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CSIR - National Metallurgical Laboratory
(Council of Scientific and Industrial Research)
Jamshedpur, Jharkhand

Summer Pro...
CERTIFICATE
This is to certify that Mr. RAKESH KUMAR SINGH B.Tech. Final Year of
Material Science & Metallurgical Engineer...
ACKNOWLEDGEMENT
First of all I am thankful of my project guide Mr. Madan Mohanasundaram
under whose guideline I was able t...
ABSTRACT
Extraction of metals is depending upon their ore processing, better route of
processing and freezing the better p...
Table of Content
 Chapter 1:- Literature Review
1. Introduction of Magnesium
1.1.
1.2.

Thermal Properties………………………………………...
List of the Figures
Fig No.
1.1
2.1
2.2
2.3
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10

Figures
FactSage Menu
The Main Menu ...
List of Tables
Table No.
1.1
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10
3.11
3.12
3.13

Table
Magnesium Ores
Magnesium Yield...
Chapter 1:- Literature Review
1. Introduction of Magnesium:
Magnesium is the lightest of all the engineering materials kno...
2. Magnesium Extraction:Ores and Minerals of the Magnesium are described below with the fair percentage
of magnesium prese...
2. Magnesium vapours are produced at the temperature 1550 oC by the reduction of
MgO by the Ca-Si-Fe alloy. At this stage,...
2.5.

Magnola Process:-

In this process first take the raw material from the Asbestos mine then make the Pure
Brine by th...
3.2 (b)

First Law in terms of Enthalpy:-

The first law of thermodynamics can be expressed in terms of the enthalpy inste...
3.4.

Heat Balance:-

Heat balanced is depending upon the first law of thermodynamics. In furnace constant
pressure can be...
3.6.

Second Law of Thermodynamics:-

There are two statements as applied to thermodynamics:
1) Heat cannot be transferred...
3.8.

Helmholtz Free Energy:-

Helmholtz Free Energy A acts like a store of work or energy available for doing work
(i.e. ...
μ = 	μ = 	μ …												
Equilibrium of a closed thermodynamic system is established if its Gibbs energy at
constant temp...
4. FactSage:FactSage was introduced in 2001 as the fusion of the FACT-Win and ChemSage
thermochemical packages[6]. The Fac...
4.1.

Info:-

The General module provides slide shows (Microsoft Power Point and Adobe PDF
presentations) of all the modul...
4.2.(b)

View Data:-

In this module enter the E-L-E-M-E-N-T or Compound or All with selecting the database
type, which we...
4.3.(d) Equilib Module:The Equilib module is the Gibbs energy minimization workhorse of FactSage and offers
great flexibil...
4.4.(a) Results Module:The Results module generates graphs from the output of complex equilibrium
calculations performed w...
Chapter 2:- Experimental Detail
5. Methodology:1. Extraction of magnesium get by the raw material Dolomite, Ferro-Silicon ...
Fig 2.1:- The Main Menu of Mixture Module[6]
3. Import all the mixture in the Equilib Module in different weight ratio of ...
4. The effective mass of magnesium is depend upon the minimum Gibbs Free
Energy for the above mixture reaction at the spec...
7. Draw the Liquidus projection Ternary Phase Diagram of the slag components
CaO, Al2O3 & SiO2 at the range of the MgO amo...
Chapter 3:- Results & Discussions
1. Take amount of the raw materials in different weight Ratio at Temperature range
1500o...
Magnesium Yield (Wt. %) is economically maximum for the ratio 5:1:1 but Amount of
Magnesium (gm.) is economically maximum ...
Means for the efficient production of Magnesium, the Optimum ratio of Dolo-3: Calcined
Bauxite: Ferro-Silicon should be in...
131
130.1064

130
129.6144
129

128.856

128.7744
128.1456

128
127.5888
127.08

Magnesium Amount (gm)

127
126

126.0864
...
Lime
0
10
20
30
40
50
Addition(gm.)
125.50 126.41 127.36 128.24 129.08 129.89
Magnesium
amount (gm.)
Solid Slag (wt.
13.81...
Fig: 3.3:- Effect of MgO at Binary Phase Diagram

Take the Solid & Liquid slag temp & Wt. % at different mass fraction of ...
6.2.

Keep Al2O3 mass fraction in range of 0-0.20 Wt. % with keep the
constant mass fraction of MgO & SiO2, draw the Binar...
From the above data we observe that as increasing the amount of Al2O3 in slag decreases
the solid slag temperature but inc...
From the above data we observe that increasing the amount of SiO2 in slag decreases
solid slag temperature with increasing...
As we observe from the above data as increasing the amount of CaO in slag Solid
temperature first decrease then again incr...
1800oC

1700oC

1600oC

1500oC

Fig: 3.8:- Liquidus Projected Ternary Phase Diagram at MgO = 4.5gm

1800oC

1700oC

1600oC...
1600oC
o
1800 C 1700 C

1500oC

o

Fig: 3.10:- Liquidus Projected Ternary Phase Diagram at MgO = 8gm
8. Now take slag comp...
As the amount of MgO increases (0-8 gm.), the viscosity of slag also increases (0.44-2.41
poise) at constant temperature a...
Chapter 4:- Conclusions
 The process conditions for the production of Magnesium by Magnotherm Process
is evaluated.
 The...
Chapter 5:- Future work

 These studies can further continued in the open system, where continuous
evaluation of the Mg c...
Chapter 6:- References
1. ASM Specialty Handbook, “Magnesium and Magnesium Alloys”.
2. H S Ray, “Extraction of Non Ferrous...
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Project reprt

