Jordan University of Science and

TechnologyFaculty of Engineering
Chemical Engineering Department

MANUFACTURING OF TITANIUM DIOXIDE

"Submitted in partial fulfillment of the graduation project (ChE 592) course"

Conducted by:
Layali Omar AL-Khawaldeh 122509

Heba Ahmad Ammar 129147

Mohammad ABDALLAH allatifeh 129626

Supervised by:

Dr Hussein Al laboun
ABSTRACT

The aim of this project is to design a plant to produce titanium dioxide from Rutile,
which contain impure titanium dioxide. The required capacity of the plant is 1 tone per
operating day with 99.5% purity. Titanium dioxide is very important material which
have several applications such as; photo catalyst oxygen sensors, pigments and others.
There are two main process that used to produce titanium dioxide which are; the
sulphate process route, and chlorine process. The sulphate process is the oldest route
which considered very complex route and required more steps. On the other hand, the
chloride process is the modern route and 60% of titanium dioxide produce by it. The
chloride process selected to be used in this project, were it consist of chlorinator,
cooler, separator, condenser, converter, oxidize burner, cyclone separator and the
finishing process unit.
The market analysis of titanium dioxide is done were the highest market growth of
pigments presence in Asia Pacific. The main raw material of chlorine process are
chlorine gas, coke, and rutile. The environmental a safety aspect of the process was
studied for the main raw material and by product of the process. The mass balance and
energy balance for the total plant was done for the main equipment's in the plant.
Furthermore, the physical and chemical properties of the desired product and raw
materials was summarized.

i
Table of Contents
ABSTRACT..................................................................................................................... i
CHAPTER ONE: INTRODUCTION ............................................................................. 1
1.1 Titanium Dioxide Overview ................................................................................. 1
CHAPTER TWO: LITERATURE SURVEY ................................................................. 3
2.1 Application and Uses ................................................................................. 3
2.2 Physical and Chemical Properties ............................................................................. 4
CHAPTER THREE: MARKET SURVEY ..................................................................... 5
3.1 Demand data ................................................................................. 5
3.2 Chlorine Price Trend ................................................................................. 7
3.3 Rutile Price Trend ................................................................................. 8
CHAPTER FOUR: PROCESS SELECTION ................................................................. 9
4.1 Sulphate Process Route ................................................................................. 9
4.2 Chlorine Process Route ............................................................................... 11
4.3 Selection Process ............................................................................... 12
CHAPTER FIVE: PROCESS DESCRIPTION............................................................. 14
5.1 Chlorine process overview ............................................................................... 14
5.2 Physical and Chemical Properties ........................................................................... 16
5.3 Chloride Process Description ............................................................................... 18
CHAPTER SIX: PLANT LAYOUT & LOCATION..................................................... 21
6.1 Plant Location ............................................................................... 21
6.2 Plant Layout ............................................................................... 24
CHAPTER SEVEN: SAFETY & ENVIRONMENTAL ASPECTS .............................. 26
7.1 Safety and Environment Aspects ............................................................................ 26
CHAPTER EIGHT: MASS AND ENERGY BALANCE .............................................. 30
8.1 Mass balance ............................................................................... 30
8.2 Energy Balance ............................................................................... 43
CONCLUSION ............................................................................................................. 50
REFERENCES ............................................................................................................. 51
APPENDIX A ............................................................................................................... 54
Mass balance ............................................................................... 54
Energy Balance ............................................................................... 65
APPENDIX B ............................................................................................................... 74

ii
LIST OF FIGURES
Figure 1: Chemical structure of titanium dioxide ................................................................ 2
Figure 2: growth rate of titanium dioxide by region (2023-2028) (Intelligence, Mordor, 2023)
........................................................................................................................................ 6
Figure 3: global market of titanium dioxide by application (Pulidindi & Mukherjee, 2020) ... 7
Figure 4: Chloride price trend (Intratec, 2023) .................................................................. 7
Figure 5: Price trend of Rutile from 2014-2021 (Economics, Consensus, 2021) .................... 8
Figure 6: process flow sheet of sulphate route to produce titanium dioxide (Lakshmanan, et
al., 2015) ....................................................................................................................... 10
Figure 7: process flow sheet of chlorine process (Lakshmanan, et al., 2015) ...................... 11
Figure 8: Block flow diagram of Titanium dioxide plant.................................................... 15
Figure 9: Process flow diagram ...................................................................................... 20
Figure 10: plant layout ................................................................................................... 25
Figure 11: Titanium dioxide pictogram ............................................................................ 26
Figure 12: hazard picograms of chlorine gas ................................................................... 27
Figure 13: hazard pictograms of TiCl4 ............................................................................. 27
Figure 14: carbon monoxide hazard pictograms ............................................................... 28
Figure 15: hazard pictograms of silicon tetrachloride ....................................................... 28
Figure 16: pictograms hazard of iron III chloride ............................................................. 29
Figure 17: Reactor inlet and outlet stream ....................................................................... 32
Figure 18: Inlet and outlet streams on cooler ................................................................... 34
Figure 19: Inlet & outlet stream of condenser .................................................................. 37
Figure 20: Converter inlet and outlet streams................................................................... 39
Figure 21: Oxidized reactor inlet and outlet streams ......................................................... 41
Figure 22: Inlet and outlet streams to the S-201 ............................................................... 42

iii
LIST OF TABLES
Table 1: The main physical and chemical properties of Rutile, titanium dioxide (Brittain, et
al., 1992).......................................................................................................................... 4
Table 2: Titanium Dioxide Industry Segmentation (Intelligence, Mordor, 2023) ................... 6
Table 3: Comparison between the two commercial routes.................................................. 12
Table 4: Chemical-physical properties of Rutile (Moodley, 2011) ...................................... 16
Table 5: physical-chemical properties of chlorine ............................................................. 17
Table 6: physical-chemical properties of coke-carbon ....................................................... 18
Table 7: the molecule weight of various component .......................................................... 30
Table 8: required amount of titanium dioxide ................................................................... 31
Table 9: inlet streams mass balance to the reactor ............................................................. 32
Table 10: outlet stream mass balance to the reactor ........................................................... 33
Table 11:inlet streams mass balance to the cooler HX-101 & S-101 ................................... 35
Table 12: outlet streams mass balance on HX-101& S-101 ................................................ 36
Table 13: inlet streams mass balance of condenser ............................................................ 37
Table 14: outlet streams mass balance of condenser .......................................................... 38
Table 15: inlet streams mass balance to the CV-201 .......................................................... 40
Table 16: inlet and outlet streams mass balance on oxidizer R-200..................................... 41
Table 17: Inlet and outlet streams mass balance of S-201 .................................................. 42
Table 18: Heat capacity of components in different temperatures ....................................... 43
Table 19:heat accompanied with rutile ............................................................................. 44
Table 20: heat through coke and chlorine ......................................................................... 44
Table 21:generated heat in the reactor .............................................................................. 45
Table 22:output stream heat............................................................................................. 45
Table 23:Heat on cooler HX-101 ..................................................................................... 46
Table 24: Condenser energy balance ................................................................................ 47
Table 25: heat carried by gas stream ................................................................................ 47
Table 26: Heat of inlet stream of R-200............................................................................ 48
Table 27: heat generated in R-200.................................................................................... 48
Table 28: heat of output stream of R-200.......................................................................... 48
Table 29: Heat energy in converter .................................................................................. 49
Table 30: requirement raw material mass flow rates .......................................................... 59
Table 31: inlet and outlet streams mass balance on R-100.................................................. 60
Table 32: Inlet and outlet streams mass flow rate on HX-101 & S-101 ............................... 61
Table 33: inlet & outlet streams on condenser................................................................... 62
Table 34: inlet and outlet mass flow rate of CV-201.......................................................... 63
Table 35: Inlet and outlet streams mass balance on oxidizer reactor ................................... 63
Table 36: Inlet & outlet stream mass balance on S-102...................................................... 64
Table 37: conversion from Celsius to kelvin ..................................................................... 65
Table 38: Heat capacity for several component in different temperature ............................. 65
Table 39: heat accompanied with rutile in the reactor ........................................................ 68
Table 40: The generated heat in the reactor....................................................................... 69
Table 41: heat output for the reactor................................................................................. 69
Table 42: cooler heat energy............................................................................................ 70
Table 43: inlet heat to the condenser at 137 ℃ .................................................................. 71
Table 44:outlet heat from R-200 ...................................................................................... 73
Table 45:energy balance on converter .............................................................................. 74

iv
CHAPTER ONE: INTRODUCTION

1.1 Titanium Dioxide Overview

Titanium dioxide consider as the whitest pigment that widely used in the manufacture

of coating and paints, with a chemical formula of TiO2, known as a Titania, is a

chemically inert semiconducting material which also exhibits photocatalytic activity in

the presence of the light and with an energy equal of more than its band-gap energy.

Titanium dioxide pigments make up around 60% of the global pigment's productions,

around 5.5 Million tons of TiO2 in 2011 were manufactured. In the past, the annual

increase of TiO2 pigment average production was around 2-5%. In 1791, titanium

dioxide was discovered by the mineralogist and clergyman "William Gregor".

(Middlemas, et al., 2015).

Titanium dioxide is a biocompatible, inexpensive and nontoxic material with a high

dielectric constant and chemical stability. TiO2 can be produced by two main process

known as a sulphate and chlorine process, with high level of purity. A naturally

occurring oxide sourced from Rutile, ilmenite and anatase, and have a main role as a

food coloring, it also can absorb and scatter UV Rays. (Middlemas, et al., 2013)

1
 Figure 1: Chemical structure of titanium dioxide

As shown in Figure one, the chemical formula of the TiO 2 which composed of two

oxygen molecules and one titanium molecule, connected to each other with a double

bond.

2
CHAPTER TWO: LITERATURE SURVEY

2.1 Application and Uses

Titanium dioxide applications may be limited due to its poor mechanical properties.

However, it has an electrical use in electro catalysis and sensors. By far it widely used

as pigment as a powder form, exploiting its optical properties. Titanium dioxide several

applications and uses are as follow: (Haider, et al., 2019)

❖ Photo Catalyst

Photo voltaic cells used Titania as a photo sensitizer, and when its used in an electrode

coating in the photo electrolysis cells, it can improve the efficiency of electrolytic

splitting of water to oxygen and hydrogen. (Brittain, et al., 1992)

❖ Pigments

The main role of TiO2 is as pigments in the powder form for providing opacity and

whiteness to such products like; coating, paints, paper, inks, plastic, food, cosmetics

and fibers. Which is a very white material and has a refractive index of "ca.2.7" that

surpassed by diamond only. The opacity that the material confers to the matrix where

the piment is housed, will be determined by the refractive index. Hence, the high

refractive index, gives low relatively levels of titanium dioxide pigment which is

required to achieve a white opaque coating. The bright white color and high refractive

index of titanium dioxide, make it an effective opacifier for the pigments. One of the

major roles of the material for exposed application is that resistance to discoloration

under the light of UV rays. (Parrino & Palmisano, 2021)

❖ Oxygen sensors

3
Titania tends to became sub stoichiometric and loss oxygen even in mildly reducing

atmospheres. In this form, the component becomes a semiconductor and correlated the

electrical resistivity to the oxygen content of the atmosphere, so TiO2 can used to sense

the amount of O2 in an atmosphere.

❖ Antimicrobial Coatings

❖ For Wastewater Remediation

2.2 Physical and Chemical Properties

Table 1: The main physical and chemical properties of Rutile, titanium dioxide (Brittain, et al., 1992)

Physical properties Chemical properties

Appearance White Stable under ordinary condition of use and storage

powder

Solubility Insoluble in Will not occur hazardous polymerization

water

Specific gravity 4.26 Incompatibilities reaction with lithium and other

Odor Odorless Reduction reactions

pH 6-7 ca. Reaction with peroxides

Melting point 1855 ℃ Should avoid condition like incompatibles and

dusting

Boiling point 2500-3000℃

Molar mass 79.87 g/mol

Density (Rutile) 4.23 g/cm3

4
CHAPTER THREE: MARKET SURVEY

3.1 Demand data

By the end of 2023, the market of titanium dioxide estimated to be more than 6 million

tons, and the market is projected to register more than 4% CAGR during the forecast

period. However, the market was impacted negatively by COVID-19, were the

construction work and the activities of the manufacturing were halted because of the

disruption of the supply chain & the labor shortages among the pandemic. Thus,

affecting the demand from several application sectors of titanium dioxide like; coating,

paints, cosmetics, plastic and others. However, the recovered condition in 2022

restoring the growth market trajectory. (Intelligence, Mordor, 2023)

Over the short term, paints and coating rabidly increasing demand will expected to be

the major driving factor of the titanium dioxide market size. Also, increasing the use of

ultrafine particles of TiO2 in construction industry and cosmetics expected to offer

opportunities through the forecast period. The following Table shows the Titanium

Dioxide Industry Segmentation.

