Literature Review on Iron Production Technologies and COREX Process Mathematical Models

by
Ahmed Wafiq Abdel Mohsen Abolnasr
M.Sc. of Chemical Engineering 2011 Cairo University

The Literature Review Chapter of the Thesis (MICROSCOPIC MODELING OF THE FREE BOARD AND FLUIDIZED BED INSIDE THE MELTER-GASIFIER OF OPTIMIZED COREX IRONMAKING PROCESS)

in Partial Fulfillment of the Requirements for the Degree of MASTER OF SCIENCE in CHEMICAL ENGINEERING
Under the Supervision of Prof. Dr. Tarek Mohamed Moustafa Dr. Ahmed Soliman Fawzy Dr. Ahmed Fayez Nassar Department of Chemical Engineering Faculty of Engineering-Cairo University FACULTY OF ENGINEERING, CAIRO UNIVERSITY GIZA, EGYPT 2011
1

LIST OF CONTENTS
IRON PRODUCTION LITERATURE REVIEW ......................................................... 4
2.1 Introduction ........................................................................................................................... 4 2.2 Principal Iron Bearing Materials ............................................................................................ 4 2.2.1 Different Iron Ores ......................................................................................................... 5 2.2.2 Impurities in Iron Ores .................................................................................................... 6 2.2.3 Classification of Iron Ores............................................................................................... 6 2.2.4 Pelletisation .................................................................................................................... 7 2.2.5 Sintering.......................................................................................................................... 8 2.3 Blast Furnace ......................................................................................................................... 9 2.3.1 Blast Furnace Process Description.................................................................................. 9 2.3.2 Blast Furnace Gas Cycle ................................................................................................ 12 2.3.3 Production and Processing of Coke .............................................................................. 13 2.3.4 Required Coke Properties............................................................................................. 14 2.3.5 Required Flux Properties .............................................................................................. 14 2.3.6 Required Air Properties ................................................................................................ 15 2.3.7 Blast Furnace Reactions................................................................................................ 15 2.3.8 The Challenge of Coal Injection .................................................................................... 18 2.3.9 Environmental Analysis for the Blast Furnace Technology .......................................... 19 2.3.9.1 Sintering Plant Pollutants ...................................................................................... 19 2.3.9.2 Coking Plant Pollutants .......................................................................................... 19 2.3.9.3 Blast Furnace Pollutants ........................................................................................ 20 2.3.9.4 Greenhouse Gas Emissions for the Whole Industry .............................................. 20 2.3.10 Drawbacks of the Blast Furnace ................................................................................. 21 2.4 General Overview on Direct Reduction ............................................................................... 21 2.4.1 Metallization ................................................................................................................. 22 2.4.2 Use of DRI in Electric Arc Furnaces (EAF) ..................................................................... 22 2.4.3 DRI Oxidation and Briquetting...................................................................................... 23 2

2.4.4 Broad Classification of DR Processes ............................................................................ 24 2.4.5 Global DRI Production .................................................................................................. 24 2.5 Gas-Based DR Processes ...................................................................................................... 25 2.5.1 MIDREX Process ............................................................................................................ 25 2.5.1.1 Main Reactions Taking Place ................................................................................. 25 2.5.1.2 Process Description ............................................................................................... 25 2.5.2 HYL III Process ............................................................................................................... 27 2.5.2.1 Process Description ............................................................................................... 27 2.5.2.2 Some Process Features .......................................................................................... 28 2.5.3 ENERGIRON Process ..................................................................................................... 28 2.5.3.1 Main Reactions Taking Place ................................................................................. 29 2.5.3.2 Process Description ............................................................................................... 29 2.5.3.3 Some Process Features .......................................................................................... 30 2.6 Coal-Based DR Processes ..................................................................................................... 31 2.6.1 General Process Description of Rotary Kiln Technologies ............................................ 31 2.6.2 Encountered Reactions during coal-based DR Processes ............................................ 33 2.6.3 Comparison between Different Rotary Kiln DR Processes in Commercial Use ............ 34 2.6.4 Advantages of Rotary Kiln Processes............................................................................ 34 2.6.5 Disadvantages of Rotary Kiln Processes ....................................................................... 35 2.7 Smelting Reduction ............................................................................................................. 35 2.7.1 Advantages of SR with respect to Blast Furnace .......................................................... 36 2.7.2 Advantages of SR with respect to DR ........................................................................... 36 2.7.3 Use of Hot Metal in Electric Arc Furnaces (EAF)........................................................... 37 2.7.4 General Features of SR ................................................................................................. 37 2.7.5 Reaction Encountered in SR Processes ........................................................................ 38 2.7.5.1 Reactions Encountered in Pre-reduction Stage .................................................... 38 2.7.5.2 Reactions Encountered in Smelting Stage ............................................................. 39 2.7.6 COREX Process .............................................................................................................. 39 2.7.6.1 History of COREX ................................................................................................... 39 2.7.6.2 COREX Process Description ................................................................................... 40 2.7.6.3 Commercial Production ......................................................................................... 41 2.7.7 FINEX Process ............................................................................................................... 41