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Project reprt

  1. 1. CSIR - National Metallurgical Laboratory (Council of Scientific and Industrial Research) Jamshedpur, Jharkhand Summer Project Report On “Evaluation of Process conditions for Magnesium Production from Dolomite Ore Using CALPHAD Method” (13th May-2013 to 21th June-2013) Under the Guidance of: Mr. Madan Mohanasundaram Scientist MEF Division NML – Jamshedpur Submitted by: Rakesh Kumar Singh MSME Department MANIT- Bhopal
  2. 2. CERTIFICATE This is to certify that Mr. RAKESH KUMAR SINGH B.Tech. Final Year of Material Science & Metallurgical Engineering, Maulana Azad National Institute of Technology, Bhopal, has done a summer project entitled, “Evaluation of Process conditions for Magnesium Production from Dolomite Ore Using CALPHAD Method” submitted at National Metallurgical Laboratory – Jamshedpur, is a record of an original work done by me under the guidance of Mr. Madan Mohanasundaram, Scientist, Metal Extraction and Forming Division (MEF), NML –Jamshedpur, during the period 13th May-2013 to 21th June-2013 and this summer project work has not been submitted for the award of any other Degree or Diploma / Associate ship / fellowship and similar project if any. RAKESH KUMAR SINGH Project Guide Date: - 21th June-2013 ~2~
  3. 3. ACKNOWLEDGEMENT First of all I am thankful of my project guide Mr. Madan Mohanasundaram under whose guideline I was able to complete my project. I am whole heartedly thankful to him for giving me his valuable time & attention & for providing me a systematic way for completing my project in time. I would like to express my sincere thanks to Mr. K.L. Hansda (Training CoOrdinate) at CSIR -National Metallurgical Laboratory, Jamshedpur, India for arranging vocational Industrial project at their esteemed organization. My first experience of Industrial/R&D project has been successfully complete, thanks to the support staff of many friends & colleagues with gratitude. I wish to acknowledge all of them. However, I wish to make special mention of the following. RAKESH KUMAR SINGH ~3~
  4. 4. ABSTRACT Extraction of metals is depending upon their ore processing, better route of processing and freezing the better process condition. So, the purpose of this project is to analyze the best process condition for extraction process for Magnesium production by Magnotherm Method using CALPHAD. In this project, the Dolomite ore along with Ferro-Silicon, Bauxite & Lime for observing the efficient production of Magnesium. A computational thermodynamic analysis was completed on a variety of slag compositions and reaction temperatures. All available thermodynamic and phase diagram data for these systems were collected and used to determine three key factors: (1) Efficient amount of Magnesium Vapors (2) Aggressiveness of the slag (3) Fraction of solid in the bulk slag. ~4~
  5. 5. Table of Content  Chapter 1:- Literature Review 1. Introduction of Magnesium 1.1. 1.2. Thermal Properties…………………………………………………………….8 Mechanical Properties…………………………………………………………8 2. Magnesium Extraction 2.1. Pidgeon Process……………………………………………………………….9 2.2. Dow Process………………………………………………………………….10 2.3. NML Process………………………………………………………………...10 2.4. Magnotherm Process…………………………………………………………10 2.5. Magnola Process……………………………………………………………..11 3. Thermodynamics 3.1. Zeroth Law…………………………………………………………………..11 3.2. First Law of Thermodynamics……………………………………………….11 3.3. Heat capacity…………………………………………………………………12 3.4. Heat Balanced………………………………………………………………..13 3.5. Mass Balance………………………………………………………………...13 3.6. Second Law of Thermodynamics……………………………………………14 3.7. Gibbs Free Energy…………………………………………………………...14 3.8. Helmholtz Free Energy……………………………………………………....15 3.9. Third Law of Thermodynamics……………………………………………...15 3.10. Gibbs Energy Minimization……………………………………………….…15 4. FactSage 4.1. Info………………………………………………………………………….18 4.2. Databases…………………………………………………………………....18 4.3. Calculate…………………………………………………………………….19 4.4. Manipulate…………………………………………………………………..20  Chapter 2:- Experimental Detail 1. Methodology………………………………………………………………..22  Chapter 3:- Results & Discussions…………………………………....26  Chapter 4:- Conclusions…………………………………………..……..39  Chapter 5:- Future work…………………………………………..…….40  Chapter 6:- References……………………………………………………41 ~5~
  6. 6. List of the Figures Fig No. 1.1 2.1 2.2 2.3 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 3.10 Figures FactSage Menu The Main Menu of Mixture Module The Main Menu of Equilib Module The Main Menu of Phase Diagram: Last system Magnesium amount at constant Temperature Magnesium amount at constant Pressure Effect of MgO at Binary Phase Diagram Effect of Al2O3 at Binary Phase Diagram Effect of SiO2 at Binary Phase Diagram Effect of CaO at Binary Phase Diagram Liquidus Projected Ternary Phase Diagram at MgO = 3gm Liquidus Projected Ternary Phase Diagram at MgO = 4.5gm Liquidus Projected Ternary Phase Diagram at MgO = 6gm Liquidus Projected Ternary Phase Diagram at MgO = 8gm ~6~ Page No. 17 23 23 25 28 29 31 32 33 34 35 36 36 37
  7. 7. List of Tables Table No. 1.1 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 3.10 3.11 3.12 3.13 Table Magnesium Ores Magnesium Yield at Different ratio of Raw Material Magnesium Amount at changing amount of Fe-Si Magnesium Amount at changing amount of Bauxite Effect of Lime Addition Feed Requirement Effect of MgO at the slag Effect of Al2O3 at the slag Effect of SiO2 at the slag Effect of CaO at the slag Effect of the MgO at the Viscosity of slag Effect of the Al2O3 at the Viscosity of slag Effect of the SiO2 at the Viscosity of slag Effect of the CaO at the Viscosity of slag ~7~ Page No. 9 26 27 27 30 30 31 33 34 37 37 38 38 38