5
Table 2: Titanium Dioxide Industry Segmentation (Intelligence, Mordor, 2023)

By grade Rutile

Anatase

By geography Coating & paints

Plastics

Pulp & paper

Cosmetics and others

By application Asia Pacific

North America

Europe

South America

Middle-East and Africa

Figure 2: growth rate of titanium dioxide by region (2023-2028) (Intelligence, Mordor, 2023)

6
As shown in Figure 2, Asia Pacific expected to have the highest growth rate of titanium

dioxide from 2023 to 2028. China is the world's second largest economy, where is

forecast to reach a projected market size about 7.8 USD by 2030. With a CAGR of

12.55 over the period from 2022 to 2030. (Intelligence, Mordor, 2023)

Figure 3: global market of titanium dioxide by application (Pulidindi & Mukherjee, 2020)

3.2 Chlorine Price Trend

Figure 4: Chloride price trend (Intratec, 2023)

7
The chlorine price trend in 2018 was increased in South Africa, and in the recently years

the price trend of chlorine witnessed an upward trajectory on the Chinese market due

to the COVID-19 all the manufacturing still dealing with the post COVID supply issues

constraints. However, the trends in the fourth quarter turned bearish eventually

registering a decline. Studies have shown that China currently has the highest

proportion of demand and export of chlorine gas due to the high rate of industries.

(Intratec, 2023)

3.3 Rutile Price Trend

Figure 5: Price trend of Rutile from 2014-2021 (Economics, Consensus, 2021)

The price of Rutile increases after the pandemic of COVID-19, were Asia Pacific was

the dominant area with the highest market size. China & India rising the disposable

income and owing to huge industrial investments, and these regions expected to drive

the market growth among the forecast period. (Economics, Consensus, 2021)

8
CHAPTER FOUR: PROCESS SELECTION

The aim of this project is to produce titanium dioxide with 99.5% purity and capacity

of 1 ton/operating day. There are two main commercial process that used to produced

titanium dioxide; the sulphate route and the thermochemical chlorine route. These

commercial routes differ from each other depends on the raw materials requirements

and the chemistry of the process. In this section, the various manufacturing processes

of titanium dioxide will be illustrated.

4.1 Sulphate Process Route

The sulphate process was he first method that developed for the manufacturing of

titanium dioxide. It was used for the first time in 1915 in Norway, and over the years it

has been undergoing continuous improvement. The Sulphate process used H 2SO4,

which is sensitive to the acid price. (McNulty, G.S., 2017)

This route uses the ilmenite ore or synthetic titanium slag as a raw material, which is

dried and finely ground in balls mills before being digestion in H 2SO4, where excess

free acid will be used to enhance the digestion efficiency. First, due to the heat of

hydration, the temperature increases to around 60 ℃, and the subsequently the

exothermic reaction will raise the temperature to reach 200 ℃. After complete the

leaching reaction, the filter cake is leached with the cold water or by diluted sulfuric

acid that recycled from the process. The following reaction is the main reaction of the

sulphate process. (Manuel Jesús Gázquez1, et al., 2014)

𝐹𝑒𝑇𝑖𝑂3 + 2 𝐻2 𝑆𝑂4 = 𝑇𝑖𝑂𝑆𝑂4 + 2𝐻2 𝑂 + 𝐹𝑒𝑆𝑂4 (1)

Equations 2 & 3 are for the secondary step:

𝑇𝑖𝑂𝑆𝑂4 + 2𝐻2 𝑂 → 𝑇𝑖𝑂(𝑂𝐻)2 + 𝐻2 𝑆𝑂4 (2)

9
𝑇𝑖𝑂(𝑂𝐻)2 → 𝑇𝑖𝑂2 + 𝐻2 𝑂 (3)

The block flow diagram of the sulphate process to produce titanium dioxide is shown

by the following Figure.

Figure 6: process flow sheet of sulphate route to produce titanium dioxide (Lakshmanan, et al., 2015)

As shown in Figure 6, the sulphate route to produce titanium dioxide including several

steps which are; acid digestion and clarification, crystallization. Precipitation and

purification, doping, calcination and grinding step. The final temperature reach around

800-850 ℃. However, the sulphate process considers as a very complicated process and

the basic chemical reactions consists of series of simple reaction like; calcination, acid

hydrolysis, and ion concentrate. (Lakshmanan, et al., 2015)

10
4.2 Chlorine Process Route

The second route that used to produce titanium dioxide is the thermochemical chlorine

process which is consider the younger process, were its developed in the 20 th century,

which depends on Rutile, chlorine and coke as a raw material of the process. In a

fluidized bed reactor, at a temperature between 800-1200℃, the chlorine reacts with a

titanium-containing mineral such a rutile which is not attacked by sulfuric acid, at the

presence of coke to form the reducing conditions, to produce anhydrous titanium

chloride. Then by condensation unit, the purification of the anhydrous tetrachloride is

done. Then the gas stream of the condensation step continues to the conversion. Then

by cyclone separation, and oxidation process the titanium dioxide form and complete

to be washed, calcined and stored. (Manuel Jesús Gázquez1, et al., 2014)

Figure 7: process flow sheet of chlorine process (Lakshmanan, et al., 2015)

11
As shown in Figure 7, the main steps of the chlorine process including, chlorination,

condensation of gas and purification of TiCl4, oxidation of tetrachloride, recovery of

titanium dioxide. The main and secondary reactions of the process illustrated as follow:

2𝑇𝑖𝑂2 + 4𝐶𝑙2 + 3𝐶 → 2𝑇𝑖𝐶𝑙4 + 𝐶𝑂2 + 2𝐶𝑂 (4)

𝐶𝑂 + 0.5 𝑂2 → 𝐶𝑂2 (5)

𝑇𝑖𝐶𝑙4 + 𝑂2 → 𝑇𝑖𝑂2 + 2𝐶𝑙2 (6)

𝑆𝑖𝑂2 + 2𝐶𝑙2 + 𝐶 → 𝑆𝑖𝐶𝑙4 + 𝐶𝑂2 (7)

2𝐹𝑒𝑂 + 3𝐶𝑙2 + 𝐶 → 2𝐹𝑒𝐶𝑙3 + 𝐶𝑂2 (8)

4.3 Selection Process

Table 3: Comparison between the two commercial routes

Aspects Chloride process Sulphate process

Purity 90-99.5% Less than 90%

Water pollution No such problem is Disposal of spent acid into water

encountered bodied may cause pollution

Water usage Less amount Huge amount

Complexity Less More

Raw material Rutile and chloride Ilmenite and sulfuric acid

Cost of product Higher Less

Operation temperature 800-1200 ℃ 600-1000℃

Particle size 190-250 nm 250-450 nm

Energy consume Less More

Color Blue Yellow

12
As shown in Table 3, the cost of titanium dioxide from chloride process is higher than

the cost from sulphate process, due to the uses of advanced equipment and high quality

of the raw materials, and the purity of it also more from the chloride route. While the

sulphate process considers as a discontinuous process with a complex process flow,

which usually required more than 20 steps in the process which needs to consume a lot

of energy and it discharging a significant amount of waste (Cahyani, Imala Septi, 2017).

While in chloride process the energy is saved due to the reason that the particles are

easy to depolymerize. Also, the whiteness of the product from the chloride process is

much better. From the above comparison between the tow process, the chloride process

has been selected for this project.

13
 CHAPTER FIVE: PROCESS DESCRIPTION

5.1 Chlorine process overview

The development of the chloride route to produce titanium dioxide started in 1940s,

where the first plant was run and owned by Dupont in the early of 1950s, and in North

America, Australia & Asia there are currently 23 chloride process plant. Were the

chloride process route can account for 60% of around 5.5 million ton/annum of titanium

dioxide pigment worldwide.

The chloride route consists a wide range of titaniferous feedstocks including high-grade

titanium dioxide like; rutile, ilmenite sand, upgraded slag, SREP, and synthetic rutile.

The selection of the raw materials depends on the percentage and the presence of heavy

metal impurities, were they can influence the purity of the desired product. The

following Figure illustrates the main stages in the chloride process, which include

reactor, heat exchanger, separation, condensation, conversation, oxidation, cyclone

separation and finishing stage.

14
Figure 8: Block flow diagram of Titanium dioxide plant

15
5.2 Physical and Chemical Properties
Table 4: Chemical-physical properties of Rutile (Moodley, 2011)

Chemical formula TiO2

Crystal system Tetragonal

Hardness 6-6.5

Class Oxide

Specific gravity 4.24

Color Red-brown-black

Cleavage Distinct/ good (110) distinct

Tenacity Brittle

Molar mass 79.8658 g/mol

Melting point 1830-3000℃

Water solubility Insoluble

Appearance Shape powder

Storage Room temperature

Density 4.17 g/mL at 25 ℃

Boiling point 2900℃

Ph <1

As shown in the above Table, Rutile is an oxide group mineral that have the chemical

formula of TiO2, which contain around 85% of titanium dioxide. Rutile has one of the

highest refractive indices at all crystal's wavelengths. Also, it characteristic by its high

dispersion & birefringence. These properties able Rutile to produce some optical

elements like polarized optics for infrared wavelengths longer than 4.5.

16
Table 5: physical-chemical properties of chlorine

Chemical formula Cl

Atomic weight 35.453 g/mol

Critical density 573.0 kg/m3

Boiling point -33.97℃

Critical pressure 7977 kPa

Critical temperature 143.75 ℃

Latent heat of vaporization 288.1 kJ/kg

Odor Penetrating and irritating odor

Color Greenish yellow

Flammability Not flammable nor explosive

Chemical reactions Reaction with water, metals, and organic

compounds

Chlorine presence at the formula of Cl2, which consists of two atoms of chlorine. It can

be combines with all atoms almost, except for the lighter noble gases. Chloride is one

of the best components that used in industry due to its high ability to reaction with

several component. Chlorine can displace heavier, less electronegative, iodine, bromide

and halogens from compounds. Also, it converts several oxides to chlorides such as the

conversion of trioxide iron into corresponding chloride. Furthermore, it can produce a

solid hydrate when reacts with water.

17
Table 6: physical-chemical properties of coke-carbon

Atomic mass 12.011 g/mol

Density 2.2 g/cm3

Melting point 3652 ℃

Boiling point 4827℃

Carbon compounds show 4 Combustion reaction (complete

reactions &incomplete)

Oxidation reaction

Addition reaction

Substitution reaction

5.3 Chloride Process Description

In this project, the selected route to produce titanium dioxide with a capacity of one ton

per operating day and with a purity of 99.5%. first, feedstock-Rutile include 85% pure

titanium dioxide and coke with chloride gas will added to the reactor R-100 at a

temperature of 900℃, and 1.5 atm pressure and the following reactions will occur in

the reactor:

2𝑇𝑖𝑂2 + 4𝐶𝑙2 + 3𝐶 → 2𝑇𝑖𝐶𝑙4 + 𝐶𝑂2 + 2𝐶𝑂

𝑆𝑖𝑂2 + 2𝐶𝑙2 + 𝐶 → 𝑆𝑖𝐶𝑙4 + 𝐶𝑂2

2𝐹𝑒𝑂 + 3𝐶𝑙2 + 𝐶 → 2𝐹𝑒𝐶𝑙3 + 𝐶𝑂2

the outlet stream from the reactor include several components which are; TiCl4, CO2,

CO, FeCl3, SiCl4, Cl2, TiO2, & Coke. Then the component will continue to be cooled

in the heat exchanger HX-101 with water and the temperature will reduce to 320℃ with

18
1.2 atm pressure. E-102 will be used to reduce the temperature to be 137℃. The outlet

streams from the separation unit S-101 contain H2O, that will be stored in tank T-104,

Coke, FeCl3, and traces of TiO2 will be stored in T-103, and the top stream from the

separation include TiCl4, CO2, CO, SiCl4, & Cl2 will continue to condensation unit -

CS-200 with a top stream include water to separate pure TiCl4 from other component

that will complete to the converter unit to convert CO to carbon dioxide.

Then, pure TiCl4 will inters to the oxide burner at a temperature of 1000℃ and oxidize

with oxygen to form TiO2 and Cl2, were the traces of TiCl4 will be stored in T-107.

Now, cyclone separation S-102 used to separate pure titanium dioxide from chloride

and the chloride gas will be recycled to the main reactor.

Pure TiO2 will inters to filtration, and dryer to enhance the purity and then packaging

in T-108. The product usually surface treatment to enhance the property of it. At the

final stage of the process the produce pure titanium dioxide provides excellent color

and high opacity but have relatively reactive surface. Therefore, the majority of

commercial pigments are coated with coating or inorganic or organic treatment. The

surface treating o titanium dioxide is done to enhance the wetting and dispersion in

several media, improve the color stability, improve durability, enhance the

compatibility with the dispersion stability ang increase air in the film of the flat latex

paints.