2.8 COREX Process for Pig Iron Production ............................................................................... 42 2.8.1 Detailed Process Description ........................................................................................ 42 2.8.1.1 RS Process Description .......................................................................................... 43 2.8.1.2 MG Process Description ........................................................................................ 43 2.8.2 Dimensions of the Encountered Reactors .................................................................... 44 2.8.3 COREX Export Gas......................................................................................................... 45 2.8.4 Raw Material Requirements for COREX Process .......................................................... 47 2.8.4.1 General Requirements .......................................................................................... 47 2.8.4.3 Use of Coke in COREX Process ............................................................................... 48 2.8.5 Factors Affecting the Efficiency of COREX Process ....................................................... 48 2.8.6 Environmental Analysis for COREX Process.................................................................. 49 2.8.7 Advantages of COREX Process ...................................................................................... 51 2.8.8 Disadvantages of COREX Process ................................................................................. 52 2.8.9 Case Study Jindal ....................................................................................................... 52 2.8.9.2 Using Iron Ore Fines .............................................................................................. 53 2.8.9.3 Recycling of various by products and plant wastes............................................... 54 2.8.9.4 Improvement in Plant Operation .......................................................................... 54 2.8.9.5 Synergetic Combination of COREX and Blast Furnace........................................... 54 2.8.10 Case Study SALDANHA............................................................................................. 55 2.9 COREX Macroscopic Analysis............................................................................................... 56 2.9.1 Reduction Shaft Macroscopic Analysis ......................................................................... 56 2.9.2 Melter-Gasifier Macroscopic Analysis .......................................................................... 57 2.9.2.1 Effect of Coal Size .................................................................................................. 57 2.9.2.2 Fuel Rate ................................................................................................................ 57 2.9.2.3 Factors Affecting Coke Addition ............................................................................ 58 2.9.2.4 Effect of amount of volatile matter in coal ........................................................... 59 2.9.2.5 Effect of Moisture .................................................................................................. 60 2.9.2.6 Minimization of Energy Consumption ................................................................... 61 2.9.2.7 Effect of %MgO and %Al2O3 on the slag ................................................................ 61 2.9.2.8 Modeling of COREX process for optimization of operational parameters ............ 62 2.10 COREX Microscopic Analysis.............................................................................................. 63 2.10.1 Reduction Shaft Microscopic Analysis ........................................................................ 63

2.10.2 Melter-Gasifier Microscopic Analysis ......................................................................... 63

References ........................................................................................................................ 65

IRON PRODUCTION LITERATURE REVIEW

In this chapter, the properties of different iron ores are discussed. The features, raw materials, modifications, and disadvantages of blast furnace are covered. Commercially applied direct reduction processes for iron production are explained. The industrially proven smelting reduction processes are described. Detailed description of the technical and commercial issues of COREX process is presented. The previous efforts in COREX macroscopic and microscopic analysis are summarized.

2.1 Introduction
In order to model and optimize certain new process for ironmaking, this should be preceded by presenting the different global techniques used in the field. Each of the three principal categories of ironmaking; blast furnace, direct reduction, and smelting reduction have advantages and disadvantages. Moreover, the direct reduction and smelting reduction comprise a lot of different processes which are competing to reach the degree of commercial application. Big steel complexes can successfully use the blast furnace together with one of the new techniques to utilize the advantages of both.

2.2 Principal Iron Bearing Materials

As will be shown later, the nature of iron bearing materials is very important parameter which can cause the success or failure of certain technology. Nearly all technologies put constraints for the nature of iron bearing materials to be used in the production of iron.

2.2.1 Different Iron Ores

The ores of iron occur exclusively as its oxides.
[1] [6]

Hematite is the most

plentiful iron mineral mined, followed by Magnetite, Goethite limonite, Siderite, Ilmenite, and Pyrite.

The following table compares the different iron ores in terms of chemical composition, percentage iron, color, crystal structure, and specific gravity.
1Table 2.1 Principal iron bearing materials [7] Parameter Hematite Magnetite FerrousFerric Oxide Fe3O4 72.36 Goethite (Limonite) Hydrous Iron Oxide Siderite Ilmenite IronTitanium Oxide FeTiO3 36.8 Pyrite

Chemical Name Chemical Formula Iron, wt%

Ferric Oxide

Iron Carbonate

Iron Sulfide

Fe2O3 69.94

HFeO2 62.85 Yellow or brown to nearly black

FeCO3 48.2 White to greenish gray to black

FeS2 46.55 Pale brassyellow

Color

Steel gray to red

Dark gray to black

Ironblack

Crystal Structure Specific Gravity

Hexagonal

Cubic

Orthorhombic Hexagonal Hexagonal

Cubic 4.955.1

5.24

5.18

3.3-4.3

3.83-3.88

4.72

Limonite is famous with its extreme reducibility; thus, it is often employed as a mixture with less reducible ores. On the other hand, Magnetite is characterized by special magnetic behavior which causes easy separation of the ore impurities.
[6]