  8. 8. Chapter 1:- Literature Review 1. Introduction of Magnesium: Magnesium is the lightest of all the engineering materials known and has good ductility, better noise and vibration damping characteristics than Aluminium and excellent cast ability. Alloying magnesium with Aluminium, manganese, rare earths, thorium, zinc or zirconium increases the strength to weight ratio making them important materials for applications where weight reduction is important, and where it is imperative to reduce inertial forces. It has good shielding ability for Electromagnetic Interface Frequency & Radio Frequency Interface. [1] Magnesium is placed in Rare earth metal group with Mg. It has Hexagonal Closed Pack crystal structure & paramagnetic behavior at the room temperature. The density of Mg is 1.738 gm-cm-3 (room temperature) & twining effect occurs across the (1013) planes. Here are some properties of Mg as followings:1.1 Thermal Properties:-  The melting point of pure Magnesium under atmospheric pressure is 650±1 o [1] C which is increases with increasing the pressure.  The boiling point of pure Magnesium under atmospheric pressure is 1090 o [1] C .  Thermal Expansion of pure Magnesium at the room temperature is 24.8 µmm-1-K-1. [1]  The Specific Heat Capacity (Cp) at the room temperature is 1.025 kJ/kg.K. [1]  The latent heat of Fusion & Vaporization (∆L) is 360 to 377 kJ/kg & 5150 to 5400 kJ/kg respectively. [1]  The Heat of combustion (∆H) of pure Magnesium under atmospheric pressure is 24900 to 25200 kJ/kg. [1] 1.2 Mechanical properties:-  The Tensile Strength and Compressive Strength of cast rod (1/2 in. diameter) of pure Magnesium is 90 MPa and 21 MPa respectively. [1]  The Hardness of the same sample is 16 (HRE) & 30 (HB). [1]  Magnesium has dynamic viscosity of liquid is 1.23 mPa.s at 650 oC and 1.13 mPa.s at 700 oC. [1] ~8~
  9. 9. 2. Magnesium Extraction:Ores and Minerals of the Magnesium are described below with the fair percentage of magnesium present:- [2] Name Composition Molecular Weight Percentage Mg Magnesite MgCO3 84 29 Dolomite MgCO3-CaCO3 184 13 Brucite Mg(OH)2 58 42 Carnalite MgCl2-KCl-6H2O 278 9 Kieserite MgSO4-H2O 138 17 Serpentino Mg3Si2O7 240 30 Enstatite MgSiO3 100 24 Olivine Mg2SiO4 140 34 Kainite MgSO4-KCl-3H2O 249 10 Table: 1.1:- Magnesium Ores Out of the above Ores; Magnesite, Dolomite & Brucite easily available in our country. There are some extraction processes for the magnesium from its ores is following: 2.1 Pidgeon Process:The Pidgeon process involved essentially solid – state reactions. During the Pidgeon Process, the following distinct stages are observed:1. The initial reaction takes place between ferrosilicon and CaO to produce a liquid Ca-Si-Fe alloy, which permeates the briquette and forms a metallic network. This reaction takes place rapidly at around 1000 oC and is mildly exothermic. ~9~
  10. 10. 2. Magnesium vapours are produced at the temperature 1550 oC by the reduction of MgO by the Ca-Si-Fe alloy. At this stage, the pressure builds up rapidly, slowly down the rate of reaction. The subsequent reaction rate is governed by the rate at which magnesium can escape from the briquettes[4]. MgO (c) + Si (c) Mg (g) + SiO (g) PSiO at 1550 K = 3.26 * 10-1mm Hg 2SiO (g) + 2CaO (c) 2CaO-SiO2 (c) + Si (c) -3 PSiO at 1550 K = 8.24*10 mm Hg 2.2. ………...(i) ………...(ii) Dow Process:The Dow Process is generally applied for extraction of Magnesium from Sea water. In this process first we add lime for thickening then mix with 10% HCl. The final product contaminated with the magnesium oxide by which Mg production occurs by the Electrolysis process[2]. MgCl2.6H2O = MgO + 2HCl + 5H2O ………...(iii) In the Electrolysis Process, there is large amount of Flux required in electrolyte composition for maintain fluidity and increases the density of bath. There are steel wall of the cell use as the cathode and graphite anode are employed. 2.3. NML Process:The raw material for Magnesium Production is Dolomite, Ferro –Silicon (75%80%), Fluorspar. Dolomite is calcined in the temperature range 950-1100 oC[2]. The calcined dolomite and the ferrosilicon are first ground and then mixed with 1% fluorspar. Then make briquette of that mix charged in the Tubular retorts and create vacuum. Magnesium is distilled from the charge and then condensed on a removable sleeve at the cold end of retorts. 2.4. Magnotherm Process:- A Magnotherm Process is essentially a ferrosilicon Reduction process similar to the Pidgeon process, except that it is carried out at a temperature of 1500 oC [2]and the bath is maintained in a molten state by the addition of alumina to form a molten slag. ~ 10 ~
  11. 11. 2.5. Magnola Process:- In this process first take the raw material from the Asbestos mine then make the Pure Brine by the acid leaching. The filtrate pure brine dry and produce Magnesium Chloride which contain the oxide of Magnesium. Then by the Electrolysis Process we can able to produce the Magnesium. 3. Thermodynamics:For economical Magnesium production, it is essential to calculate the raw material requirement for the optimized temperature & pressure. Thermodynamics is required to proceed in the right direction. Computational Thermochemistry based on the Calphad method is a modern tool that supplies quantitative data to guide the development or the optimization of materials processing. It enables the calculation of multicomponent phase diagrams and the tracking of individual compounds, species or slag during Extraction process in Furnace/Retort. There are some basic laws of thermodynamics which describe below: 3.1. Zeroth Law:According to Zeroth Law of thermodynamics “Two systems in thermal equilibrium with a third are in thermal equilibrium with each other”. 3.2. First law of thermodynamics:- The first law of thermodynamics is nothing but a statement of the law of conservation of energy means “Energy cannot be created or destroyed, but it can be converted from one form to another”. 3.2(a) First Law in Terms of Internal Energy:- The absorption of heat q increases the internal energy dE of the body by the amount ∂q and performance of work w by the body decreases its internal energy dE by amount ∂w. dE = ∂q - ∂w ~ 11 ~ …..(1)