The surface treatment depends on the end of application is usually a combination of

zirconia or alumina silica, after that, the desired product dried and intensively milled

and packaging. The detailed process flow diagram of titanium dioxide plant from

impure titanium dioxide in Rutile is shown below.

19
 CL2 TiCL4
99.99% S4 CO2 S5
purity CO
T-102 TIO2 H2O
T-101 ORA
SIO2
FeCL3 S8
30 C (Rutile) 30 C R-100 SiCL4
9atm FEO 900 C
9 atm CL2
1.5 atm Coke TiCL4
TiO2 HX-101 H2O CO
S3 S2 320 C CO2
S-101
1.2 atm CL2
137 C
SiCL4
1atm
S1
S6
S7
P-101 V-101 E-101
Coke
S1 E-102
FeCL3
TiO2 V-102
H2O
S14 Coke Coke S9
CO2
SiCL4 S12 T-103 T-104
CL2
CV-201 E-104 H2O
200 C CO
2 atm CO2 E-103
CL2 CS-200
T-105 SiCL4 137 C
O2 1 atm
H2O
S13 O2
S10 S15
T-106 R-200 Pure
1000 C TiCL4
Recycle S-102 1 atm
CL2 40 C
1atm
S19
S18 TiO2
TiO2 CL2
E-105

S11
D-201 S17
TiO2 F-201

T-108
TiO2 S16
O2
TiCL4

T-107

Cool Air

Pipeline List
Equipment List streams number Total mass flow rate kg/hr
Displayed Text Description s tream 1 12.64
CS-200 Condenser s tream 2 60.21
s tream 3 107.77
CV-201 conventer
s tream 4 180.077
D-201 dryer s tream 5 200
E-101/105 heater or cooler s tream 6 200
F-201 filter s tream 7 18.306
HX-101 heat exchanger-cooling s tream 8 161.77
s tream 9 150
P-101 pump
s tream 10 150
R-100 reactor s tream 11 109.64
R-200 oxidation burner s tream 12 52.12
S-101 seperation (L/G) s tream 13 200
S-102 Cyclone seperator s tream 14 252.12
T-101/108 storage tank s tream 15 18.45
s tream 16 12.81
V-101-102 Valve
s tream 17 115.29
s tream 18 73.83
s tream 19 41.46

Figure 9: Process flow diagram

20
CHAPTER SIX: PLANT LAYOUT & LOCATION

6.1 Plant Location

One of the critical decisions that are taken in building factories in general is choosing

the location of the factory, as it has a significant impact on its operations, costs, and

success in general. Referring to the market analysis in the previous part, it was found

that the best location for the factory is the countries of the Asia Pacific, specifically

China, for several main factors which are summarized as follow:

• Availability of Raw Materials

One of the crucial and greatly affecting production, supply chains and comprehensive

business operations in various chemical industries is the availability of raw materials,

as it plays a crucial role in determining the location for the establishment of any

industrial activity. The price and availability of suitable raw materials will usually

determine the site location, where the plant must be near tot the raw material sources to

decrease the cost of transfer it. It was important for those in charge of the industries in

general to carefully monitor the availability of raw materials and develop their sourcing

strategies accordingly.

• Nearness to the Market

Approaching consumption markets allows industrial producers to reduce transportation

costs and logistical expenses associated with delivering their products to customers, and

also provides better access to potential customers, and may also reduce lead times that

start from the moment the order is submitted to the moment of delivery and has an

impact on storage costs as products can be produced and delivered on time fitting,

reducing the need for warehousing and inventory holding.

21
 • Transportation

Transportation directly affects cost efficiency, supply chain management, market

accessibility, business activities, customer satisfaction, and industry competitiveness.

Industrial producers need reliable, affordable, and efficient transportation options to

improve their operations, expand their market reach, and deliver products in a timely

manner. The transport from and into the plant will be an over ridding consideration in

the selection of the plant location. The selected site should be closed to at least of the

type of transport road such as; rail, sea port, or water way. Rail transport is cheaper for

the long-distance transport of the raw materials.

• Water supply

Water supplies are essential to industrial production, as they are essential for

manufacturing operations, equipment operation, cleaning, sanitation, wastewater

treatment, environmental sustainability, meeting stakeholder expectations, and

ensuring business continuity. Access to adequate water supplies is essential for the

efficient and sustainable operation of industrial processes in various sectors.

• Utilities and Energy

Utilities and energy are essential to industrial production because they provide power

for production processes, for heating and cooling, lighting and visibility, ensure power

quality and reliability, support energy-intensive operations, facilitate renewable energy

integration, contribute to energy efficiency and cost savings, and help achieve

regulatory compliance. Access to affordable and reliable utilities and energy is critical

to the smooth and efficient operation of industrial facilities and to achieving

sustainability goals. So, located firms close to the power industries and coal beds may

highly reduce the money, efforts and time.

22
 • Government Policies

When selection the plant location it's important to know the local government policies

like; institutional finance, licensing policies, government subsides, etc.

• Suitability of Climate

One of the most essential factors that influencing the site selection is the climate change,

were some industrial required a dry and cool conditions. The climate can affect the

productivity, labor efficiency, and maintenance cost.

• Availability of Facilities

In design of any plant, the availability of facilities like school, hospital, and housing is

very important factor, which can motivate the workers and increase the efficiency of

them.

• Waste Disposal &Treatment

The disposal and treatment of waste is vital to industrial production because it mitigate

environmental impacts, ensure regulatory compliance, enhance resource conservation,

protect worker health and safety, enhance reputation and stakeholder satisfaction,

manage costs, positively impact communities, and stimulate innovation and

competitiveness. By implementing effective waste management strategies, industrial

producers can reduce their environmental footprint, improve sustainability, and

contribute to a more sustainable and responsible industrial ecosystem.

• Labor supply

Labor provision is critical to industrial production because it ensures workforce

availability, provides skilled labor and experience, drives innovation and productivity,

enables flexibility and adaptability, contributes to cost management, supports training

23
and development, fuels industry growth and economic impact, and enhances social

stability and well-being. Access to skilled and available labor is essential to the success,

competitiveness, and sustainability of industrial producers.

6.2 Plant Layout

The buildings and process units must be arranged in such a way that allows for the most

economical flow of people and materials. Dangerous process with high temperature and

pressure need to be a safe distance from others, and the layout of the plant must be

allowed for the future expansion. Usually the process units laid out first which allows

for smooth flow of the materials between the steps of the process. The distance of any

equipment from another must be at least 30 m. also the primary ancillary buildings

location is sited as to decrease the time of traveling between buildings. Next, the

laboratory and administrative offices are located away from the dangerous materials.

Also, the processing equipment's must be close to the control room.

The utility building must be located as to minimize piping between the plant units.

Storage section must be located between the loading and unloading facilities and close

to the process unit. Hazard materials tanks must be placed at least 70 m away from the

plant. The essential factors that considered when planning the plant layout are listed as

follow:

• Process requirements: such as elevation of the column base to give more net

positive suction head for the pump.

• Economic and Operation cost: construction costs may decrease by arranging

buildings and process units that minimize the pipes between the units.

24
• Modular construction: occurs when some section of the plant constructed

outside, then transported by road to the site, which improve the quality, less

cost, and less the requirements for the skilled labors.

• Future Expansion: such as oversized the pipe to be able to allow more flow

capacity of the materials in future.

• Maintenance Convenience: easy access to the equipment that required

maintenance.

• Safety

Figure 10: plant layout

25
 CHAPTER SEVEN: SAFETY &

ENVIRONMENTAL ASPECTS

7.1 Safety and Environment Aspects

This section illustrated the safety and environmental impact of the desired product, raw

materials and by products of the titanium dioxide plant. The plant designed to produce

1 ton per operation day, with 99.5% purity, (APPENDIX B) contain the material safety

data sheet of titanium dioxide and the main raw material (chlorine gas). From the

material safety data sheet, the safety and environmental aspects of the materials are

described as follow:

❖ Titanium Dioxide

Titanium dioxide may cause critical hazards to environment and man, were it can

irritate the respiratory tract if formed a breathable dust (carcinogenicity with category

2). It should be handling in accordance & good industrial hygiene and safety and store

in a closed. Dry and cool place. According to HMIS rating it classify as category 1 of

health, flammability and physical hazards in category 0. (Global, management safety,

2014)

Figure 11: Titanium dioxide pictogram

❖ Chlorine gas

According to OSHA-hazard communication standard, the material considered

hazardous. It classifying as an oxidizing gas in category 1, aquatic hazard in category

26
1, skin corrosion in category 1, acute toxicity in class 2, and cause serious aye damage

in class 1. Chlorine gas must store locked up, in well ventilated area and protect from

sunlight. (Airgas, 2021)

Figure 12: hazard picograms of chlorine gas

❖ Rutile

According to US agency for toxic material, rutile is not classified as a hazardous

substance. It not toxic, low hard to skin, but at high concentration it can be irritating if

inhaled. The employee must avoid breathing dust and wash after handling. Dust mask

and safety glasses with side shields must be use for personal protection.

❖ Titanium Tetrachloride

Titanium tetrachloride classified hazardous chemicals according to OSHA 2012. May

cause skin corrosion -1B, acute inhalation toxicity-2, eye irritation -1, target organs-

respiratory system-3 and fatal if inhaled. It must be store locked up and in well-

ventilated place and the container must keep tightly closed. (Fisher , Company

Scientific, 2023)

Figure 13: hazard pictograms of TiCl4

27
 ❖ Carbon dioxide

According to OSHA standards the material is consider hazardous, which it may explode

if heated, contain gas under pressure, may cause rapid suffocation, and can increase

respiration and heart rate. Should be protect from sunlight and in a well-ventilated

place. (Aldrich, Sigma, 2023)

❖ Carbon monoxide

Related to OSHA standards, carbon monoxide considered a hazardous material, which

it classifies as a flammable gas in category 1, compressed gases, acute toxicity in

category 3, toxic to reproduction in category 1, and specific target organ toxicity in

category 1. Must store locked up and in a well-ventilated area. (Airgas, 2020)

Figure 14: carbon monoxide hazard pictograms

❖ Silicon Tetrachloride

The substance is considered a hazardous according to OSHA standard. Where its

danger, fatal if inhaled, causes a skin irritation (category 2), cause serious eye irritation

(category 2A), and may cause a respiratory irritation (Category 3). Must store locked

up and the container must keep tightly closed. And disposal in accordance with national,

local and regional regulations. (Airgas, 2020)

Figure 15: hazard pictograms of silicon tetrachloride

28
 ❖ Iron (III) Chloride

Iron III chloride considered a dangerous material according to EC regulation-2008,

which cause a serious eye damage and irritation, skin corrosives, acute toxicity,

corrosive to metals and may cause skin sensitisation. And it must store in a dry place.

(ROTH, 2021)

Figure 16: pictograms hazard of iron III chloride

29
 CHAPTER EIGHT: MASS AND ENERGY
BALANCE
8.1 Mass balance

The mass and energy balance of the main equipment of the chlorine process will show

in the following Tables, were in (APPENDIX A) the mass and energy balance

calculations steps will be illustrated.