2.2.2 Impurities in Iron Ores

Beside the iron oxide contained in any ore, there are also different percentages of impurities (called gangue) which will affect the purity of the produced iron especially if one of the direct reduction technologies (DR) is to be used. Thus, DR technologies have big constraints on the purity of iron ore. The following table shows the composition (in wt%) of 2 different iron ores; one from a Swedish mine and the other from an Egyptian mine. It is apparent that the iron ore from both mines greatly differ from each other. It is also apparent that the iron percentage in the Egyptian mine is low, and thus it is not a suitable raw material for the production of DRI.
2 Table 2.2 Iron ore composition from 2 different mine s Composition Fe Al2O3 BaO CaO K2 O MgO MnO Na2O P2O5 S SiO2 TiO2 V2O5 Swedish Ore[8] 66.74 0.25 0 0.47 0.035 1.45 0.085 0.041 0.021 0.0005 2 0.195 0.21 Egyptian Ore[9] 58 2 1.5 0.7 0.3 0.02 3.5 0.3 0.2 0.1 8 0.02 0

2.2.3 Classification of Iron Ores

The most famous classification of iron ores is Bessemer versus nonBessemer. A Bessemer ore is one in which the phosphorous is low enough to make the pig iron only contains 0.1 % phosphorous or less.
[6]

Iron ores can

also be classified according to the particle form. So, it is frequent to hear that the iron ore is classified into lump, fine, pellets, and sinter.

2.2.4 Pelletisation
Pelletisation is a process of agglomeration of iron ore fines. It is one of the industry trademarks. In this process , the particles smaller than 200 m of which about 50% with 50 m size are converted into 12 -15 mm pellets with nodular shape as shown in figure 2.1. These iron ore fines are mainly

generated at mines. However, further grinding is also needed to reach the size stated above. For efficient pelletizing process, the iron ore should be of very high quality (low gangue). Thus, low grade ore fines should be first grinded and cleaned.
[10]

The ground ore is mixed with the proper amount of water and binder, normally bentonite (Al2O3.4SiO2.H2O), and then rolled into small balls 9 15 mm in diameter in a balling drum or disk. These green (wet) pellets are dried, then heated to 1200 1375oC to bond the small particles, and are finally cooled. As shown in figure 2.2, the heating can be done on a traveling grate, in a shaft furnace, or by a combination of a traveling grate and a rotary kiln (grate kiln). The traveling grate and grate kiln are the most commonly used pelletizing processes. [1]

1Figure 2.1 Iron ore pellets

2Figure 2.2 Pellet-Firing system: a) Shaft furnace, b) Grate furnace, c) Travelling grate furnace [10]

2.2.5 Sintering
Sintering is a principal section in integrated steel plants. Sintering consists of igniting a mixture of wet iron-bearing limestone and coke fines on a traveling grate to produce a clinker-like aggregate (sinter) suitable for use in the blast furnace. The iron-bearing fines can include iron ore fines, flue dust, or other steel mill wastes. As shown in figure 2.3, the traveling grate is shaped like an endless loop of conveyor belt. The bed of material on the grate is first ignited by passing under an ignition burner that is fired with natural gas and air; then, as the grate moves slowly toward the discharge end, air is pulled down through the bed. As the coke fines burn in the bed, the heat generated sinters the particles. At the discharge end of the machine, the sinter is crushed to remove extra-large lumps, then cooled, and is then finally screened.
[1]

When the coke fines are combusted on the grate, partial fusion takes place for the charge. On cooling, the different mineral phases crystallize and bond the

structure together to form a strong sinter.

[11]

The sinter bed permeability

mainly controls the performance of sintering. It was found that water addition, particle size distribution, ore porosity are very important factors in determining the beds permeability.
[12], [13]

Water Sinter Machine ESP

Main Fan Emission Monitoring Quench Fan Water Fine Scrubbers

Mashing Stage Sludge Water Process Air

Mashing Water

Recycling Fe-Components Nat. Gas Reheating Thickener Sludge Tank Floating Sludge to BF Sludge Cleaned Water
[14]

Discharge Water

Water Treatment

Slag Immobilisation

Depot

3Figure 2.3 Flow sheet of iron ore sintering

2.3 Blast Furnace

The blast furnace is the dominant unit operation for iron production till now. Continuous improvements to the blast furnace have enabled it to compete with the fast growing new direct reduction and smelting reduction technologies.

2.3.1 Blast Furnace Process Description

As shown in Figure 2.4, a hopper at the top discharges raw materials into the furnace by using a pressurized gas seal system known as double bell.
[1]

This system prevents gases and dust from escaping into the atmosphere. As shown in figure 2.5, the charge consists of alternating loads of coke and a mixture of iron bearing materials (iron ore, pellets, sinter) and flux (mainly

limestone, and dolomite).

[3]

These solids form a column that descends through

[15]

the furnace with a total residence time of about eight hours.