  12. 12. 3.2 (b) First Law in terms of Enthalpy:- The first law of thermodynamics can be expressed in terms of the enthalpy instead of energy. dH = ∂q + VdP …..(2) Where, “d” indicates a differential element of a state function or state property. “∂” indicates a differential element of some quantity which is not a state function. 3.3. Heat Capacity:- The Heat capacity, “C” of a substance is defined as the amount of heat required to raise its temperature by one degree. C= ……(3) Heat Capacity at the constant volume is given by Cv = ( )v = ( )v …..{from equation (1) } Heat Capacity at the constant Pressure is given by Cp = ( )p= [ ( ) ]p …..{from equation (1) } Heat Capacity at the constant Pressure is also depending upon the temperature changes of species which is denoted below in polynomial form:- Cp (T) = a + bT + cT-2 + dT2 Where, a, b, c & d are the arbitrary constant which are stored for every species. ~ 12 ~ …….. (4)
  13. 13. 3.4. Heat Balance:- Heat balanced is depending upon the first law of thermodynamics. In furnace constant pressure can be created easily than the constant volume, means at constant volume:Heat input = Heat output (at constant pressure) ∆H = q Means the enthalpy increases of the system must be equal to the heat lost by the surroundings. A Heat Balanced may be prepared in which the increases in enthalpy of the system are tabulated in one column and the losses of the heat by the surroundings are tabulated in other column. Any lack of balance of the two columns is due to experimental error. 3.5. Mass Balance:- Mass balance for any reactive system is denoted by the below diagram. In – Out + gen – cons = accumulation [3] FA 0 Rate o f flow in FA R a te of flo w ou t Sy s tem GA Rate o f g en er atio n / con su mp t io n Where, GA = ∫ V is volume of the system, rA is total material flow rate in the system A mass balance for a system is FAo- FA + GA = Where, N is the mass of A inside the system. ~ 13 ~ ……… (5)
  14. 14. 3.6. Second Law of Thermodynamics:- There are two statements as applied to thermodynamics: 1) Heat cannot be transferred from low temperature to high temperature without aid of external agency. Thus the law states the irreversible nature of spontaneous heat flow. 2) A spontaneous (non – equilibrium), irreversible change, the entropy (S) of an isolated system always increases. ∆S = +ve ∆S = Sprod - Sreact Where Entropy is a state function which is defines as: …………(6) dS = The standard entropy, So in terms of specific heat:- So(T) = Sref + ∫ ( ) dT ………….(7) The enthalpy of formation, Ho in terms of specific heat:- Ho(T) = Href + ∫ ( ) dT …………(8) Where, Sref & Href are the entropy and enthalpy of the species at the reference temperature Tref. 3.7. Gibbs free energy:- Gibbs free energy is a state function and acts as a store of non-mechanical work or energy available to the system for doing non-mechanical work. dG is a measure of the work obtainable from a reversible, isothermal process occurring at constant pressure and gives a direct indication of possibility of chemical reaction. dG = dH – TdS ~ 14 ~ ………….(9)
  15. 15. 3.8. Helmholtz Free Energy:- Helmholtz Free Energy A acts like a store of work or energy available for doing work (i.e. mechanical work and non- mechanical work together ) for the system , Hence, when work ∂W is done, A decreases by dA. dA = dE – TdS 3.9. …………..(10) Third Law Of Thermodynamics:- According the third Law of Thermodynamics “The entropy of any homogeneous substance, which is in complete internal equilibrium, may be taken as zero at the absolute zero temperature (i.e., So = 0 at T = 0 K). The third law of thermodynamics is finding of the Nernst who has given Nernst heat theorem as following: dG = dH – TdS [Since, ( ∆ ) p = - ∆S …..{From equation (9)} ] Put the value in above equation and differentiate with respect to T at constant pressure at T=0 K. ( ∆ ) p, = ( ∆ )p This means that ∆G and ∆H are not zero at absolute zero but approach zero at absolute zero, but their curves of ∆G vs. T and ∆H vs. T meet and both have the same slope at absolute zero. 3.10. Gibbs Energy Minimization:- The minimization algorithm determines internally the best set of independent system components that it should use during the minimization procedure. So each phase constituent is composed of one or more system components. At equilibrium the chemical potential µ of each system component at each phase is equal: ~ 15 ~
  16. 16. μ = μ = μ … Equilibrium of a closed thermodynamic system is established if its Gibbs energy at constant temperature and pressure has reached its minimum: G’ (T, p, ) ≤ G (T, p, ni) Gibbs energy of the system of one or more phases is then given as[3]: G=∑ ∑ (μ + ) ……….. (10) The minimum value of Gibbs energy is found so that the masses of the system components remain constant (mass balance constraints): bj = ∑ ∑ ………… (11) Where, bj is the molar amount of the system component j, ni is the molar amount of the constituent i in phase α, aij is the stoichiometric coefficient of the system component j in constituent i. There are several software/database packages with applications in materials science. These packages all contain large critically evaluated databases for thousands of compounds and hundreds of solution phases, as well as user interfaces of varying degrees of user-friendliness[6]:      HSC Chemistry MTS-NPL Thermo-Calc Thermodata FactSage This is a complete database because all the other thermodynamic properties (H, Cp, µ, etc.) can be calculated by taking the appropriate derivatives of the G functions. For a given set of constraints (such as temperature, total pressure and total mass of each element) the software calculates the equilibrium conditions by minimizing the total Gibbs energy of the system. This is mathematically equivalent to solving all the equilibrium constant equations simultaneously. ~ 16 ~
  17. 17. 4. FactSage:FactSage was introduced in 2001 as the fusion of the FACT-Win and ChemSage thermochemical packages[6]. The FactSage package runs on a PC operating under Microsoft Windows and consists of a series of information, database, calculation and manipulation modules that enable one to access and manipulate pure substances and solution databases. The software calculates the equilibrium conditions by minimizing the total Gibbs energy of the system for given a set of constraints. Fig.1.1 FactSage Menu The FactSage package runs on a PC operating under Microsoft Windows the FactSage Menu (Fig.1) offers access to the various modules of the package. The modules are grouped into four categories: 1. Info 2. Databases 3. Calculate 4. Manipulate ~ 17 ~