Table 7: the molecule weight of various component

Component Molar mass g/mol

Cl2 71.12

TiO2 79.87

TiCl4 190.11

CO2 44

O2 32

C 12

SiO2 60.06

FeCl3 162.22

FeO 71.85

SiCl4 169.89

CO 28

30
2𝑇𝑖𝑂2 + 4𝐶𝑙2 + 3𝐶 → 2𝑇𝑖𝐶𝑙4 + 𝐶𝑂2 + 2𝐶𝑂

𝐶𝑂 + 0.5 𝑂2 → 𝐶𝑂2

𝑇𝑖𝐶𝑙4 + 𝑂2 → 𝑇𝑖𝑂2 + 2𝐶𝑙2

𝑆𝑖𝑂2 + 2𝐶𝑙2 + 𝐶 → 𝑆𝑖𝐶𝑙4 + 𝐶𝑂2

2𝐹𝑒𝑂 + 3𝐶𝑙2 + 𝐶 → 2𝐹𝑒𝐶𝑙3 + 𝐶𝑂2

Table 8: required amount of titanium dioxide

required amount of TiO2/day 1 ton/operating day

required amount of TiO2 /year 300 ton/year

Purity 0.995

real amount 298.5 ton/year

real amount 41.45833 kg/hr

31
R-100 MASS BALANCE

Figure 17: Reactor inlet and outlet stream

Table 9: inlet streams mass balance to the reactor

Inlet stream S1, S2 & S3

Component mass flow rate mass mw molar flow rate mole

kg/hr fraction kg/kmol kmol/hr fraction

Chloride 107.222 0.595 71.12 1.507630 0.4519

Coke 12.6393 0.0701 12 1.05327 0.3157

TiO2 (0.85) 51.187 0.2842 79.87 0.64083 0.1921

FeO (0.1) 6.0215 0.0334 71.85 0.083 0.0251

SiO2 (0.05) 3.0107 0.0167 60.06 0.05012 0.0150

Total 180.07 1 294.9 3.335676 1

32
Table 10: outlet stream mass balance to the reactor

Outlet stream S4

Component Mass flow rate Mass Mw Molar flow rate Mole fraction

kg/hr fraction kg/kmol kmol/hr

TiCl4 109.6454 0.608 190.11 0.5767 0.3025

SiCl4 8.516485 0.0472 169.89 0.05012 0.0264

FeCl3 13.5951 0.075 162.22 0.0838 0.043

CO2 16.7378 0.092 44 0.38040 0.1993

CO 16.1489 0.089 28 0.5767 0.3022

Cl2 10.7222 0.0595 71.12 0.1507 0.07914

Coke 0.4070 0.002 12 0.0339 0.01779

TiO2 4.30417 0.0239 79.87 0.05389 0.02826

Total 180.071 1 757.21 1.9064 1

𝑚𝑎𝑠𝑠 𝑒𝑛𝑡𝑒𝑟𝑖𝑛𝑔 = 𝑚𝑎𝑠𝑠 𝑙𝑒𝑎𝑣𝑖𝑛𝑔 = 180.077 𝑘𝑔/ℎ𝑟

33
HX-101 & S-101 MASS BALANCE

Figure 18: Inlet and outlet streams on cooler

34
Table 11:inlet streams mass balance to the cooler HX-101 & S-101

Inlet streams S4& S5

Stream 4

Component mass flow mass mw molar flow mole fraction

rate kg/hr fraction kg/kmol rate kmol/hr

TiCl4 109.6454 0.6088 190.11 0.57675 0.30253

SiCl4 8.51648 0.047293 169.89 0.05013 0.02629

FeCl3 13.59519 0.07549 162.22 0.08387 0.043961

CO2 16.73789 0.0929 44 0.38041 0.19954

CO 16.148927 0.08967 28 0.57674 0.30253

Cl2 10.72226 0.05954 71.12 0.15076 0.07908

Coke 0.407067 0.002260 12 0.03392 0.01779

TiO2 4.30417 0.02390 79.87 0.05388 0.0282

Total 180.0774 1 757.21 1.90641 1

Stream 5

H2O IN 200 1 18 11.1111 1

35
Table 12: outlet streams mass balance on HX-101& S-101

Outlet streams S6, S7 & S8

Component mass flow mass mw kg/kmol molar flow mole fraction

rate kg/hr fraction rate

kmol/hr

stream 6

H2O Out 200 1 18 11.111 1

Stream 7

FeCl3 13.59519 0.742645 162.22 0.08380 0.48833

Coke 0.40706 0.022236 12 0.03392 0.197660

TiO2 4.30417 0.2351 79.87 0.05388 0.31400

Total 18.306 1 254.09 0.1716199 1

Stream 8

TiCl4 109.6454 0.67778 190.11 0.5767 0.33245

SiCl4 8.51648 0.052645 169.89 0.05012 0.02889

CO2 16.7378 0.10346 44 0.3804 0.21928

CO 16.1489 0.099825 28 0.57674 0.33245

Cl2 10.72226 0.066281 71.12 0.15076 0.086905

Total 161.771 1 503.12 1.73479 1

𝑚𝑎𝑠𝑠 𝑒𝑛𝑡𝑒𝑟𝑖𝑛𝑔 = 𝑚𝑎𝑠𝑠 𝑙𝑒𝑎𝑣𝑖𝑛𝑔 = 380.077 𝑘𝑔/ℎ𝑟

36
MASS BALANCE ON CONDENSER CS-200

Figure 19: Inlet & outlet stream of condenser

Table 13: inlet streams mass balance of condenser

Inlet streams S8 & S9

STREAM 8

Component mass flow rate mass mw molar flow rate mole

kg/hr fraction kg/kmol kmol/hr fraction

TiCl4 109.6454482 0.67778176 190.11 0.5767474 0.332458736

SiCl4 8.516485028 0.052645306 169.89 0.050129407 0.028896462

CO2 16.73789423 0.103466579 44 0.380406687 0.219280618

CO 16.14892719 0.099825834 28 0.5767474 0.332458736

Cl2 10.72226771 0.066280521 71.12 0.150763044 0.086905448

Total 161.7710223 1 503.12 1.734793938 1

STREAM 9

H2O In 150 1 18 8.333333333 1

37
Table 14: outlet streams mass balance of condenser

STREAM 10

H2O Out 150 1 18 8.333333333 1

STREAM 12

CO2 16.73789423 0.321107144 44 0.380406687 0.328489982

CO 16.14892719 0.30980814 28 0.5767474 0.498034734

Cl2 10.72226771 0.205700712 71.12 0.150763044 0.13018738

SiCl4 8.516485028 0.163384004 169.89 0.050129407 0.043287904

Total 52.12557416 1 313.01 1.158046538 1

STREAM 11

TiCl4 109.6454482 1 190.11 0.5767474 1

𝑚𝑎𝑠𝑠 𝑖𝑛 = 𝑚𝑎𝑠𝑠 𝑜𝑢𝑡 = 311.77 𝑘𝑔/ℎ𝑟

38
CONERTER MASS BALANCE CV-201

Figure 20: Converter inlet and outlet streams

39
Table 15: inlet streams mass balance to the CV-201

INLET STREAMS S12 & S13

STREAM 12

Component mass flow rate mass mw molar flow rate mole

kg/hr fraction kg/kmol kmol/hr fraction

CO2 16.73789423 0.321107144 44 0.380406687 0.328489982

CO 16.14892719 0.30980814 28 0.5767474 0.498034734

CL2 10.72226771 0.205700712 71.12 0.150763044 0.13018738

SiCl4 8.516485028 0.163384004 169.89 0.050129407 0.043287904

Total 52.12557416 1 313.01 1.158046538 1

STREAM 13

O2 200 1 32 6.25 1

OUTLET STREAM 14

CO2 232.8868214 0.923693767 44 5.292882305 0.963432711

CL2 10.72226771 0.042527489 71.12 0.150763044 0.027442524

SiCl4 8.516485028 0.033778743 169.89 0.050129407 0.009124766

Total 252.1255742 1 285.01 5.493774757 1

𝑚𝑎𝑠𝑠 𝑖𝑛 = 𝑚𝑎𝑠𝑠 𝑜𝑢𝑡 = 252.12 𝑘𝑔/ℎ𝑟

40
OXIDATION REACTOR MASS BALANCE-R-200

Figure 21: Oxidized reactor inlet and outlet streams

Table 16: inlet and outlet streams mass balance on oxidizer R-200

INLET STREAMS S11&S15

STREAM 11

Component mass flow mass mw molar flow rate mole

rate kg/hr fraction kg/kmol kmol/hr fraction

TiCL4 109.64 1 190.11 0.576 1

STREAM 15

O2 18.455 1 32 0.57 1

STREAM 16

TiCL4 10.9645 0.8559 190.11 0.057 0.5

O2 1.84559 0.144 32 0.057 0.5

SUM 12.8101 1 222.11 0.11534 1

STREAM 17

TIO2 41.458 0.359 79.87 0.5190 0.333

CL2 73.8328 0.6404 71.12 1.03814 0.6666

SUM 115.291 1 150.99 1.55721 1

41
 𝑚𝑎𝑠𝑠 𝑖𝑛 = 𝑚𝑎𝑠𝑠 𝑜𝑢𝑡 = 128.101 𝑘𝑔/ℎ𝑟

MASS BALANCE ON CYCLONE SEPARATOR S-201

Figure 22: Inlet and outlet streams to the S-201

Table 17: Inlet and outlet streams mass balance of S-201

STREAM 17

Component Mass flow Mass Mw Molar flow rate Mole

rate kg/hr fraction kg/kmol kmol/hr fraction

TiO2 41.458 0.3595 79.87 0.5190 0.3333

Cl2 73.832 0.640 71.12 1.0381 0.6666

Sum 115.2 1 150.99 1.557 1

STREAM 18

Cl2 73.83 1 71.12 1.0381 1

STREAM 19

TiO2 41.458 1 79.87 0.519 1.0000

𝑚𝑎𝑠𝑠 𝑖𝑛 = 𝑚𝑎𝑠𝑠 𝑜𝑢𝑡 = 115.3 𝑘𝑔/ℎ𝑟

42
8.2 Energy Balance

Table 18: Heat capacity of components in different temperatures

Molecular heat capacity kj/kmol. K

Component 298 1173 1273 593 410

TiO2 56.8164 86.2223 89.3915 67.5818

CL2 33.8806 37.9354 38.7654 36.4043 35.2192

FeO 50.9981

SiO2 44.8546

Coke 8.9417 23.6303 16.2731

CO2 56.4886 47.2195 41.6730

CO 33.6420 30.4050 29.4131

TiCl4 149.0000 149.4400 149.1000 149.1000

FeCL3 77.7800 77.7800

SiCL4 135.6000 136.8800 136.5000 136.5000

O2 26.0900 26.0900

43
R-100 ENERGY BALANCE

Table 19:heat accompanied with rutile

heat accompanied with rutile

component mw kg/kmol molar flow rate kmol/hr Q Kj/hr

TiO2 79.87 0.51907266 8788.563337

FeO 71.85 0.08380716 1273.653052

SiO2 60.06 0.050129407 670.0638607

SUM 211.78 0.653009227 10732.28025

Table 20: heat through coke and chlorine

heat through coke

component mw kg/kmol molar flow rate kmol/hr Q Kj/hr

Coke 12.0000 1.0533 2806.5916

heat accompanied with chlorine

component mw kg/kmol molar flow rate kmol/hr Q Kj/hr

CL2 71.120 1.038 51230.701

0.469 4740.119

55970.820

44
Table 21:generated heat in the reactor

generated heat

component mw kg/kmol molar flow rate kmol/hr Q Kj/hr

TICl4 190.110 0.577 144.089

FeCL3 162.220 0.084 165.234

SiCL4 169.890 0.050 8.692

SUM 522.220 0.711 318.015

Table 22:output stream heat

Heat associated with output stream

component mw kg/kmol molar flow rate kmol/hr Q Kj/hr

TICl4 190.11 0.58 100802.18

CO2 44.00 0.38 25206.17

CO 28.00 0.58 22759.63

FeCL3 162.22 0.08 7646.22

CL2 71.12 0.15 6708.68

SiCL4 169.89 0.05 8048.79

Coke 12.00 0.03 940.27

TiO2 79.87 0.05 5450.35

Sum 757.21 1.91 177562.30

Heat added to the system =107734.58 kj/hr

45
COOLER ENERGY BALANCE

Table 23:Heat on cooler HX-101

Cooler HX-101

Component mw molar flow rate Q Kj/hr

kg/kmol kmol/hr

TICl4 190.1 0.5767 50993.8711

CO2 44.0 0.3804 10651.8292

CO 28.0 0.5767 10398.8392

FeCL3 162.2 0.0838 3865.4829

CL2 71.1 0.1508 3254.6319

SiCL4 169.9 0.0501 4057.6998

Coke 12.0 0.0339 327.3485

TiO2 79.9 0.0539 2159.6893

Sum 757.2 1.9064 85709.3919

heat in to the cooler 177562.3 KJ/HR

Heat out 85709.4 KJ/HR

Cooing water required 199.7 KG/HR

heat removed 91852.9 KJ/HR

heat in =heat out+ 177562.3 KJ/HR

removed

46
CONDESER ENERGY BALANCE

Table 24: Condenser energy balance

CONDENSER

component mw kg/kmol molar flow rate kmol/hr Q Kj/hr

TiCL4 190.11 0.58 50993.87

SiCL4 169.89 0.05 4057.70

CO2 44.00 0.38 10651.83

CO 28.00 0.58 10398.84

CL2 71.12 0.15 3254.63

Total 503.12 1.73 79356.87

Table 25: heat carried by gas stream

47
R-200 ENERGY BALANCE

Table 26: Heat of inlet stream of R-200

OXIDIZE BURNER

Component mw kg/kmol molar flow rate kmol/hr Q Kj/hr

O2 32.0000 0.5767 4484.1072

TICL4 190.1100 0.5767 35257.1453

Total 39741.2525

Table 27: heat generated in R-200

HEAT GENERATEED

component mw kg/kmol molar flow rate kmol/hr Q Kj/hr

TIO2 79.87 0.51907266 270.1773194

CL2 71.12 1.038145319

sum 150.99 1.557217979

Table 28: heat of output stream of R-200

heat output

component mw kg/kmol molar flow rate kmol/hr Q Kj/hr

TIO2 79.87 0.51907266 59068.07729

CL2 71.12 1.038145319 51230.70076

TiCL4 190.11 0.05767474 10971.87643

O2 32 0.05767474 1915.526339

SUM 123186.1808

heat added 83174.75099 kj/hr

48
CONVERTER ENERGY BALANCE

Table 29: Heat energy in converter

Heat output

Component mw kg/kmol molar flow rate kmol/hr Q Kj/hr

TIO2 79.87 0.51907266 59068.07729

CL2 71.12 1.038145319 51230.70076

TiCL4 190.11 0.05767474 10971.87643

O2 32 0.05767474 1915.526339

SUM 123186.1808

heat added 83174.75099 kj/hr

49
CONCLUSION

Titanium dioxide pigments is one of the most essential components that used in the

industry, which is characteristics by its physical properties as brightness and whiteness,

and provide opacity to a vast range of products from plastics and coating to others. The

manufacturing process of titanium dioxide was illustrated in this report which are the

sulphate and chloride routes which they used to produced more than 4.5 million per

annum worldwide. Sulphate and chloride route both start from an impure titanium

dioxide-based feedstock such as utile, illumine and other. Titanium dioxide is a simple

inorganic compound with a white powder form and it has a high refractive index of ca.