Around the

circumference of the furnace near the bottom, water cooled nozzles (called tuyeres) inject preheated air, often enriched with oxygen, into the furnace. In most cases, gaseous, liquid, or powdered fuel are introduced together with the preheated air. The heated air burns the injected fuel, and coke to produce the heat required for the process, and to provide reducing gases that removes oxygen from the ore.
[16]

The reducing gases rapidly ascend through the

column and are expelled through a pair of stacks at the top in less than 20 seconds.[3] The reduced iron melts, and settles in the bottom. The flux combines with the impurities of the ore and coke to produce slag which also melts and accumulates on the top of the molten iron. The gases exiting the furnace are cleaned, and then are utilized in different ways.

4Figure 2.4 Double bell system used in blast furnaces

10

5Figure 2.5 Blast furnace

The charging to blast furnaces is continuous, while the tapping of the hot metal and slag is performed in batches. So, the process is considered semicontinuous. The slags tapping hole is about 1.4 meters above the hot metals tapping hole. From the operating experiences, the slag is tapped before the hot metal.
[17]

The hot metal is poured into refractory-lined railcars which are used

for transportation to the steelmaking section.

11

2.3.2 Blast Furnace Gas Cycle

The off-gases leave the top of the furnace through uptake pipes, reverse their direction in a down-comer, and enter the dust catcher. In the latter, dust is separated from the gases. The dust is emptied into a rail car for transport to a sinter plant for recycle or to a landfill. After leaving the dust catcher, the off-gas is washed in a Venturi scrubber to get rid of the remaining solid particles, and to condense the water vapor to achieve higher gas calorific value.
[18]

The cleaned gas can be utilized in steam

generation and power generation, firing steelmaking furnaces, firing of coke ovens in the coke-processing nearby plant, and firing the blast furnace stoves. The blast furnace stoves (also known as cawpers) are used for preheating the air used in the blast furnace. There are usually three or four stoves lined with refractory materials. Mainly air passes by one of the stoves, and the others are being heated by the combustion of blast furnace gases. Thus, the stoves alternate between absorbing heat generated by combustion of the blast furnace off-gas, and releasing heat to the cold blast air as it passes down through the stove. After leaving the stoves, the hot blast enters a large refractory-lined bustle pipe which distributes the air on the tuyeres shown in figure 2.6. [1]

12

6Figure 2.6 Tuyeres around the blast furnace

2.3.3 Production and Processing of Coke

As shown in the blast furnace process description, coke is a main raw material. Coke is produced from coking coals in a plant nearby the blast furnace inside the integrated steel complex. The process of producing coke involves heating coal in absence of oxygen to about 2000oF in a distillation-like process.
[19]

Many of the organic

substances inside the coal volatilize leaving the coke as the only solid product. The volatilized gas is then subjected to sequentially lower temperature direct contact condensing chambers, which capture tar (a mixture of many relatively heavy organic compounds), oils, light oils, and finally low-molecular-weight gases. Coke is pushed into a quenching car that transports it to quenching towers. Here, the coke is sprayed with water to lower its temperature.
[20]

Because of the direct contact of water with the coke oven gases and coke, wastewater streams from the coking plant contain high concentrations of

13

ammonia, phenol, sulfides, thiocyanates, and cyanides. Moreover, airborne emissions also include SOx, NOx, ammonia, and particulate matters.
[21]

2.3.4 Required Coke Properties

Coke has three primary functions in the blast furnace. First, the coke is a reductant. It is gasified with the hot air to produce CO rich reducing gas that converts the iron ore feed into iron. Second, the coke is a fuel. It provides sufficient heat to melt the iron and the slag and promote the endothermic reactions involved in the blast furnace. Third, the coke serves as a packed bed. It provides a self-supporting porous bed that facilitates the contact between the descending iron ore charge, and the ascending reducing gases. It also facilitates the drainage of molten iron and slag phases. The composition of coke is known by conducting proximate analysis where four parameters are measured: Fixed carbon, volatiles, ash content, and moisture . Sulfur is the most undesirable impurity in the industry. Despite being partially removed during coking, still coke can contain about 1% sulfur.
[17] [6]

Size control is important in order to guarantee appropriate bed permeability, so the minimum used size is about 15 mm.

Through continuous research, and as an attempt to reduce the coke consumption in the blast furnace, it is customary now to have solid, liquid, or gaseous fuels, e.g. coal, fuel oil, or natural gas, added to the hot air blast at the tuyeres to replace some of the coke. [1]

2.3.5 Required Flux Properties

If iron ores are reduced without flux, the impurities of the iron ore (mainly silica and alumina) will react with iron oxides to form double silicates of iron which is a heavy loss of iron. By the addition of a fluxing material (e.g.: limestone), silica and alumina will have a great tendency to react with lime

14

than iron. Flux also reacts with coke ash. Moreover, flux reacts with sulfur (mainly from coke), and thereby reduces its concentration in the hot metal. Fluxes are usually added in the form of either limestone or dolomite. The main flux impurities are silica, alumina, sulfur, and phosphorous. The presence of such impurities will reduce the percentage of lime and magnesia, and this will require additional amount of flux to get rid of them.
[6]