  18. 18. 4.1. Info:- The General module provides slide shows (Microsoft Power Point and Adobe PDF presentations) of all the modules as well as database documentation. The module also includes information on the FactSage Family of Products and Services. These products include[6]: ChemApp - The thermochemical teaching package based on FactSage Applications. - The thermochemistry library dynamically linked for software ChemSheet - The spreadsheet tool for process simulation. SimuSage - The component library for rapid process modeling. CSFAP - ChemSage File Administrator Program. OLI Systems - FactSage Interface: the link to the OLI aqueous databanks. METSIM - FactSage Link for coupled chemical process simulation. FactSage-Teach 4.2. Databases:- In FactSage there are two types of thermochemical databases – compound (pure substances) databases and solution databases. Compound databases contain data for stoichiometric compounds (of fixed composition) giving the properties as functions of T and P. Solution databases contain parameters of models giving the properties of solution phases as functions of composition as well as of T and P. The Documentation, View Data, Compound and Solution modules permit one to list and manipulate the database files. 4.2.(a) Documentation:Introducing extensive documentation and displaying calculated phase diagrams of different compositions of material at particular Temperature, Pressure range. ~ 18 ~
  19. 19. 4.2.(b) View Data:- In this module enter the E-L-E-M-E-N-T or Compound or All with selecting the database type, which we wish to view in the database. We can able to get the entire database [i.e. Cp (T), H (T), G (T), S (T)] at different phase in the Temperature range. 4.2.(c) Solution & Compound:- In these modules create the private compound & solution database which is not present database. These compound/solution got by the experimental data for any chemical reaction process. Once when we find the new compound/solution which is not present in the database, input here in the define group as present in database. 4.3. Calculate:- There is Reaction, Predom, EpH, Equilib, Phase Diagram and Optisage modules to calculate the different data require for the compositions. 4.3.(a) Reaction Module:The Reaction module calculates changes in extensive thermochemical properties (H, G, V, S, and Cp) & potential (volts) relative to the H2(g)/2H [+] standard reference electrode for a single species, a mixture of species or for a Chemical Reaction. 4.3.(b) Predom Module:The Predom module one can calculate and plot isothermal predominance area diagrams for one-, two- or three-metal systems using data retrieved from the compound databases. 4.3.(c) EpH Module:- The EpH module is similar to the Predom module and permits one to generate Eh vs. pH (Pourbaix) diagrams for one, two or three-metal systems using data retrieved from the compound databases that also include infinitely dilute aqueous data. ~ 19 ~
  20. 20. 4.3.(d) Equilib Module:The Equilib module is the Gibbs energy minimization workhorse of FactSage and offers great flexibility in the way the calculations may be performed. Equilib calculates the concentrations of chemical species with a wide variety of tabular and graphical output modes when specified elements or compounds react or partially react to reach a state of chemical equilibrium under a large range of constraints. Equilib accesses both compound and solution databases. 4.3.(e) Phase Diagram Module:The Phase Diagram module used to generate various types of phase diagrams for systems containing stoichiometric phases as well as solution phases, and any number of system components where the axes can be various combinations of T, P, V, composition, activity, chemical potential, etc. The Phase Diagram module accesses the compound and solution databases. The graphical output of the Phase Diagram module is handled by the Figure module. 4.3.(f) OptiSage Module:The OptiSage Module is used to generate a consistent set of Gibbs energy parameters from a given set of experimental data using known Gibbs energy data from wellestablished phases of a particular chemical system. The assessor (user of OptiSage) has to use his best judgment as to which of the known parameters should remain fixed, which sets of parameters need refinement in the optimization and which new parameters have to be introduced, especially when assessing data for non-ideal solutions. . 4.4. Manipulate:- It consist Results, Mixture, Fact-XML, Figure, Viscosity, Reset & Quit module which are not directly use in FactSage. There are mainly use first five modules for examine the data and phase diagram etc. which described below:- ~ 20 ~
  21. 21. 4.4.(a) Results Module:The Results module generates graphs from the output of complex equilibrium calculations performed with Equilib Results (Equi*.Res) files. Depending upon the selected axis variable(s) it may be necessary to specify in addition to the variable itself a species or phase to which this variable is related. 4.4.(b) Mixture Module:Use Mixture to edit mixtures and streams for input to Equilib. The mixture module use in making the mixture of the elements or compounds which are act as the reactants in the reaction process. In the stream module is use to take the mixture of the product gasses as and use them as a reactants which is very much helpful in recycling of heat/energy in the chemical process. 4.4.(c) Fact-XML:- The Fact-XML is an add-in to the Equilib program that enables you to edit the results of a calculation and save customized outputs as templates. There is no limitation to the number of templates. In this module we can change the unit, activity of species, graph setup and draw etc. 4.4.(d) Figure Module:Use of Figure to Manipulate, edit and plot figure and phase diagrams already calculated by FactSage. Graphical output from calculation modules such as Reaction, Predom, Equilib or Phase Diagram can be Post-viewed and edited using the Figure module. 4.4.(e) Viscosity Module:The viscosity module for single-phase, liquid slags and glasses has been developed. It is distinct from other viscosity models in that it directly relates the viscosity to the structure of the melt, and the structure in turn is calculated from the thermodynamic description of the melt using the Modified Quasichemical Model. ~ 21 ~