2.7. the chloride process was selected to be used in order to design the desired product,

which is much simple than sulphate process route and produce titanium dioxide with

more purity percentage than the other route. The plant total mass and energy balance

was illustrated in this report, and the environment aspects of each component in the

process was also show. furthermore, the market analysis of titanium dioxide with the

trend price of the raw materials was shown and the location of the plant selected to be

in China. The site was chosen depends in several factors such as the availability of

labor, raw materials transportation and others.

50
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Brittain, H., G., B., G., D. & J., Newman, A. W, 1992. TITANIUM DIOXIDE.

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53
APPENDIX A

Mass balance

In this section the detailed mass balance for each stream in titanium dioxide plant will

be illustrated, where the required capacity of the plant is 1 ton/operated day with 99.5%

purity. The capacity will be converted into kg/hr for 300 operating day per annum as

shown:

𝑡𝑜𝑛 𝑡𝑜𝑛 𝑘𝑔
𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑇𝑖𝑂2 = 1 = 300 = 41.6667 (9)
𝑑𝑎𝑦 𝑦𝑟 ℎ𝑟

𝑡𝑜𝑛
𝑟𝑒𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 300 𝑦𝑟
𝑇𝑖𝑂2 = 𝑃𝑢𝑟𝑖𝑡𝑦 × 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑇𝑖𝑂2 (10)

𝑡𝑜𝑛 𝑡𝑜𝑛
𝑟𝑒𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 300 𝑇𝑖𝑂2 = 300 × 0.995 = 298.5
𝑦𝑟 𝑦𝑒𝑎𝑟

𝑘𝑔 298.5 × 1000 𝑘𝑔
𝑅𝑒𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 = = 41.458
ℎ𝑜𝑢𝑟 300 × 24 ℎ𝑟

For the reaction of tetrachloride with oxygen, the required amount of titanium dioxide

and chloride gas are shown below:

𝑇𝑖𝐶𝑙4 + 𝑂2 → 𝑇𝑖𝑂2 + 2𝐶𝑙2 (11)

𝑀𝑤𝑇𝑖𝐶𝐿4
𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑇𝑖𝐶𝑙4 = 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦 × (12)
𝑀𝑤𝑇𝑖𝑂2

190.11 𝐾𝐺
𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑇𝑖𝐶𝑙4 = 41.458 × ( ) = 98.68
79.87 𝐻𝑟

𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓𝑇𝑖𝐶𝑙4

𝐴𝑐𝑡𝑢𝑎𝑙 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑇𝑖𝐶𝑙4 = (13)
𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛

The reaction conversion assumed to be 90%. So, the actual amount of tetrachloride is:

98.68 𝑘𝑔
𝐴𝑐𝑡𝑢𝑎𝑙 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑇𝑖𝐶𝑙4 = = 109.64
0.9 ℎ𝑟

54
The required amount of oxygen is calculated depends on the amount of tetrachloride as

a main reactant as shown:

𝑀𝑤𝑂2
𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑂2 = 𝐴𝑐𝑡𝑢𝑎𝑙 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡𝑇𝑖𝐶𝑙4 × 𝑀𝑊 (14)
𝑇𝑖𝐶𝑙4

32 𝐾𝑔
𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑂2 = 109.64 × ( ) = 18.45
190.11 ℎ𝑟

The chloride gas is product in the reaction above so the required amount of it is:

2×𝑀𝑤𝐶𝐿2
𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐶𝑙2 = 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦 × (15)
𝑀𝑤𝑇𝑖𝑂2

2 × 71.12 𝐾𝑔
𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐶𝑙2 = 41.458 × = 73.832
79.87 ℎ𝑟

There are 10% of the marital do not convert in the reaction, as follow:

Unreacted TiCl4:

𝑈𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡𝑇𝑖𝐶𝑙4 = 𝐴𝑐𝑡𝑢𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡𝑇𝑖𝐶𝑙4 × (1 − 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛) (16)

𝑘𝑔
𝑈𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡𝑇𝑖𝐶𝑙4 = 109.64 × (1 − 0.9) = 10.96
ℎ𝑟

Unreacted O2:

𝐾𝑔
𝑈𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡𝑂2 = 18.45 × (1 − 0.90) = 1.84
ℎ𝑟

The main reaction of the process is the reaction of impure titanium dioxide with chloride

gas and coke to produce tetrachloride, carbon monoxide & carbon dioxide as shown:

2𝑇𝑖𝑂2 + 4𝐶𝑙2 + 3𝐶 → 2𝑇𝑖𝐶𝑙4 + 2𝐶𝑂 + 𝐶𝑂2 (17)

Required amount of titanium dioxide:

2×𝑀𝑤𝑇𝑖𝑂2
𝑇𝑖𝑂2 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 = 𝐴𝑐𝑡𝑢𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡𝑇𝑖𝐶𝐿4 × (2×𝑀𝑊 ) (18)
𝑇𝑖𝐶𝑙4

55
 159.74 𝑘𝑔
𝑇𝑖𝑂2 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 = 109.64 × ( ) = 46.064
380.22 ℎ𝑟

Assumed the conversion of the main reaction to be 90%, the required amount of each

material is shown below:

𝑇𝑜𝑡𝑎𝑙 𝑅𝑢𝑡𝑖𝑙𝑒 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 𝑇𝑖𝑂2 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 × 0.85 × 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 (19)

𝑘𝑔
𝑇𝑜𝑡𝑎𝑙 𝑅𝑢𝑡𝑖𝑙𝑒 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 46.06 × 0.85 × 0.9 = 60.215
ℎ𝑟

Rutile including 85% impure TiO2, 10% FeO, & 5% SiO2, the amounts of rutile

components are:

𝑘𝑔
𝐹𝑒𝑂 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = 10% × 𝑇𝑜𝑡𝑎𝑙 𝑅𝑢𝑡𝑖𝑙𝑒 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 6.02 ℎ𝑟 (20)

SiO2 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = 5% × 𝑇𝑜𝑡𝑎𝑙 𝑅𝑢𝑡𝑖𝑙𝑒 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 3.01 𝑘𝑔/ℎ𝑟 (21)

TiO2 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = 85% × 𝑇𝑜𝑡𝑎𝑙 𝑅𝑢𝑡𝑖𝑙𝑒 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 51.183 𝑘𝑔/ℎ𝑟 (22)

3×𝑀𝑊𝐶
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝑐𝑜𝑘𝑒 = TiO2 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 × ( ) (23)
2×𝑀𝑤𝑇𝑖𝑂2

The required mass flow rate of coke in the reaction is:

36 𝐾𝑔
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝑐𝑜𝑘𝑒 = 51.183 × ( ) = 11.53
159.74 ℎ𝑟

The required mass flow rate of chloride gas in the reaction is:

4×𝑀𝑊𝐶𝐿2
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝐿2 = TiO2 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 × ( ) (24)
2×𝑀𝑤𝑇𝑖𝑂2

284.48 𝐾𝑔
𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝑐𝑜𝑘𝑒 = 51.183 × ( ) = 91.15
159.74 ℎ𝑟

The formed mass flow rate of carbon dioxide:

56
 𝑀𝑤
𝑓𝑜𝑟𝑚𝑒𝑑 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑂2 = 𝐴𝑐𝑡𝑢𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡𝑇𝑖𝐶𝐿4 × (2×𝑀𝑊𝐶𝑂2 ) (25)
𝑇𝑖𝐶𝑙4

44 𝐾𝑔
𝑓𝑜𝑟𝑚𝑒𝑑 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑂2 = 109.64 × ( ) = 12.68
380.22 ℎ𝑟

The formed mass flow rate of carbon monoxide:

2×𝑀𝑤𝐶𝑂
𝑓𝑜𝑟𝑚𝑒𝑑 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑂 = 𝐴𝑐𝑡𝑢𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡𝑇𝑖𝐶𝐿4 × (2×𝑀𝑊 ) (26)
𝑇𝑖𝐶𝑙4

56 𝐾𝑔
𝑓𝑜𝑟𝑚𝑒𝑑 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑂 = 109.64 × ( ) = 16.148
380.22 ℎ𝑟

The required amount of the following reaction is illustrated below:

𝑆𝑖𝑂2 + 2𝐶𝑙2 + 𝐶 → 𝑆𝑖𝐶𝑙4 + 𝐶𝑂2 (27)

𝐾𝑔
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝑆𝑖𝑂2 = 3.01
ℎ𝑟

The required mass flow rate of chloride gas is:

2×𝑀𝑊𝐶𝐿2 𝑘𝑔
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑙2 = 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝑆𝑖𝑂2 × ( 𝑀𝑤 ) = 7.13 ℎ𝑟 (28)
𝑆𝑖𝑂2

The required mass flow rate of coke is:

𝑀𝑤𝐶 𝑘𝑔
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝑐𝑜𝑘𝑒 = 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝑆𝑖𝑂2 × (𝑀𝑤 ) = 0.6015 ℎ𝑟 (29)
𝑆𝑖𝑂2

The formed mass flow rate of SiCl4:

𝑀𝑤𝑆𝑖𝐶𝑙4 𝑘𝑔
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝑆𝑖𝐶𝑙4 = 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝑆𝑖𝑂2 × ( ) = 8.516 (30)
𝑀𝑤𝑆𝑖𝑂2 ℎ𝑟

The formed mass flow rate of CO2:

𝑀𝑤𝐶𝑂 2 𝑘𝑔
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑂2 = 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝑆𝑖𝑂2 × ( ) = 2.205 (31)
𝑀𝑤𝑆𝑖𝑂2 ℎ𝑟

57
Now for the reaction between FeO and chloride gas at the presence of coke, the required

mass flow rate of the reactant material and products is shown below:

2𝐹𝑒𝑂 + 3𝐶𝑙2 + 𝐶 → 2𝐹𝑒𝐶𝑙3 + 𝐶𝑂2

(32)

𝐾𝑔
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐹𝑒𝑂 = 6.021
ℎ𝑟

Required mass flow rate of chloride gas in the reaction:

3×𝑀𝑤𝐶𝐿2
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑙2 = 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐹𝑒𝑂 × (2×𝑀𝑤 ) (33)
𝐹𝐸𝑂

213.36 𝐾𝑔
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑙2 = 6.021 × = 8.94
143.7 ℎ𝑟

Required mass flow rate of coke in the reaction:

𝐶𝑜𝑘𝑒 𝑀𝑤
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑜𝑘𝑒 = 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐹𝑒𝑂 × (2×𝑀𝑤 ) (34)
𝐹𝑒𝑂

𝐾𝑔
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑙2 = 0.502
ℎ𝑟

Formed mass flow rate of FeCl3 in the reaction:

2×𝑀𝑤𝐹𝑒𝐶𝑙3
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐹𝑒𝐶𝑙3 = 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐹𝑒𝑂 × ( 2×𝑀𝑤 ) (35)
𝐹𝑒𝑂

𝐾𝑔
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐹𝑒𝐶𝑙3 = 13.595
ℎ𝑟

Formed mass flow rate of CO2 in the reaction:

𝑀𝑤
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑂2 = 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐹𝑒𝑂 × (2×𝑀𝑤𝐶𝑂2 ) (36)
𝐹𝑒𝑂

𝐾𝑔
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑂2 = 1.843
ℎ𝑟

58
Now the reaction between carbon dioxide and oxygen is shown below:

𝐶𝑂 + 0.5 𝑂2 → 𝐶𝑂2 (37)

𝑘𝑔
𝐶𝑂 𝐹𝑜𝑟𝑚𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑐ℎ𝑙𝑜𝑟𝑖𝑛𝑎𝑡𝑜𝑟 = 16.148
ℎ𝑟

𝐾𝑔
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝑂2 = 4.613
ℎ𝑟

𝑀𝑤𝐶𝑂2
𝑓𝑜𝑟𝑚𝑒𝑑 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑂2 = 𝐶𝑂 𝐹𝑜𝑟𝑚𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑐ℎ𝑙𝑜𝑟𝑖𝑛𝑎𝑡𝑜𝑟 × ( ) (38)
𝑀𝑤𝑐𝑜

44 𝑘𝑔
𝑓𝑜𝑟𝑚𝑒𝑑 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑂2 = 16.144 × ( ) = 25.37
28 ℎ𝑟

Now after determine the raw material requirements in each reaction, the following

Table summarized the amount of raw material.