2.3.6 Required Air Properties

Air may also be considered a raw material. Over 1.5 ton of air is required to produce 1 ton of hot metal.
[1]

If the moisture content of the air is increased, the higher air temperatures could be used satisfactorily. The added moisture promotes the endothermic water gas reaction (C + H 2O = CO + H 2), and thus the temperature in the combustion zones isnt extremely high, and consequently the furnace runs more smoothly. After further research, it was possible to inject auxiliary fuels as pulverized coal, fuel oil, and natural gas with the air through the tuyeres in order to decrease the coke consumption. Moreover, it is now possible to use oxygen enriched air as high as 30%. Oxygen enrichment causes high production rates. However, a good economic analysis is needed to determine the optimum percentage of oxygen enrichment.
[22]

So, recently the air used in the tuyeres is preheated to 900 - 1300 o C, and is mainly associated with moisture, oxygen, and auxiliary fuels.

2.3.7 Blast Furnace Reactions

Inside the blast furnace, many different unit operations occur simultaneously including heat and mass transfer, reduction by gases, reduction by solid carbon, high temperature gas generation, and finally smelting and

15

liquid drainage. [23] The countercurrent flow of gas and solids include heat transfer from gases to solids, and oxygen transfer from solids to gases. [24] From an overall heat and mass balance point of view, the blast furnace can be divided into 4 zones:

a) Combustion zone As the coke descends through the furnace, it is heated by the ascending gases. When it reaches the raceway in front of the tuyeres, it reacts immediately with the oxygen in the hot blast air according to equation 1. The latter is actually the combination of coke combustion (equation 2) and coke gasification (equation 3, also referred to as solution loss). C + 0.5 O2 C + O2 C + CO2 C + H2O CO CO2 2 CO CO + H2 (1) (2) (3) (4)

Coke gasification occurs just outside the raceway area where gaseous oxygen is no longer available to completely combust the CO to CO 2. The net heat effect is exothermic; however, and as stated before, the endothermic water gas reaction (equation 4) allows control of the temperature in front of the tuyeres by controlling the moisture in the hot blast.

b) Melting (fusion) zone and final reduction of wustite: H2 and CO from the previous reactions rise through the burden, contact wustite (FeO) formed from previous reduction reactions in the upper part of the furnace, and reduces it to iron. CO + FeO H2 + FeO CO2 + Fe H2O + Fe (5) (6)

16

The iron absorbs carbon through contact with the coke, and melts owing to its decreased melting point. Equations 3 and 4 combine with equations 5 and 6 in a cycle which effectively regenerates CO. Owing to the highly endothermic nature of equation 3, the gases cool as they rise in the furnace.

c) Thermal reserve zone: Once the gases have cooled to about 925 oC, the thermodynamics for equation 3 are no longer favorable. Because the predominant reaction is now equation 5 which is slightly exothermic, and because the mildly endothermic equation 6 occurs to a much lesser extent, the gases do not cool appreciably, resulting in a thermal reserve zone. The net relative amounts of CO 2 and H2O produced by reduction are determined by equilibrium of the water gas reaction.

d) Reduction of hematite to wustite (upper shaft): Only slight amounts of CO or H 2 are required to reduce hematite to wustite. CO + Fe2O3 H2 + Fe2O3 CO2 + 2 FeO H2O + 2 FeO (7) (8)

Moreover, calcination and magnesium carbonate decomposition (from the flux) takes place in this zone: CaCO3 MgCO3 CaO + CO2 MgO + CO2 (9) (10)

In this zone, the gas temperature falls off rapidly because of cooling by the incoming materials, evaporation of moisture, and the net endothermic nature of the above reactions.

17

In addition to the principal reactions discussed, several others are also important, including: Fluxing of the sulfur into the slag, S + CaO + C CaS + CO (11)

Reduction of other metallic oxides, MnO + C SiO2 + C P2O5 + 5 C Mn + CO Si + 2 CO 2 P + 5 CO (12) (13) (14)

Equations 1013 result from contact between hot metal and slag, where the produced manganese, silicon, and phosphorus are dissolved into the hot metal. [1]

2.3.8 The Challenge of Coal Injection

Despite that the new technologies have already started competing with the blast furnace; experts believe that blast furnace will remain the principal method for ironmaking. This is essentially because of the developments that have taken place over the years in the technology, and engineering aspects.
[25]

However, experts also see that the blast furnace would only be competitive on the long run in case of increasing the coal usage, and decreasing the dependence on coke.
[5]

This trend has really started all over the world, and
[26]

coke rates of 300 kg/THM (Ton Hot Metal) with 190-200 kg/THM of coal injection have already been achieved. The coal injection is adopted till the

maximum possible extent ensuring stable operation of the furnace. However, still the coke is the dominant fuel in the blast furnace, and this is one of its main drawbacks.