  22. 22. Chapter 2:- Experimental Detail 5. Methodology:1. Extraction of magnesium get by the raw material Dolomite, Ferro-Silicon & Bauxite with the following compositions (in Wt. %):- Ferro – Silicon:Si Fe Al Ca = = = = 70.10 % 27.19% 2.02% 0.53 % Calcined Bauxite:Al2O3 CaO SiO2 Fe (T) = = = = 87.34% 1.35% 4.66% 3.5% MgO CaO SiO2 Al2O3 Fe2O3 Na K = = = = = = = 20.80% 29.87% 0.54% 1.12% 1.24% 0.12% 0.04% Dolomite Ore (Dolo-3):- 2. By using the Mixture Module in FactSage, make mixture of Ferro-Silicon, Calcined Bauxite & Dolomite ore. Its to be mentioned mention that compositions are in mass percent unit and not in the “mole”. Save those mixtures for further process as shown in below fig: ~ 22 ~
  23. 23. Fig 2.1:- The Main Menu of Mixture Module[6] 3. Import all the mixture in the Equilib Module in different weight ratio of FerroSilicon, Calcined Bauxite & Dolomite ore. Then calculate the weight of Magnesium vapours at the specific temperature and pressure. Be sure that the mass unit in the Equilib module should not in “Mole”. Fig: 2.2:- The Main Menu of Equilib Module[6]
  24. 24. 4. The effective mass of magnesium is depend upon the minimum Gibbs Free Energy for the above mixture reaction at the specific temperature and pressure by the below formula: Pure Condensed Phases G= ∑ ni ( + RT ln Pi ) + ∑ ni + ∑ ni ( + RT ln Xi + RT lnγi) Ideal Gas + ∑ ni ( Solution - 1 + RT ln Xi + RT ln γi) …… [6] ……(12) Solution - 2 Where, ni : Moles Pi : Gas Partial Pressure Xi : Mole Fraction γi : Activity Coefficient : Standard Molar Gibbs Energy Since, Pi=Mg = * PTotal 5. When we get the best process condition for Magnesium Production from these raw materials. Then add the Lime at that process condition and observed the influence of lime at the production of Magnesium. 6. Then by using the Phase Diagram Module for components of slag ( i. e. MgO, CaO, Al2O3 & SiO2 ) draw the binary phase diagram keep constant amount of two components for looking the effect of other two components on slag formation temperature & Calcium Silicate + slag temperature by which it’ll easy to determine the Low melting temperature of slag economically, Make sure about the below condition[8]:- = 1.8 but for the furnace process this ratio can be use the range of 2.2- 2.4 = 0.26 but for the furnace process this ration can be use the range of 0.30– 0.33 …………. (iv) Slag components weight percentage should be in the following range: CaO SiO2 Al2O3 MgO = = = = ~ 24 ~ 54-58% 23-28% 11-15% 3-8%
  25. 25. 7. Draw the Liquidus projection Ternary Phase Diagram of the slag components CaO, Al2O3 & SiO2 at the range of the MgO amount (3-8 wt. %) and the temperature range (1400oC – 1800oC) for looking the Liquidus area shrinkage and growing with the MgO amount And Temperature by superimpose all diagrams. 0.026136 atm Fig 2.3:- The menu of Phase Diagram: Last system 8. For low viscosity of the slag use the Viscosity module, in which keep different slag composition ratio of the MgO, CaO, Al2O3 & SiO2 components with keep in mind above ratio and slag components amount at the temperature range 1400oC – 1700oC. 9. Finally with keep in mind Low slag Viscosity, Low Slag melting Temperature & optimum temperature and Pressure, determine the amount of raw material. ~ 25 ~
  26. 26. Chapter 3:- Results & Discussions 1. Take amount of the raw materials in different weight Ratio at Temperature range 1500oC-1700oC & Pressure 10mm – 30mm Hg. 1.1. Keep Calcined Bauxite & Ferro –Silicon Amount constant, increase the amount of Dolomite (Dolo-3). Ratio ( Dolo-3:Bauxite:Ferro-Silicon) (x100 gm.) Magnesium Yield (wt. %) at 1600 4.68 1.59 0.06 9.69 5.12 2.84 9.11 6.96 6.19 1600 10.13 8.30 7.37 11.27 10.22 9.01 13.14 11.01 10.28 1600 13.13 12.13 11.36 13.51 13.11 12.57 1500 13.91 13.31 12.84 1600 14.37 13.89 13.51 1700 14.64 14.34 14.08 1500 14.43 13.98 13.67 1600 14.75 14.38 14.13 1700 14.93 14.66 14.47 1500 13.93 13.45 13.07 1600 14.16 13.94 13.77 1700 14.29 14.12 13.99 1500 12.45 12.13 11.88 1600 12.72 12.56 12.42 1700 7:1:1 0.05 1700 6:1:1 0.29 1500 5:1:1 1.58 1700 4:1:1 30mm Hg 1500 3:1:1 20mm Hg 1700 2:1:1 10mm Hg 1500 1:1:1 Temperature (oC) 12.80 12.74 12.68 Table: 3.1:- Magnesium Yield at different ratio of Raw ~ 26 ~
  27. 27. Magnesium Yield (Wt. %) is economically maximum for the ratio 5:1:1 but Amount of Magnesium (gm.) is economically maximum at the ratio 6:1:1. So, it has been decided to choose the latter Ratio for the further procedure from above table. 1.2. Increase amount of Ferro –Silicon from 100gm to 130gm at constant Dolomite & Bauxite amount. Ratio ( Dolo-3:Bauxite:FerroSilicon) Temperature(oC) Magnesium amount(gm.) 118.43 115.42 113.42 1600 120.52 117.99 116.27 121.63 119.73 118.39 1500 122.98 119.59 117.31 1600 125.33 122.53 120.59 1700 126.49 124.30 122.75 1500 125.89 122.26 119.73 1600 128.48 125.50 123.37 1700 6:1:1.3 30 mm 1700 6:1:1.2 20 mm 1500 6:1:1.1 10 mm 129.77 127.54 125.87 Table: 3.2:- Magnesium Amount at changing the amount of Ferro-Silicon Since, we know that the Ferro-Silicon provide the Si which increase the reactant concentration by which reaction proceed forward that’s why magnesium amount increases as shown in reaction (i). 1.3. Increase the Amount of Calcined Bauxite at Ratio 6:1:1.3 with keeping the constant amount of Dolomite & Ferro-Silicon. Ratio ( Dolo-3:Bauxite:Ferro-Silicon) Temperature(oC) Magnesium amount(gm.) 10 mm 30 mm 1500 121.84 117.19 114.03 1600 125.43 121.85 107.27 1700 6:1.5:1.3 20 mm 127.48 124.91 122.97 Table: 3.3:- Magnesium Amount at changing the amount of Bauxite ~ 27 ~