Table 30: requirement raw material mass flow rates

Raw materials requirement Mass flow rate kg/hr

Chloride 33.38978195

Carbon 12.63934384

Oxygen 23.06989599

TiO2 ore 60.2154442

The material balance on chlorinator R-100 is:

𝑘𝑔
𝑠𝑡𝑟𝑒𝑎𝑚 1 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑜𝑘𝑒 = 11.53 + 0.6015 + 0.502 = 12.639
ℎ𝑟

𝑘𝑔
𝑠𝑡𝑟𝑒𝑎𝑚 2 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝑟𝑢𝑡𝑖𝑙𝑒 = 51.18 + 6.02 + 3.01 = 60.215
ℎ𝑟

59
 𝑘𝑔
𝑠𝑡𝑟𝑒𝑎𝑚 3 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑙2 = 91.157 + 7.13 + 8.9 = 107.22
ℎ𝑟

𝐾𝑔
𝐼𝑛𝑙𝑒𝑡 𝑚𝑎𝑠𝑠 𝑏𝑎𝑙𝑎𝑛𝑐𝑒 𝑜𝑛 𝑅 − 100 = 107.22 + 12.63 + 60.21 = 180.077
ℎ𝑟

𝑆𝑡𝑟𝑒𝑎𝑚 4 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒

= 109 + 8.5 + 13.59 + 16.7 + 16.14 + 10.72 + 0.4 + 4.3

𝑘𝑔
= 180.077
ℎ𝑟

𝑘𝑔
𝑜𝑢𝑡𝑙𝑒𝑡 𝑚𝑎𝑠𝑠 𝑏𝑎𝑙𝑎𝑛𝑐𝑒 𝑜𝑛 𝑅 − 100 = 180.077
ℎ𝑟

Table 31: inlet and outlet streams mass balance on R-100

mass balance on chlorinator

inlet stream S1, S2 & S3

component mass flow rate kg/hr mass fraction mw kg/kmol molar flow rate kmol/hr mole fraction
chloride 107.223 0.595 71.120 1.508 0.452
coke 12.639 0.070 12.000 1.053 0.316
TiO2 (0.85) 51.183 0.284 79.870 0.641 0.192
FeO(0.1) 6.022 0.033 71.850 0.084 0.025
SIO2 (0.05) 3.011 0.017 60.060 0.050 0.015
total 180.077 1.000 294.900 3.336 1.000

outlet stream S4
component mass flow rate kg/hr mass fraction mw kg/kmol molar flow rate kmol/hr mole fraction
TiCL4 109.645 0.609 190.110 0.577 0.303
SiCL4 8.516 0.047 169.890 0.050 0.026
FeCL3 13.595 0.075 162.220 0.084 0.044
CO2 16.738 0.093 44.000 0.380 0.200
CO 16.149 0.090 28.000 0.577 0.303
CL2 10.722 0.060 71.120 0.151 0.079
Coke 0.407 0.002 12.000 0.034 0.018
TiO2 4.304 0.024 79.870 0.054 0.028
total 180.077 1.000 757.210 1.906 1.000

The material balance on HX-101 & S-101:

𝑘𝑔
𝑆𝑡𝑟𝑒𝑎𝑚 4 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = 180.077
ℎ𝑟

Assuming the mass flow rate of inlet & outlet water to be 200 kg/hr (stream 5 & 6).

60
 𝑘𝑔
𝑆𝑡𝑟𝑒𝑎𝑚 7 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = 13.59 + 0.4 + 4.3 = 18.306
ℎ𝑟

𝑘𝑔
𝑆𝑡𝑟𝑒𝑎𝑚 8 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = 109.64 + 8.5 + 16.73 + 16.14 + 1.7 = 161.77
ℎ𝑟

𝑘𝑔
𝐼𝑛𝑙𝑒𝑡 𝑚𝑎𝑠𝑠 = 𝑂𝑢𝑡𝑙𝑒𝑡 𝑚𝑎𝑠𝑠 = 380.077
ℎ𝑟

Table 32: Inlet and outlet streams mass flow rate on HX-101 & S-101

MASS BALANCE ON HX-101 & S-101

inlet streams S4& S5

stream 4
component mass flow rate kg/hr mass fraction mw kg/kmol molar flow rate kmol/hr mole fraction
TiCL4 109.645 0.609 190.110 0.577 0.303
SiCL4 8.516 0.047 169.890 0.050 0.026
FeCL3 13.595 0.075 162.220 0.084 0.044
CO2 16.738 0.093 44.000 0.380 0.200
CO 16.149 0.090 28.000 0.577 0.303
CL2 10.722 0.060 71.120 0.151 0.079
Coke 0.407 0.002 12.000 0.034 0.018
TiO2 4.304 0.024 79.870 0.054 0.028
total 180.077 1.000 757.210 1.906 1.000
stream 5
H2O IN 200.000 1.000 18.000 11.111 1.000
Outlet streams S6, S7,& S8
component mass flow rate kg/hr mass fraction mw kg/kmol molar flow rate kmol/hr mole fraction
stream 6
H2O OUT 200.000 1.000 18.000 11.111 1.000
Stream 7
FeCL3 13.595 0.743 162.220 0.084 0.488
Coke 0.407 0.022 12.000 0.034 0.198
TiO2 4.304 0.235 79.870 0.054 0.314
total 18.306 1.000 254.090 0.172 1.000
stream 8
TiCL4 109.645 0.678 190.110 0.577 0.332
SiCL4 8.516 0.053 169.890 0.050 0.029
CO2 16.738 0.103 44.000 0.380 0.219
CO 16.149 0.100 28.000 0.577 0.332
CL2 10.722 0.066 71.120 0.151 0.087
total 161.771 1.000 503.120 1.735 1.000

Material balance on CS-200:

The inlet streams to the condenser are S8 & S9, and the outlet streams are S10, S11,

& S12. The inlet mass flow rate of water assumed to be 150 kg/hr.

𝑘𝑔
𝑖𝑛𝑙𝑒𝑡 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑇𝑖𝐶𝑙4 = 𝑜𝑢𝑡𝑙𝑒𝑡 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑇𝑖𝐶𝑙4 = 109.64
ℎ𝑟

𝑀𝑎𝑠𝑠 𝑓𝑙𝑜𝑤𝑟𝑎𝑡𝑒𝑇𝑖𝐶𝑙4
𝑋𝑇𝑖𝐶𝑙4 𝑖𝑛 𝑆8 = (39)
𝑡𝑜𝑡𝑎𝑙𝑚𝑎𝑠𝑠 𝑓𝑜𝑤 𝑟𝑎𝑡𝑒

61
= 109.645/161.77 = 0.678

𝑀𝑜𝑙𝑎𝑟 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑜𝑓𝑇𝑖𝐶𝑙4 = 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝑇𝑖𝐶𝑙4 /𝑀𝑤𝑇𝑖𝐶𝑙4 (40)

109.645 0.577𝑘𝑚𝑜𝑙𝑒
𝑀𝑜𝑙𝑎𝑟 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑜𝑓𝑇𝑖𝐶𝑙4 = =
190.110 ℎ𝑟

𝑘𝑔
𝑖𝑛𝑙𝑒𝑡 𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 = 𝑜𝑢𝑡𝑙𝑒𝑡 𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 = 311.77
ℎ𝑟

Table 33: inlet & outlet streams on condenser

MASS BALANCE ON CONDENSER

Inlet streams S8 & S9
STREAM 8
component mass flow rate kg/hr mass fraction mw kg/kmol molar flow rate kmol/hr mole fraction
TiCL4 109.645 0.678 190.110 0.577 0.332
SiCL4 8.516 0.053 169.890 0.050 0.029
CO2 16.738 0.103 44.000 0.380 0.219
CO 16.149 0.100 28.000 0.577 0.332
CL2 10.722 0.066 71.120 0.151 0.087
total 161.771 1.000 503.120 1.735 1.000
STREAM 9
H2O IN 150.00 1.00 18.00 8.33 1.00
STREAM 10
H2O OUT 150.000 1.000 18.000 8.333 1.000
STREAM 12
CO2 16.73789 0.32111 44.00000 0.38041 0.32849
CO 16.14893 0.30981 28.00000 0.57675 0.49803
CL2 10.72227 0.20570 71.12000 0.15076 0.13019
SICL4 8.51649 0.16338 169.89000 0.05013 0.04329
TOTAL 52.12557 1.00000 313.01000 1.15805 1.00000
STREAM 11
TiCL4 109.645 1.000 190.110 0.577 1.000

The material balance on CV-201:

The inlet streams to the converter are S12 & S13, and the outlet stream is S14. Stream

12 contain CO2, CO, & SiCl4, were stream 13 contain oxygen with a mass flow rate

assumed to be 200 kg/hr.

𝐾𝑔
𝑖𝑛𝑙𝑒𝑡 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑖𝑛 𝑆12𝐶𝑂2 = 16.738
ℎ𝑟

16.738
𝑚𝑎𝑠𝑠 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛𝐶𝑂2 = = 0.321
52.126

62
 𝑖𝑛𝑙𝑒𝑡 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑖𝑛 𝑆12𝐶𝑂2 𝑘𝑚𝑜𝑙𝑒
𝑀𝑜𝑙𝑎𝑟 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑂2 𝑖𝑛 𝑆12 = = 0.38 (41)
𝑀𝑤𝐶𝑂2 ℎ𝑟

𝑀𝑜𝑙𝑎𝑟 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝐶𝑂2 𝑖𝑛 𝑆12

𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛𝐶𝑂2 = = 0.328 (42)
𝑇𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑎𝑟 𝑓𝑙𝑜𝑤

Table 34: inlet and outlet mass flow rate of CV-201

MASS BALANCE ON CONVERTER

INLET STREAMS S12 & S13
STREAM 12
component mass flow rate kg/hr mass fraction mw kg/kmol molar flow rate kmol/hr mole fraction
CO2 16.738 0.321 44.000 0.380 0.328
CO 16.149 0.310 28.000 0.577 0.498
CL2 10.722 0.206 71.120 0.151 0.130
SICL4 8.516 0.163 169.890 0.050 0.043
TOTAL 52.126 1.000 313.010 1.158 1.000
STREAM 13
O2 200 1 32 6.25 1
STREAM 14
CO2 232.887 0.924 44.000 5.293 0.963
CL2 10.722 0.043 71.120 0.151 0.027
SICL4 8.516 0.034 169.890 0.050 0.009
TOTAL 252.126 1.000 285.010 5.494 1.000

𝑘𝑔
𝐼𝑛𝑙𝑒𝑡 𝑚𝑎𝑠𝑠 = 𝑜𝑢𝑡𝑙𝑒𝑡 𝑚𝑎𝑠𝑠 = 252.126
ℎ𝑟

Material mass balance on R-200

Table 35: Inlet and outlet streams mass balance on oxidizer reactor

MASS BALAMCE ON OXIDIZER

INLET STREAMS S11&S15

STREAM 11
component mass flow rate kg/hr mass fraction mw kg/kmol molar flow rate kmol/hr mole fraction
TiCL4 109.6454482 1 190.11 0.5767474 1
STREAM 15
O2 18.45591679 1 32 0.5767474 1
STREAM 16
TiCL4 10.96454482 0.855927243 190.11 0.05767474 0.5
O2 1.845591679 0.144072757 32 0.05767474 0.5
SUM 12.81013649 1 222.11 0.11534948 1
STREAM 17
TIO2 41.45833333 0.359596596 79.87 0.51907266 0.333333333
CL2 73.83289512 0.640403404 71.12 1.038145319 0.666666667
SUM 115.2912285 1 150.99 1.557217979 1

63
 𝑘𝑔
𝑚𝑎𝑠𝑠 𝑖𝑛 = 𝑚𝑎𝑠𝑠 𝑜𝑢𝑡 = 128.101
ℎ𝑟

Material mass balance on S-102

Table 36: Inlet & outlet stream mass balance on S-102

MASS BALANCE ON CYCLON SEPERATOR

STREAM 17
component mass flow rate kg/hr mass fraction mw kg/kmol molar flow rate kmol/hr mole fraction
TIO2 41.45833333 0.3595966 79.87 0.51907266 0.333333333
CL2 73.83289512 0.6404034 71.12 1.038145319 0.666666667
SUM 115.2912285 1 150.99 1.557217979 1

STREAM 18
CL2 73.83289512 1 71.12 1.038145319 1

STREAM 19
TIO2 41.45833333 1 79.87 0.51907266 1.0000

𝐹𝑜𝑟𝑚𝑒𝑑𝑇𝑖𝑂2
𝑝𝑢𝑟𝑖𝑡𝑦 𝑜𝑓 𝑇𝑖𝑂2 =
𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑝𝑙𝑎𝑛𝑡

41.458
𝑝𝑢𝑟𝑖𝑡𝑦 𝑜𝑓 𝑇𝑖𝑂2 = = 99.5%
41.667

The formed amount of Titanium dioxide then inters to filter, and dryer before

packaging.