18

2.3.9 Environmental Analysis for the Blast Furnace Technology

The blast furnace route for steel production is always criticized for its bad environmental impacts, and there are increased pressures on it from the environmental associations. The pollutants are mainly generated from the sintering and coking plants. 2.3.9.1 Sintering Plant Pollutants Emissions from the sintering process arise primarily from materialshandling operations, which result in airborne dust, and from the combustion reaction on the traveling grate. Combustion gases from the latter source contain CO, CO2, SOx, NOx, volatile organic compounds (VOCs), dioxins and furans, and oily mill scale. Iron sintering has been identified as a source of polychlorinated dibenzoparadioxins (PCDD) and polychlorinated

dibenzofurans (PCDF). Combustion gases are most often cleaned in electrostatic precipitators (ESPs), which significantly reduce dust emissions but have minimal effect on the gaseous emissions. There are no appreciable wastewater streams in the sintering plant. [27] 2.3.9.2 Coking Plant Pollutants The coke oven is a major source of fugitive air emissions. Table 2.3 shows the approximate amounts of emissions resulting for every ton of coke produced if there is no vapor recovery system.
3 Table

2.3Approximate amounts of emissions resulting for every ton of coke produced in the absence of vapor recovery system [21] Pollutant Particulate matter (PM) SOx NOx Ammonia VOCs Amount produced in kg per ton of coke 0.7 to 7.4 0.2 to 6.5 1.4 0.1 3 (including 2 kg of benzene)

19

Table 2.4 shows the approximate wastewater concentration resulting from the coking plant. PAH stands for polycyclic aromatic hydrocarbons.
4 Table

2.4Approximate wastewater concentration resulting from the coking

plant

[21]

Pollutant BOD5 COD TSS Benzene Phenol Ammonia Cyanide PAH

Concentration in mg/lit 1000 1500 1600 200 10 150-2000 0.1-2 0.1-0.6 30

2.3.9.3 Blast Furnace Pollutants As mentioned above, blast furnace gas is scrubbed before being used as a fuel. The wastewater stream from the scrubbing process contains iron oxide and carbon particulates. Moreover, it also contains ammonia and cyanide which were absorbed from the gases.
[1]

Another source of pollution occurs during tapping the blast furnace where appreciable amount of dust emerges. Finally, when the blast furnace gas is used as a fuel, SOx and NOx result from the combustion. 2.3.9.4 Greenhouse Gas Emissions for the Whole Industry The blast furnace route followed by the basic oxygen furnace (BOF) used for steelmaking results in emissions of about 1 ton of CO2 per ton of steel. Thus, the industry is one of the largest contributors to greenhouse gas emissions. Unfortunately, currently there is no economic substitute for the reductant and energy requirements of the industry. So the only choice to reduce these emissions is to improve the energy efficiency of the existing plants and processes.
[1]

20

2.3.10 Drawbacks of the Blast Furnace

Despite being the predominant technology for iron production, and despite being modified all the over the years, the blast furnace route for iron production suffers from a lot of disadvantages that enabled the new technologies to compete with it. The drawbacks of the blast furnace can be summarized in the following points: The capital cost of a conventional integrated iron and steelmaking complex is very high, and very large new plants are required to assure profit. This investment is difficult to be afforded by the private investors. On the other hand, mini-mills can produce quality products at competitive cost at a much smaller scale. Thus, this option is more attractive to the nowadays investors. [2] The inherent dependence of the process on the scarce coking coal. [5] Any reduction in production rate results in a negative effect on the metal quality, both in terms of chemistry and temperature. [4] Since all the different unit operations takes place in a single reactor, there are no means of ascertaining the efficiencies of individual process steps taking place in the blast furnace. [5]

Extremely high negative environmental impacts. [2]

2.4 General Overview on Direct Reduction

Direct reduction (DR) includes many processes in which iron ore in the form of lump or pellets is reduced in the solid state by either solid or gaseous reducing agents. Reformed natural gas or non-coking coal is generally used as the reductant. [5] In the DR processes, the final product is solid. So, the gangue won't be separated from the iron product as was the case in blast furnace.

21

Consequently, and as DRI retains the chemical purity of the iron ore from which it is produced, the iron ore should be very low in residual elements such as copper, chrome, tin, nickel, and molybdenum. Direct reduced iron (DRI) can be produced in pellet, lump, or briquette form as DRI retains the shape and form of the iron oxide material fed to the DR process. [1]

2.4.1 Metallization
Metallization is defined as the percent of total iron in the DRI which has been converted to metallic iron. For example, DRI having a total iron content of 90% and a metallic iron content of 77% has 85.5% metallization. 100

% =

DRI normally should at least have 85% metallization. Processes producing solid <85% metallized, are classified as prereduction processes. The partially reduced product, called prereduced iron, is not acceptable for steelmaking but can be used as a feed for iron smelting.