  28. 28. Means for the efficient production of Magnesium, the Optimum ratio of Dolo-3: Calcined Bauxite: Ferro-Silicon should be in 6:1:1.3. 2. Take the Magnesium amount at the optimum ratio of raw material at pressure range 10 mm-30 mm Hg at constant temperature range 1500oC-1700oC. 131 1550 oC 130.1064 129.6144 130 129 128.7744 1600 oC 128.1456 128 127.5888 1700 oC 127.8216 127.08 126.9408 125.688 127 Magnesium Amount (gm) 1650 oC 128.856 125.7144 126.0864 126 1500 oC 126.9168 125.9016 125 126.108 124.98 124.5528 124 123.9984 124.1784 123.528 123 122.904 122.3544 122 121.7856 121 120.9696 120 119.7528 119 118 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 Pressure (mm Hg) Fig: 3.1:- Magnesium amount at constant Temperature 3. Take the Magnesium amount at the optimum ratio of raw material at constant pressure range 10 mm-30 mm at temperature range 1500oC-1700oC. ~ 28 ~
  29. 29. 131 130.1064 130 129.6144 129 128.856 128.7744 128.1456 128 127.5888 127.08 Magnesium Amount (gm) 127 126 126.0864 125.688 126.9408 125.7144 125.9016 125 127.8216 126.9168 126.108 124.98 124.5528 124 123.9984 124.1784 123.528 123 122 121 120 20 mm 122.904 122.3544 25 mm 121.7856 10 mm 120.9696 15 mm 30 mm 119.7528 119 118 1475 1500 1525 1550 1575 1600 1625 Temperature (oC) 1650 1675 1700 1725 Fig: 3.2:- Magnesium amount at constant Pressure By comparing both Fig 3.1 & Fig 3.2, we observe that at 20mm Hg pressure and 1600 oC we get the efficient amount of Magnesium 125.72 gm. Per 830 gm. Raw Materials. 4. Now add the Lime in the amount range (0 gm.-80 gm.) at 1600 oC & 20 mm Atmospheric pressure at the optimum Ratio of raw material for observing its effect on the Magnesium Production Rate. ~ 29 ~
  30. 30. Lime 0 10 20 30 40 50 Addition(gm.) 125.50 126.41 127.36 128.24 129.08 129.89 Magnesium amount (gm.) Solid Slag (wt. 13.816 16.95 19.91 22.67 25.24 27.58 %) 1.003 0.99 0.977 0.962 Viscosity (poise) 1.024 1.014 Table: 3.4:- Effect of Lime Addition 60 70 80 130.65 131.37 132.04 29.7 31.57 33.19 0.945 0.928 0.909 When we add lime then from Reaction (ii), we observe that Partial Pressure of SiO is Low than Reaction (i) that’s why the Magnesium production increases. 5. Then Feed requirement for the 1 ton Magnesium and the slag composition of the process with increasing the amount of lime will be following: Dolomite ore (ton) 4.781 4.745 4.711 4.679 4.648 4.619 4.592 4.567 4.544 Calcined Bauxite (ton) 0.797 0.791 0.785 0.779 0.775 0.769 0.765 0.761 0.757 FerroSilicon (ton) 1.036 1.028 1.021 1.014 1.007 1.001 0.995 0.989 0.985 Total Energy Amount Requirement (ton) (kWh/ton) 0 6.614 1.4226*10^4 0.079 6.643 1.4336*10^4 0.157 6.674 1.4447*10^4 0.234 6.706 1.4559*10^4 0.309 6.739 1.4674*10^4 0.385 6.774 1.4790*10^4 0.459 6.811 1.491*10^4 0.523 6.84 1.5033*10^4 0.606 6.892 1.5159*10^4 Table: 3.5:- Feed requirement Lime (ton) Slag(ton) Solid 0.765 0.944 1.115 1.278 1.431 1.575 1.707 1.827 1.935 Liquid 4.771 4.624 4.486 4.358 4.241 4.134 4.04 3.959 3.894 6. Now draw the binary phase diagram between the Temperatures Vs. mass fraction of slag constituents for observing the Lowest Liq-Slag & Solid Slag (Ca2SiO4) formation temperature with keep in mind equation (iv). 6.1. Keep MgO mass fraction in range of 0-0.08 Wt. % with keep the constant mass fraction of Al2O3 & SiO2, draw the Binary Phase Diagram. ~ 30 ~
  31. 31. Fig: 3.3:- Effect of MgO at Binary Phase Diagram Take the Solid & Liquid slag temp & Wt. % at different mass fraction of MgO from above Binary Phase Diagram. MgO(mass Fraction) 0.05 0.06 0.07 0.08 Solid Slag Temp. 1480.77 1524.62 1560 1590.15 Liquid Slag Temp. 1861.54 1831.08 1791.38 1745.23 Solid slag % 39.85 31.83 23.91 16.03 Liquid slag % 60.15 68.17 76.09 83.97 Table: 3.6:- Effect of the MgO at the slag From the above data, we observe that as increasing the amount of MgO in slag Solid Slag temperature increase as decreasing the Liquid Slag temperature. Since as increasing the MgO in slag decreases the Magnesium amount as in reaction (i). That’s why solid slag percentage also decreases with increasing the amount of MgO in slag. ~ 31 ~
  32. 32. 6.2. Keep Al2O3 mass fraction in range of 0-0.20 Wt. % with keep the constant mass fraction of MgO & SiO2, draw the Binary Phase Diagram. Fig: 3.4:- Effect of Al2O3 at Binary Phase Diagram Take the Solid and Liquid Slag wt. % in the slag at the efficient solid slag temperature at different mass fraction of Al2O3 from above Binary Phase Diagram. Al2O3(mass Fraction) .095 .098 .1 .105 Solid Slag Temp. 1652 1502.46 1436.92 1436.92 Liquid Slag Temp. 1748.92 1824.62 1897.54 1906.77 Solid slag % 12.03 31.68 44.69 70.02 Liquid slag % 87.97 68.32 55.31 29.98 Table: 3.7:- Effect of the Al2O3 at the slag ~ 32 ~
  33. 33. From the above data we observe that as increasing the amount of Al2O3 in slag decreases the solid slag temperature but increases the liquid slag temperature. Since alumina in slag also increases the CaO in slag that’s why solid slag will be increase as in reaction (ii). 6.3. Keep SiO2 mass fraction in range of 0-0.32 Wt. % with keep the constant mass fraction of MgO & Al2O3, draw the Binary Phase Diagram. Fig: 3.5:- Effect of SiO2 at Binary Phase Diagram Take the Solid and Liquid Slag wt. % in the slag at the efficient solid slag temperature at different mass fraction of SiO2 from above Binary Phase Diagram. SiO2(mass Fraction) .31 .3 .29 .29 Solid Slag Temp. 1436.92 1436.85 1577.69 1637.69 Liquid Slag Temp. 1832 1791.54 1746.15 1735.38 Solid slag % 58.33 46.79 29.46 12.82 Liquid slag % 41.67 53.21 70.54 87.18 Table: 3.8:- Effect of the SiO2 at the slag ~ 33 ~