64
Energy Balance

In this section, the energy balance of titanium dioxide plant will be illustrated for the main

equipment, such as reactor 101, cooler 101, condenser, converter, oxidized reactor and

other. First, the heat of reactions is shown below:

𝐾𝐽
𝑇𝑖𝐶𝑙4 + 𝑂2 → 𝑇𝑖𝑂2 + 2𝐶𝑙2 ∆𝐻 = −173.5 𝑘𝑚𝑜𝑙

𝐾𝐽
2𝑇𝑖𝑂2 + 4𝐶𝑙2 + 3𝐶 → 2𝑇𝑖𝐶𝑙4 + 2𝐶𝑂 + 𝐶𝑂2 ∆𝐻 = −249.83 𝑘𝑚𝑜𝑙

𝐾𝐽
𝑆𝑖𝑂2 + 2𝐶𝑙2 + 𝐶 → 𝑆𝑖𝐶𝑙4 + 𝐶𝑂2 ∆𝐻 = −173.4 𝑘𝑚𝑜𝑙

𝐾𝐽
2𝐹𝑒𝑂 + 3𝐶𝑙2 + 𝐶 → 2𝐹𝑒𝐶𝑙3 + 𝐶𝑂2 ∆𝐻 = −1971.6 𝑘𝑚𝑜𝑙

Table 37: conversion from Celsius to kelvin

T© T (K)
25 298
900 1173
1000 1273
320 593
137 410

The heat capacity Cp (KJ/ kmol. K) for several components in different temperature are

summarized in the following Table.

Table 38: Heat capacity for several component in different temperature

molecular heat capacity kj/kmol.k

component 298 1173 1273 593 410
TiO2 56.81636805 86.2223132 89.39151057 67.58184467
CL2 33.88060501 37.93538116 38.76535295 36.40426614 35.21922
FeO 50.99807162
SiO2 44.85463844
coke 8.941691284 23.63030375 16.27310881
CO2 56.48858355 47.21949729 41.67302
CO 33.64197861 30.40496627 29.41313
TiCl4 149 149.44 149.1 149.1
FeCL3 77.78 77.78
SiCL4 135.6 136.88 136.5 136.5
O2 26.09 26.09

65
The heat capacity for the component calculated depends on the following equations:

1.75×10−5
𝐶𝑝 𝑜𝑓 𝑇𝑖𝑂2 = 49.4 + (0.0315 𝑇) − ( ) (43)
𝑇2

𝐾𝑗
1.75 × 10−5 56.816
𝐶𝑝 𝑜𝑓 𝑇𝑖𝑂2 𝑎𝑡 298 𝐾 = 49.4 + (0.0315 × 298) − ( )= 𝐾𝑚𝑜𝑙
2982 𝑘

𝐶𝑝 𝑜𝑓 𝐶𝐿2 = 26.93 + (0.033 𝑇) − (3.869 × 10−5 𝑇 2 ) + 1.547 × 10−8𝑇 3 (44)

𝐶𝑝 𝑜𝑓 𝐶𝐿2 𝑎𝑡 298

= 26.93 + (0.033 × 298) − (3.869 × 10−5 × 2982)

𝑘𝑗
+ 1.547 × 10−8 × 2983 = 33.88
𝑘𝑚𝑜𝑙. 𝐾

3.188×10−5
𝐶𝑝 𝑜𝑓 𝐹𝑒𝑂 = 52.8 + (0.006 𝑇) − ( ) (45)
𝑇2

3.188 × 10−5 𝑘𝑗
𝐶𝑝 𝑜𝑓 𝐹𝑒𝑂 𝑎𝑡 298 = 52.8 + (0.006 × 298) − ( 2
) = 50.998
298 𝑘𝑚𝑜𝑙. 𝐾

1.01×106
𝐶𝑝 𝑜𝑓 𝑆𝑖𝑂2 = 45.5 + (0.036 𝑇) − ( ) (46)
𝑇2

1.01 × 106 𝑘𝑗
𝐶𝑝 𝑜𝑓 𝑆𝑖𝑂2 𝑎𝑡 298 = 45.5 + (0.036 × 298) − ( 2
) = 44.85
298 𝑘𝑚𝑜𝑙. 𝐾

4.89×105
𝐶𝑝 𝑜𝑓 𝐶𝑜𝑘𝑒 = 11.2 + (0.0109 𝑇) − ( ) (47)
𝑇2

4.89 × 105 𝑘𝑗
𝐶𝑝 𝑜𝑓 𝐶𝑜𝑘𝑒 𝑎𝑡 298 = 11.2 + (0.0109 × 298) − ( 2
) = 8.9416
298 𝑘𝑚𝑜𝑙. 𝐾

𝐶𝑝 𝑜𝑓 𝐶𝑂2 = 19.8 + (0.073 𝑇) − (5.602 × 10−5𝑇 2 ) + 1.7115 × 10−8 𝑇 3 (48)

66
 𝐶𝑝 𝑜𝑓 𝐶𝑂2 𝑎𝑡 1173 𝐾

= 19.8 + (0.073 × 1173) − (5.602 × 10−5 × 11732 )

𝐾𝐽
+ 1.7115 × 10−8 × 1733 = 56.48
𝐾𝑚𝑜𝑙. 𝐾

𝐶𝑝 𝑜𝑓 𝐶𝑂 = 30.87 + (0.01285 𝑇) − (2.789 × 10−5𝑇 2) + 1.272 × 10−8 𝑇 3 (49)

𝐶𝑝 𝑜𝑓 𝐶𝑂 𝑎𝑡 1173

= 30.87 + (0.01285 × 1173) − (2.789 × 10−5 11732 )

𝑘𝑗
+ 1.272 × 10−8 11733 = 33.6419
𝑘𝑚𝑜𝑙. 𝐾

R-100 Energy balance:

𝐻𝑒𝑎𝑡 𝑖𝑛 + 𝐻𝑒𝑎𝑡 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 + 𝐻𝑒𝑎𝑡 𝑎𝑑𝑑𝑒𝑑 = 𝐻𝑒𝑎𝑡 𝑜𝑢𝑡

𝑄 = 𝑚𝐶𝑝 ∆𝑇 (50)

Where

Q: is the heat of the system kj/hr

M: molar flow rate of the component kmol/hr

Cp: specific heat of the component kj/ kmol. K.

∆𝑇: Is the difference between inlet and outlet temperature within the system.

The ore (Rutile) containing impure titanium dioxide, FeO, & SiO 2, and the heat

accompanied with ore calculated as follow;

𝐾𝑚𝑜𝑙
𝑚𝑜𝑙𝑎𝑟 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒𝑇𝑖𝑂2 𝑖𝑛 𝑅 − 100 = 0.51907
𝐻𝑟

𝑘𝑗
𝑄𝑇𝑖𝑂2 = 𝑚𝐶𝑝 ∆𝑇 = 0.51907 × 56.816 × 298 = 8788.563
ℎ𝑟

67
When the heat capacity of FeO & SiO2 at 298 K temperature equal 50.998 & 44.856

kj/kmol. K respectively, the duty of them is calculated at the same procedure and it shown

in the following Table.

Table 39: heat accompanied with rutile in the reactor

heat accompanied with rutile

component mw kg/kmol molar flow rate kmol/hr Q Kj/hr
TiO2 79.87 0.51907266 8788.563337
FeO 71.85 0.08380716 1273.653052
SiO2 60.06 0.050129407 670.0638607
SUM 211.78 0.653009227 10732.28025

The heat through coke calculated in the following equation.

𝑘𝑗
𝑄𝐶𝑜𝑘𝑒 = 𝑚𝐶𝑝 ∆𝑇 = 1.0533 × 298 × 8.94164 = 2806.592
ℎ𝑟

The heat accompanied with Chlorine gas at 298 & 1173 K temperatures are:

𝑘𝑗
𝑄𝐶𝐿2 𝑎𝑡 298 𝐾 = 𝑚𝐶𝑝 ∆𝑇 = 0.469 × 298 × 33.8806 = 4740.119
ℎ𝑟

𝑘𝑗
𝑄𝐶𝐿2 𝑎𝑡 1173 𝐾 = 𝑚𝐶𝑝 ∆𝑇 = 1.03814 × 1173 × 37.935 = 51230.7
ℎ𝑟

𝑘𝑗
𝑄 𝑡𝑜𝑡𝑎𝑙 = 𝑄𝐶𝐿2 𝑎𝑡 298 𝐾 + 𝑄𝐶𝐿2 𝑎𝑡 1173 𝐾 = 55970.82 ℎ𝑟 (51)

Generated heat for the products estimated by multiplied the molar flow rate of the material

with the heat of reaction as shown.

∆𝐻𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 = ∑ 𝑚𝑖 × ∆𝐻𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 (52)

∆𝐻𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 𝑜𝑓 𝑇𝐼𝐶𝐿4 = 𝑀𝑜𝑙𝑎𝑟 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 × ∆𝐻𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 (53)

𝑘𝑗
∆𝐻𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 𝑜𝑓 𝑇𝐼𝐶𝐿4 = 0.5767 × 297.83 = 144.088
ℎ𝑟

68
The generated heat from SiCl4 & FeCl3 is calculated by the same procedure and shown in

the following Table.

Table 40: The generated heat in the reactor

generated heat
component mw kg/kmol molar flow rate kmol/hr Q Kj/hr
TICl4 190.11 0.5767474 144.0888029
FeCL3 162.22 0.08380716 165.2341959
SiCL4 169.89 0.050129407 8.692439248
SUM 522.22 0.710683967 318.0154381

𝑘𝑗
𝑇𝑜𝑡𝑎𝑙 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 ℎ𝑒𝑎𝑡 = 𝑄𝑇𝑖𝐶𝑙4 + 𝑄𝑆𝑖𝐶𝑙4 + 𝑄𝐹𝑒𝐶𝑙3 = 318.0154 (54)
ℎ

Now the heat of the output stream which contain several components, estimated as follow:

𝑘𝑗
𝑄𝑇𝐼𝐶𝑙4 = 𝑚𝐶𝑝 ∆𝑇 = 0.5756 × 1173 × 149 = 100802.18
ℎ𝑟

The same procedure for the other component, where it estimated at 1173 K temperature,

and it shown in the following Table:

Table 41: heat output for the reactor

Heat associated with output stream

component mw kg/kmol molar flow rate kmol/hr Q Kj/hr
TICl4 190.11 0.5767474 100802.1803
CO2 44 0.380406687 25206.16877
CO 28 0.5767474 22759.62948
FeCL3 162.22 0.08380716 7646.224989
CL2 71.12 0.150763044 6708.684413
SiCL4 169.89 0.050129407 8048.789688
coke 12 0.033922283 940.269583
TiO2 79.87 0.053889796 5450.347818
sum 757.21 1.906413176 177562.295

𝑇𝑜𝑡𝑎𝑙 𝑜𝑢𝑡 ℎ𝑒𝑎𝑡 = 𝑄𝑇𝑖𝐶𝑙4 + 𝑄𝐶𝑂2 + 𝑄𝐶𝑂 + 𝑄𝐹𝑒𝐶𝑙3 + 𝑄𝐶𝑙2 + 𝑄𝑆𝑖𝐶𝑙4 + 𝑄𝐶𝑜𝑘𝑒 + 𝑄 𝑇𝐼𝑂2 =

𝐾𝐽
177562.295 𝐻𝑟 (55)

𝑒𝑛𝑒𝑟𝑔𝑦 𝑏𝑎𝑙𝑎𝑛𝑐𝑒 𝑜𝑛 𝑅 − 100 = 𝐻𝑒𝑎𝑡 𝑖𝑛 + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 𝐻𝑒𝑎𝑡 + 𝐻𝑒𝑎𝑡 𝐴𝑑𝑑𝑒𝑑 = 𝐻𝑒𝑎𝑡 𝑜𝑢𝑡

69
𝐻𝑒𝑎𝑡 𝑎𝑑𝑑𝑒𝑑 𝑡𝑜 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 = 𝐻𝑒𝑎𝑡 𝑜𝑢𝑡 − (𝐻𝑒𝑎𝑡 𝑖𝑛 + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 𝐻𝑒𝑎𝑡) (56)

𝐻𝑒𝑎𝑡 𝑎𝑑𝑑𝑒𝑑 𝑡𝑜 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 = 177562.298 − (318.15 + 55970.819 + 2806.59 + 10732.28)

𝑘𝑗
= 107734.58
ℎ𝑟

𝑒𝑛𝑒𝑟𝑔𝑦 𝑏𝑎𝑙𝑎𝑛𝑐𝑒 𝑜𝑛 𝑅 − 100 = 𝐻𝑒𝑎𝑡 𝑖𝑛 + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 𝐻𝑒𝑎𝑡 + 𝐻𝑒𝑎𝑡 𝐴𝑑𝑑𝑒𝑑 = 𝐻𝑒𝑎𝑡 𝑜𝑢𝑡

𝑘𝑗
= 177562.295
ℎ𝑟

Cooler HX-101 Energy Balance

The heat exchanger temperature is 320℃, and it used water as a coolant for the system,

where its inlet at 25℃, and out with 135 ℃.

