feed stream line & waste stream from the column have more water compare
with other substances. So Assume specific heat of solution is equal to the water specific heat
2 bar saturated steam is used for column heating
Apply energy balance for the system bounded by boundary line

Quantity of Energy supply to the column = Energy out from boundary- Energy in through boundary

Energy out from boundary


Waste steam energy
Waste steam is have column bottom T at 105 C, Cp same as water
Waste steam energy =
= 880,666,741.8 kJ/day
Heat loss from HE = 8,993,674 kJ/day
Heat carried from cool water =1061.655 175.2 18
=3,348,035.5 kJ/day
Heat carried from cool NH 3 , CO 2 mixture = flow rate Cp

temperature

=12,696,681.8 kJ/day

Chapter10

ENERGYBALANCE

Energy in through boundary


Ca(OH) 2 mixture inlet energy

=
=284135.4*3.6183*(60+273)
=342,353,062 kJ/day

NH 4 Cl solution inlet energy


=
= 22.42 14752.8 4.2 (273+30)
= 421,023,166 kJ/day

Quantity of Energy supply to the column using steam


= 880,666,741.8 +8,993,674 +3,348,035.5 +12,696,681.8 - 342,353,062 - 421,023,166 kJ/day
= 135,632,833.6 kJ/day
2 bar saturated steam enthalpy change = 2211.6 kJ/kg
Steam consumption

=135,632,833.6/2211.6
=61,328 kg/day
= 2.555330108 t/hour

Chapter10

ENERGYBALANCE

10.9 Carbonation of Ammoniated Brine Column

NH 3
CO 2
N2

57
394
1,604

kmole
kmole
kmole

NH3 , CO2, N2 Mixture

H2O
NH 4 OH
NaCl
Na 2 SO 4
Temperature
flow rate
mole weight

13054
1136
1477
15
36
15,683
23.0302373

kmole
kmole
kmole
kmole
C
kmole/day
kg/kmole

Ammoniated brine

N2
CO 2
H2O

Carbonation tower
Cooling Water

Cooling water
Flow rate

Out let temperature

22
1666.8

C
m3/day

45

Cooling System

CO2, N2 mixture

C
NaHCO3 Solution

Temperature
H2O
NaHCO 3
NaCl
NH 4 Cl
NH 4 HCO 3
Na 2 SO 4
flow rate
mole weight

28
13,359
1,047
430
1,047
32
15
15,931
25.71239

C
kmole
kmole
kmole
kmole
kmole
kmole
kmole/day
kg/kmole

Figure 10.9- Carbonation column

1,604
1,474
305
40

kmole
kmole
kmole
C

Chapter10

ENERGYBALANCE

Objective

To Calculate Cooling water requirement


Assumptions
Ammoniated brine water specific heat 3.85kJ/kg k , Density 1025kg/m3
NaHCO 3 Solution has more water compare with other substances so assume water properties
of the mixture
10% heat loss to the surround from column
Pressure is constant inside unit. Enthalpy change can calculated as follows
H c 0 =

C p = a + b T c /T2

a, b, c constants are gave in upper part of this chapter

Cooling water is feed to the system at 22 C and heat up to 45 C

Reaction in the carbonation tower


NH 4 OH (aq) + NaCl (aq) + CO 2 (g)

NaHCO 3

(s)

+ NH 4 Cl (aq)

Formation energy
NH 4 OH (aq) -367.08 kJ/mole
NaCl (aq)

-408.74 kJ/mole

CO 2 (g)

-395.0 kJ/mole

NaHCO 3

-949.2 kJ/mole

(s)

NH4Cl (aq)
Reaction energy

-299.04 kJ/mole
=
=

-77.3976kJ/mole

Energy Equation for the unit


Cooling water enthalpy change = energy out NaHCO 3 Solution + Energy out exit gases +reaction
relies energy -energy input from ammoniated brine solution - energy input CO2 mixture - heat loss
Energy out NaHCO 3 Solution = Mole flow rate heat capacity Average molecular weight
= 517,836,893 kJ/day
Energy out exit gases

= Flow Rate

Cp

T (this down as before section)

Chapter10

ENERGYBALANCE

= 6,057,972 kJ/day
Total Reaction relies energy = reacted mole

reaction relies energy

= 81,049,391 kJ/day
Energy input from ammoniated brine solution = Mole flow rate heat capacity Avarage molecular
weight