2.4.2 Use of DRI in Electric Arc Furnaces (EAF)

As stated before, the world is currently witnessing a gradual shift from integrated steel plants (using the blast furnace for iron production followed by basic oxygen furnace for steel production) to mini-mills. The latter mainly use electric arc furnace (EAF) for steelmaking. EAF has the advantages of lower investment costs and better flexibility towards the raw materials.
[29] [28]

EAF-based plants currently represent about one third of global steelmaking capacity, and will systematically increase in the future. Over 95% of the worlds DRI production is consumed in electric arc furnace steelmaking. The desired portion of DRI used in the EAF charge depends on economics, the type of steel being produced, and the available scrap quality. [1]

22

2.4.3 DRI Oxidation and Briquetting

The removal of oxygen from the iron oxide during direct reduction leaves voids. Thus, DRI (also called sponge iron) tends to have very small size of grains, lower apparent density, greater porosity, and more specific surface area than iron ore. [30] Thus, DRI is subjected to oxidation during transportation. In general, oxidation of DRI takes place in 2 forms: Reoxidation and Corrosion. [31] Reoxidation occurs when the metallic iron in hot DRI reacts with oxygen in the air to form either Fe 3O4 or Fe2O3. On the other hand, corrosion occurs when the metallic iron in DRI is wetted with fresh or saltwater and reacts with oxygen from air to form rust, Fe(OH) 3. Small amounts of hydrogen may be generated when DRI reacts with water. if it is stored in closed environment.
[1]

This can form an explosive mixture

[29]

Moreover, DRI saturated with water

can cause steam explosions if it is batch charged into an electric arc furnace. Hot briquetting was found to be the best method for preventing reoxidation of DRI. When DRI is hot briquetted, it is called HBI. HBI is produced by molding hot (700 oC) DRI into pillow-shaped briquettes using roll press. HBI is almost twice as dense as non-briquetted DRI and it has substantially less surface area, which makes it 100 times more resistant to reoxidation. 2.7 shows the difference between the HBI and Pellet DRI.
[1]

Figure

7 Figure

2.7 HBI and Pellet DRI

23

2.4.4 Broad Classification of DR Processes

DR Processes are mainly classified according to the type of reductant used: Reformed Natural gas, or non-coking coal. Table 2.5 shows a comparison between gas-based and coal-based DR processes.
5Table 2.5 Comparison between gas -based and coal-based DR processes Parameter Reaction Kinetics Temperatures Needed Product's Purity Energy Consumption Raw Materials [30] Capital Cost [32] Gas-Based Faster Lower Higher Lower Natural Gas and Pellets Higher Coal-Based Slower Higher Lower Higher Non-coking coal and Lump ore Lower

2.4.5 Global DRI Production

As stated before, the blast furnace share in ironmaking decreases with time. Figure 2.8 shows the growth of DRI production globally from 1975 to 2007.
[30]

. Midrex shown in the figure is the most dominant DRI production

technology, and it will be well-discussed in the following section.

8 Figure 2.8 Growth of global DRI production from 1975 to 2007

24

2.5 Gas-Based DR Processes

In 2008, 75% of the DRI production was from the gas-based processes.
[34] [33]

In the gas based processes, the reduction of iron oxide is carried out by a mixture of CO and H 2 at a temperature of about 750-950C. technologies for gas-based DR will be discussed below. The main

2.5.1 MIDREX Process

Surface Combustion Division of Midland-Ross Corporation developed the Midrex Process. In the mid-1960s the Midrex division became a part of famous German Korf Industries. The first commercial Midrex plant was installed near Portland Oregon in USA and started production in 1969. By 1983, more than twenty Midrex modules were installed having a total capacity of about 9 million metric ton per year. 2.5.1.1 Main Reactions Taking Place Reforming: CH4 + H2O CH4 + CO2 Iron Ore Reduction: H2 + Fe2O3 CO + Fe2O3 H2 + FeO CO + FeO 2.5.1.2 Process Description As shown in figure 2.9, reducing process gas enters the reducing furnace through a bustle pipe and ports located at the bottom of the reduction zone. The reducing gas flows counter currently to the descending solids.
[34] [34]

CO + 3 H2 2 CO + 2 H2 H2O + 2 FeO CO2 + 2 FeO H2O + Fe CO2 + Fe

(1) (2)

(3) (4) (5) (6)

The

latter may be lump ore or pellets; however, pellets are preferred owing to their

25

superior physicochemical characteristics.

[35]

Iron oxide reduction takes place

according to the reduction reactions above. The partially spent reducing top gas, containing about 70% carbon monoxide plus hydrogen, flow from an outlet pipe located near the top of the DRI furnace into the top gas scrubber where it is cooled and scrubbed to remove the dust particles. The largest portion (about two third) of the top gas is recompressed, enriched with natural gas, preheated to about 400 oC and piped into the reformer tubes. In the catalyst tubes, the gas mixture is purified to form carbon monoxide and hydrogen according to the reforming reactions (1 & 2) above. The hot reformed gas (over 900 oC) which is about 95% carbon monoxide plus hydrogen is then recycled to the DRI furnace. The balance top gas (about one third) provides fuel for the burner in the reformer. Hot flue gas from the reformer is used to reheat combustion air for the reformer burners and also to preheat the process gas before reforming. This has decreased the energy consumption to about 11.5 million kilojoules per metric ton of DRI. Cooling gases flow countercurrent to the burden in the cooling zone of shaft furnace. The gas then leaves at the top of the cooling zone and flow through the cooling gas scrubber. The cleaned and cooled gas is compressed, passed through a demister, and is recycled to the cooling zone.
[34]

When incorporating hot briquetting in the MIDREX process, the cooling gas circuit is eliminated, and the hot DRI is continuously discharged from the shaft furnace into a hopper and directly fed into a hot briquetting machine.