ℎ𝑒𝑎𝑡 𝑖𝑛 𝑡𝑜 𝑡ℎ𝑒 𝑐𝑜𝑜𝑙𝑒𝑟 = ℎ𝑒𝑎𝑡 𝑜𝑢𝑡 𝑓𝑟𝑜𝑚 𝑐ℎ𝑙𝑜𝑟𝑖𝑛𝑒𝑟𝑎𝑡𝑜𝑟 = 177562.2950 𝑘𝑗/ℎ𝑟

𝑘𝑗
𝑄𝑇𝐼𝐶𝑙4 𝑖𝑛 𝑐𝑜𝑜𝑙𝑒𝑟 = 𝑚𝐶𝑝 ∆𝑇 = 0.5756 × 593 × 149.1 = 50993.87
ℎ𝑟

𝑘𝑗
𝑄𝐶𝑂2 𝑖𝑛 𝑐𝑜𝑜𝑙𝑒𝑟 = 𝑚𝐶𝑝 ∆𝑇 = 0.3804 × 593 × 47.219 = 10651.83
ℎ𝑟

The same calculation procedure for other components and its summarized in the following

Table.

𝑇𝑜𝑡𝑎𝑙 ℎ𝑒𝑎𝑡 𝑜𝑢𝑡 𝑜𝑓 𝑐𝑜𝑜𝑙𝑒𝑟 = 𝑄𝑇𝑖𝐶𝑙4 + 𝑄𝐶𝑂2 + 𝑄𝐶𝑂 + 𝑄𝐹𝑒𝐶𝑙3 + 𝑄𝐶𝑙2 + 𝑄𝑆𝑖𝐶𝑙4 + 𝑄𝐶𝑜𝑘𝑒 +

𝐾𝐽
𝑄𝑇𝐼𝑂2 = 85709.39 ℎ𝑟 (57)

Table 42: cooler heat energy

cooler HX-101
component mw kg/kmol molar flow rate kmol/hr Q Kj/hr
TICl4 190.11 0.5767474 50993.87112
CO2 44 0.380406687 10651.82923
CO 28 0.5767474 10398.83924
FeCL3 162.22 0.08380716 3865.48288
CL2 71.12 0.150763044 3254.631866
SiCL4 169.89 0.050129407 4057.69982
coke 12 0.033922283 327.3484529
TiO2 79.87 0.053889796 2159.689272
sum 757.21 1.906413176 85709.39188

70
 𝑘𝑗
ℎ𝑒𝑎𝑡 𝑟𝑒𝑚𝑜𝑣𝑒𝑑 = ℎ𝑒𝑎𝑡 𝑖𝑛 − ℎ𝑒𝑎𝑡 𝑜𝑢𝑡 = 177562.29 − 58709.39 = 91852.9 ℎ𝑟

(58)

𝑄 91852.9 𝑘𝑔
𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 𝐶 = 4.182∗(135−25) = 200 ℎ𝑟 (59)
𝑃∆𝑇

𝑘𝑗
ℎ𝑒𝑎𝑡 𝑖𝑛 = ℎ𝑒𝑎𝑡 𝑜𝑢𝑡 + ℎ𝑒𝑎𝑡 𝑟𝑒𝑚𝑜𝑣𝑒𝑑 = 177562.2950 ℎ𝑟 (60)

Condenser Energy Balance CS-101

The condenser operated at 137℃ and contains several materials, with water stream. The

duty of each component shown below:

ℎ𝑒𝑎𝑡 𝑖𝑛 = ℎ𝑒𝑎𝑡 𝑜𝑢𝑡 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡𝑠 𝑓𝑟𝑜𝑚 𝑐𝑜𝑜𝑙𝑒𝑟 (61)

ℎ𝑒𝑎𝑡 𝑖𝑛 = 𝑄𝑇𝑖𝐶𝑙4 + 𝑄𝐶𝑂2 + 𝑄𝐶𝑂 + 𝑄𝐶𝑙2 + 𝑄𝑆𝑖𝐶𝑙4 (62)

𝑘𝑗
ℎ𝑒𝑎𝑡 𝑖𝑛 = 50993.87 + 4057.69 + 10651.82 + 10398.83 + 324.63 = 79356.87
ℎ𝑟

the temperature of out stream from condenser is 137 ℃, and its separate into three outlet

streams, water, pure tetrachloride titanium, and gas stream.

Table 43: inlet heat to the condenser at 137 ℃

71
ℎ𝑒𝑎𝑡 𝑐𝑎𝑟𝑟𝑖𝑒𝑑 𝑏𝑦 𝑔𝑎𝑠 𝑠𝑡𝑟𝑒𝑎𝑚 = 𝑄𝐶𝑂2 + 𝑄𝐶𝑂 + 𝑄𝐶𝑙2 + 𝑄𝑆𝑖𝐶𝑙4 (63)

𝑘𝑗
𝑄𝐶𝑂2 = 0.3804 × 410 × 41.67 = 6499.605
ℎ𝑟

6955.21𝑘𝑗
𝑄𝐶𝑂 = 0.5756 × 410 × 29.41 =
ℎ𝑟

2177𝑘𝑗
𝑄𝐶𝑙2 = 0.1507 × 410 × 35.21 =
ℎ𝑟

2805.49𝑘𝑗
𝑄𝑆𝑖𝐶𝑙4 = 0.05 × 410 × 136.5 =
ℎ𝑟

18437.31𝑘𝑗
ℎ𝑒𝑎𝑡 𝑐𝑎𝑟𝑟𝑖𝑒𝑑 𝑏𝑦 𝑔𝑎𝑠 𝑠𝑡𝑟𝑒𝑎𝑚 =
ℎ𝑟

35257.14𝑘𝑗
ℎ𝑒𝑎𝑡 𝑜𝑓 𝑝𝑢𝑟𝑒 𝑇𝑖𝐶𝑙4 = 0.5756 × 410 × 149.1 =
ℎ𝑟

ℎ𝑒𝑎𝑡 𝑖𝑛 𝑡𝑜 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 = ℎ𝑒𝑎𝑡 𝑟𝑒𝑚𝑜𝑣𝑒𝑑 + ℎ𝑒𝑎𝑡 𝑜𝑓 𝑝𝑢𝑟𝑒 𝑇𝑖𝐶𝑙4 +

ℎ𝑒𝑎𝑡 𝑐𝑎𝑟𝑟𝑖𝑒𝑑 𝑏𝑦 𝑔𝑎𝑠 𝑠𝑡𝑟𝑒𝑎𝑚 (64)

25662.4𝑘𝑗
ℎ𝑒𝑎𝑡 𝑟𝑒𝑚𝑜𝑣𝑒𝑑 = 79356.87 − (18437.31 + 35257.14) =
ℎ𝑟

𝑄𝑅𝑒𝑚𝑜𝑣𝑒𝑑
𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = (65)
𝐶𝑃∆𝑇

256624 𝐾𝑔
𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = = 150
4.182 × (65.9 − 25) ℎ𝑟

The outlet temperature of the water will be 65.9 ℃. So, the energy balance on the condenser

will be:

ℎ𝑒𝑎𝑡 𝑖𝑛 𝑡𝑜 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 = ℎ𝑒𝑎𝑡 𝑟𝑒𝑚𝑜𝑣𝑒𝑑 + ℎ𝑒𝑎𝑡 𝑜𝑓 𝑝𝑢𝑟𝑒 𝑇𝑖𝐶𝑙4 +

𝑘𝑗
ℎ𝑒𝑎𝑡 𝑐𝑎𝑟𝑟𝑖𝑒𝑑 𝑏𝑦 𝑔𝑎𝑠 𝑠𝑡𝑟𝑒𝑎𝑚 = 79356.87 (66)
ℎ𝑟

Energy Balance on Oxidize Burner R-200

72
 𝑘𝑗
𝐻𝑒𝑎𝑡 𝑖𝑛 𝑜𝑓 𝑇𝑖𝐶𝑙4 = ℎ𝑒𝑎𝑡 𝑜𝑓 𝑝𝑢𝑟𝑒 𝑇𝑖𝐶𝑙4 𝑖𝑛 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 = 35257.14
ℎ𝑟

4484.1072𝑘𝑗
𝑄𝑂2 𝑖𝑛 𝑜𝑥𝑖𝑑𝑖𝑧𝑒 𝑏𝑢𝑟𝑛𝑒𝑟 = 𝑚𝐶𝑃 ∆𝑇 = 0.5767 × 298 × 26.06 =
ℎ𝑟

39741.25𝑘𝑗
𝑄 𝑖𝑛 = 35257.14 + 4484.107 =
ℎ𝑟

𝑄𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 = 𝑄𝐶𝑙2 + 𝑄𝑇𝑖𝑂2 (67)

270.177𝑘𝑗
𝑄𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 = (0.51907 + 1.038) + 173.5 =
ℎ𝑟

𝑄 𝑂𝑢𝑡 𝑎𝑡 1273 = 𝑄𝑂2 + 𝑄𝐶𝑙2 + 𝑄𝑇𝑖𝑂2 + 𝑄𝑇𝑖𝐶𝑙4 (68)

Table 44:outlet heat from R-200

heat output
component mw kg/kmol molar flow rate kmol/hr Q Kj/hr
TIO2 79.87 0.51907266 59068.07729
CL2 71.12 1.038145319 51230.70076
TiCL4 190.11 0.05767474 10971.87643
O2 32 0.05767474 1915.526339
SUM 123186.1808

𝐾𝐽
𝑄 𝑂𝑢𝑡 𝑎𝑡 1273 = 123186.1808
𝐻𝑅

𝐻𝑒𝑎𝑡 𝑎𝑑𝑑𝑒𝑑 = ℎ𝑒𝑎𝑡 𝑜𝑢𝑡 − (ℎ𝑒𝑎𝑡 𝑖𝑛 + ℎ𝑒𝑎𝑡 𝑔𝑒𝑛𝑒𝑟𝑡𝑒𝑑) (69)

83174.75𝑘𝑗
𝐻𝑒𝑎𝑡 𝑎𝑑𝑑𝑒𝑑 = 123186.18 − (39741.25 + 270.177) =
ℎ𝑟

Converter Energy Balance

ℎ𝑒𝑎𝑡 𝑖𝑛 + ℎ𝑒𝑎𝑡 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 = ℎ𝑒𝑎𝑡 𝑜𝑢𝑡 (70)

𝑘𝑔
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑂2 = 200
ℎ𝑟

73
 𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑜𝑓𝑂2 200 𝐾𝑚𝑜𝑙
𝑚𝑜𝑙𝑎𝑟 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑂2 = = = 6.25
𝑀𝑊 32 ℎ𝑟

𝐾𝐽
𝑄𝑂2 = 𝑚𝐶𝑃 ∆𝑇 = 6.25 × 298 × 26.09 = 48592.625
𝐻𝑅

110.52𝑘𝑗
𝐻𝑒𝑎𝑡 𝑜𝑓 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 = (71)
𝑘𝑚𝑜𝑙

𝐾𝑗
𝑄𝐶𝑂 = 110.52 × 0.5657 = 63.74
ℎ𝑟

𝑘𝑗
67029.94 + 63.74 = 67093.63
ℎ𝑟

Table 45:energy balance on converter

converter
HEAT IN =HEAT CARRIED BY THE GAS STREAM FROM CONDENSER
O2 200 KG/HR
6.25 KMOL/HR
48592.625 KJ/HR
HEAT IN 67029.94168
HEAT OF FORMATION 110.52 KJ/KMOL
63.74212262
HEAT OUT 67093.6838 KJ/HR

APPENDIX B

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