T
= 429,670,827 kJ/day

Energy input CO 2 mixture = Flow Rate

Cp

=32,197,304 kJ/day
Heat loss to the surrounding = (reaction energy relies + CO 2 mixture energy) 0.01
= 11,324,669 kJ/day
From the above energy equation, substituting this value
Cooling water enthalpy change = 131,751,455 kJ/day
Cooling water quantity = 131,751,455/(4.2
=1,363,886.7 kg/day
=1,363.9 m3/day

(45-22)) kg/day

Chapter11

CONCLUSION

CHAPTER 11

CONCLUSION

The final outcome of the chemical process design


is based on the process selection, material
balance and the energy balance. These are some
of the essential elements and preliminary stages
of design that leads to a superior, cost-effective
and technologically sound design. The final
outcome of these components, presented in the
form of a summary form the basis for the project
conclusion.

This diagram shows the comparison of parameters calculated for the proposed plant with those obtained from literature for a plant of similar capacity. It
can be clearly seen that the calculated values are very much similar to those obtained from existing plants.
Data extracted from similar existing
process plant

values obtained by our calculation

INPUT
Main raw material

kg/t soda ash

1050 - 1600

Limestone
Raw brine

NaCl (1530 - 1800) + water (4500 - 5200)

1476.8
6538.6

NH 3 make up

0.8 - 2.1

0.1

Water
Process(1)
Cooling

m3/t soda ash


6.0
27.8
GJ/t soda ash
3.3

2.5 - 3.6
50 -100
Energy

Fuels (lime kiln)

2.2 - 2.8

out put
kg/t soda ash

Gaseous emissions
CO 2

200 - 400

372.9

NH 3

< 1.5

1.9
kg/t soda ash

850 - 1100
340 - 400
160 - 220
1-11
0.3 - 2
90 - 700

1051
461
259
28
0.035
176

Liquid emissions
-

Cl
Ca2+
Na+
SO4-2
NH4+
Suspended solids

REFERENCE
PERRY'S CHEMICAL ENGINEERING HANDBOOK,byROBERT H. PERRY, DON W. GREEN
RICHARDSON, J.F., HARKER, J.H., BACKHURST, J.R. Coulson and Richardsons CHEMICAL
ENGINEERING VOLUME 2. 5th ed. 2002.
RICHARDSON, J.F., HARKER, J.H., BACKHURST, J.R. Coulson and Richardsons CHEMICAL
ENGINEERING VOLUME 6. 5th ed. 2002.
RULE OF THUMB FOR CHEMICAL ENGINEERS A manual of quick, accurate solutions to every
day process engineering problems. By CARL BRANAN.
CHEMICAL ENGINEERING DESIGN PROJECT, A case study approach BY MARTYN S.RAY and
DAVID W.JOHNSTON
CHEMICAL ENGINEERING DESIGN PROJECT, A case study approach, Second edition By
MARTYN S.RAY and MARTIN G. SNEESBY.
A TEXT BOOK OF CHEMICAL TECHNOLOGY Volume 1 BY S.D. SHUKLA and G.N.PENDAY

Note: These references from internet were observed in July October 2008

www.laxmi-group.com/kiln.html

www.amazon.co.uk/Small-scale-Vertical-Shaft-Lime-Kiln

www.massbalance.org/projects

http://minerals.usgs.gov/minerals/pubs/commodity/soda_ash/soda_myb05.pdf

http://www.webcitation.org/5WGM2f75m

http://www.webcitation.org/5W0IxdohY

http://www.cavemanchemistry.com/cavebook/chammonia.html

http://www.businessknowledgesource.com/manufacturing/daily_safety_measures_for_manufac
turing_plants_025095.html

http://www.imec.org/imec.nsf/All/Solutions_Source_Implement_a_Safety_Plan?OpenDocume
nt

http://pottery.about.com/od/safetyinceramics/tp/kilnsafe.htm

Msds sheets over the internet

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Software Resources
Microsoft Office
Microsoft Office Visio Professional 2003
Google Earth Version 4.0.2737
Microsoft Paint
Microsoft picture manager
PhysProps Version 1.6.1

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