  34. 34. From the above data we observe that increasing the amount of SiO2 in slag decreases solid slag temperature with increasing the liquid slag temperature. Since increasing silica in slag increase the CaO [reaction (iv)] that’s why solid slag will form more as in reaction (ii). 6.4. Keep CaO mass fraction in range of 0-0.58 Wt. % with keep the constant mass fraction of MgO & Al2O3, draw the Binary Phase Diagram. Fig: 3.6:- Effect of CaO at Binary Phase Diagram Take the Solid and Liquid Slag wt. % in the slag at the efficient solid slag temperature at different mass fraction of CaO from above Binary Phase Diagram. CaO(mass Fraction) 0.54 0.55 0.56 0.57 Solid Slag Temp. 1662 1524 1437 1481 Liquid Slag Temp. 1786 1853.54 1906.5 1941.33 Solid slag % 16.58 34.91 47.01 53.93 Liquid slag % 83.42 65.09 52.98 46.07 Table: 3.9:- Effect of the CaO at the slag ~ 34 ~
  35. 35. As we observe from the above data as increasing the amount of CaO in slag Solid temperature first decrease then again increase and liquid slag temperature increases. As increase CaO in slag also increase the silica [reaction(iv)] by which the slag formation will be more. 7. Draw the ternary phase diagram of slag components Al2O3, SiO2 and CaO at Magnesium amount range 3gm-8gm and Temperature range 1500 oC – 1700 o C at constant pressure 20mm Hg for observing the effective Liquidus Projection with combine effect of slag components: 1800oC 1600oC 1500oC 1700oC Fig: 3.7:- Liquidus Projected Ternary Phase Diagram at MgO = 3gm ~ 35 ~
  36. 36. 1800oC 1700oC 1600oC 1500oC Fig: 3.8:- Liquidus Projected Ternary Phase Diagram at MgO = 4.5gm 1800oC 1700oC 1600oC 1500oC Fig: 3.9:- Liquidus Projected Ternary Phase Diagram at MgO = 6gm ~ 36 ~
  37. 37. 1600oC o 1800 C 1700 C 1500oC o Fig: 3.10:- Liquidus Projected Ternary Phase Diagram at MgO = 8gm 8. Now take slag composition of the components at the temperature range for measuring the viscosity of slag in melts state. 8.1. First keep Magnesium amount constant in the range of 1-8 wt. % and make different composition of slag. Slag Compositions (wt. %) MgO CaO Al2O3 SiO2 62.17 8.5 28.33 1 62.94 8.5 26.56 2 61.6 7.4 28 3 57.47 9.5 29.03 4 56.23 8 30.77 5 56 8.53 29.47 6 55.37 8 29.63 7 55.43 8 28.57 8 o 1400 C 2.18 2.012 2.061 2.351 2.41 2.31 2.281 2.173 Viscosity(poise) 1500 oC 1600 oC 1.235 0.744 1.145 0.693 1.173 0.709 1.333 0.803 1.365 0.823 1.314 0.794 1.299 0.786 1.242 0.753 Table: 3.10:- Effect of the MgO at the Viscosity of slag ~ 37 ~ 1700 oC 0.472 0.441 0.452 0.51 0.522 0.505 0.501 0.481
  38. 38. As the amount of MgO increases (0-8 gm.), the viscosity of slag also increases (0.44-2.41 poise) at constant temperature and decreases with increasing temperature. 8.2. Now make the compositions of slag components (i. e. Al2O3, SiO2 & CaO) with observing viscosity of slag at different temperature. Slag Compositions (wt. %) MgO CaO Al2O3 SiO2 4 56 30 10 4.1 56.1 30.2 9.6 4.2 56.3 30.5 9 4.4 56.5 30.7 8.4 4.5 56.8 30.8 7.9 o 1400 C 2.521 2.504 2.478 2.441 2.403 Viscosity(poise) 1500 oC 1600 oC 1.425 0.857 1.415 0.851 1.402 0.843 1.382 0.831 1.361 0.819 1700 oC 0.543 0.539 0.534 0.527 0.520 Table: 3.11:- Effect of the Al2O3 at the Viscosity of As the amount of Alumina increases (7.9-10 gm.), the viscosity of slag also increases (2.521-0.520 poise) at constant temperature and decreases with increasing temperature. Slag Compositions (wt. %) MgO CaO Al2O3 SiO2 5 55 10 30 5.5 55.5 9.5 29.5 6 56 9 29 6.3 56.2 9.3 28.2 6.4 56.3 9.4 27.9 o 1400 C 2.520 2.406 2.301 2.242 2.219 Viscosity(poise) 1500 oC 1600 oC 1.426 0.858 1.365 0.823 1.309 0.791 1.277 0.773 1.265 0.767 1700 oC 0.544 0.523 0.504 0.493 0.489 Table: 3.12:- Effect of the SiO2 at the Viscosity of slag As the amount of Silica increases (27.9-30 gm.), the viscosity of slag also increases (2.520-0.489 poise) at constant temperature and decreases with increasing temperature Slag Compositions (wt. %) MgO CaO Al2O3 SiO2 5.5 9.5 28.5 56.5 5.8 9.6 29 55.6 6 9.7 29.3 55 6.2 9.8 29.5 54.5 6.3 9.9 29.8 54 o 1400 C 2.291 2.357 2.402 2.435 2.483 Viscosity(poise) 1500 oC 1600 oC 1.303 0.788 1.339 0.809 1.364 0.823 1.382 0.834 1.408 0.849 1700 oC 0.501 0.514 0.523 0.530 0.539 Table: 3.13:- Effect of the CaO at the Viscosity of slag As the amount of CaO increases (54-56.5 gm.), the viscosity of slag also decreases (2.483-0.501 poise) at constant temperature and also decreases with increasing temperature ~ 38 ~
  39. 39. Chapter 4:- Conclusions  The process conditions for the production of Magnesium by Magnotherm Process is evaluated.  The optimum ratio of the raw materials is found to be Dolomite: Bauxite: FerroSilicon: Lime:: 6:1:1.3:0.5.  The optimum range of the operating process conditions are; 1600oC temperature & 20mm Hg Pressure for the given raw material and the feed ratio.  Maintenance of the liquid slag is evaluated through the phase diagrams and the calculation of the viscosity of the given slag. From the calculations, it is known that the minimization of silica in the slag and optimized use of the amount of Magnesia and Alumina leads to the maintenance of the slag in liquid form. ~ 39 ~
  40. 40. Chapter 5:- Future work  These studies can further continued in the open system, where continuous evaluation of the Mg can be obtained, which is an actual situation.  The kinetic study of the rate of dissolution of the ore in the slag bath is an important parameter for the Mg production.  CFD of the Magnesium reactor is important, as to access the internal process parameters and its distribution over the entire domain. ~ 40 ~
  41. 41. Chapter 6:- References 1. ASM Specialty Handbook, “Magnesium and Magnesium Alloys”. 2. H S Ray, “Extraction of Non Ferrous Metals”. 3. Gaskell, “Introduction to thermodynamics of materials”. 4. J.M Toguri and L.M. Pidgeon, Can. J. Chem. 39, 540 (1961). & O. Kubaschewski and E. Ll. Evans. “Metallurgical thermochemistry”. Pergamon Press Ltd., London. 1958. 5. Ursula R. Kattner NIST-Gaithersburg. “Thermodynamic Modeling of Multicomponent Phase Equilibria”. JOM 49 (12) (1997) 14-19. 6. FactSage® 6.4 Manual. 7. Melissa Marshall and Zi-Kui Liu, “A Computational Thermodynamic Analysis of Atmospheric Magnesium Production”. TMS (2001) 8. United states Patent 4190434, “Thermal Processes for the Production of Magnesium”.(14th Jun-1978) ~ 41 ~

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