26

9Figure 2.9 Flow sheet of MIDREX process for DRI production

2.5.2 HYL III Process

The HYL-III process was developed by Hylsa steel company in Mexico in 1980. It was a modification to the original batch HYL process. However, in the HYL III process, a single shaft furnace with a moving bed is used in place of the four original fixed bed reactors. The reactions taking place are the same stated in MIDREX process. [34] 2.5.2.1 Process Description The HYL III process is similar to the MIDREX process, however, it uses a conventional steam reformer and pressurized shaft furnace. As shown in figure 2.10, fresh reducing gas is generated by reforming natural gas with steam. The natural gas is preheated in the reformer's stack, desulfurized to less than 1 ppm sulfur. It is then mixed with superheated steam, further preheated to 620 oC in the reformer's stack, and then reformed in alloy tubes filled with nickel-based catalyst at a temperature of 830oC. The reformed gas is quenched to remove water vapor, mixed with clean recycled top gas from the shaft furnace, reheated to 925oC in an indirect fired heater, and injected into the shaft furnace. For high (above 92%) metallization a CO2 removal unit is added in

27

the top gas recycle line in order to upgrade the quality of the recycled top gas and reducing gas. [1] 2.5.2.2 Some Process Features The process can utilize high sulfur feed natural gas since it is equipped with sulfur removal step. Utilizing a CO2 removal circuit (typically PSA) in the circulating gas system results in more positive control for the CO to H2 ratio in the reducing gas. This allows controlling the % metallization of DRI The higher gas pressure system reduces the tendency for bed fluidization, and thus permits higher capacity. [16]

10Figure 2.10 Flow sheet of HYL III process for DRI production

2.5.3 ENERGIRON Process

For more than 50 years, HYL (now Tenova HYL) has developed technologies designed to improve
[36]

steelmaking

competitiveness

and

productivity for steel facilities.

ENERGIRON is the innovative HYL direct

28

reduction technology jointly developed by two premier companies Tenova and Danieli. [37] 2.5.3.1 Main Reactions Taking Place There are 3 sources for generating reducing gases in this scheme; selfreforming in the furnace, feeding natural gas as make-up to the reducing gas circuit, and injecting oxygen at the furnace's inlet.

Reforming and Oxidation: CH4 + H2O CO2 + H2 CH4 + 0.5 O2 2 H2 + O2 CO + 3 H2 CO + H2O CO + 2 H2 2 H2O (1) (2) (3) (4)

Iron Ore Reduction: Reactions from 3 to 6 shown above in the MIDREX process 2.5.3.2 Process Description As shown in figure 2.11, the natural gas stream is mixed with the reducing gas recycle stream from the CO 2 removal system. The reducing gas stream is passed through the gas heater where it is heated up to 930 oC. The reducing gas temperature is further increased up to about 1020oC after the partial combustion with oxygen before the furnace. The rest of the process is the same as HYL III.

29

Since all reducing gases are generated in the reduction section, utilizing the catalytic effect of the metallic iron inside the furnace, an external reducing gas reformer is not required. This is called zero-reformer process (ZR). The basic scheme can also use the conventional steam-natural gas reforming and other reducing agents such as hydrogen, gases from coal gasification, petroleum coke and similar fossil fuels and coke-oven gas. [36]

11Figure 2.11 Flow sheet of ENERGIRON process for DRI production

2.5.3.3 Some Process Features HYTEMP system allows the immediate transportation of hot DRI emerging from the furnace to the EAF by the means of pneumatic transport system. The ENERGIRON process can process high sulfur iron ores as the sulfur is eliminated along with the CO2 in the CO2 absorption system, which is part of the reduction circuit. [36]

30

2.6 Coal-Based DR Processes

In 2008, 25% of the DRI production was from the coal-based processes.
[33]

Despite not being a big percentage, the share of coal-based processes in DRI production is gradually increasing. This may be attributed to the high global reserves of coal which exceeds the natural gas as shown in figure 2.12.

12Figure 2.12 Global energy reserves

Moreover, experts are sure that on the long run coal will continue to be less expensive and its price will be more stable than other forms of energy.
[23]

In coal-based processes, rotary kilns are used as the reducing reactor. The main differences in the individual processes are related to the control system especially for temperature.
[30]

2.6.1 General Process Description of Rotary Kiln Technologies

In all coal-based DR processes, lump ore or pellets (or both) together with coarse fraction of non-coking coal are fed to the inlet end of the rotary kiln. The size ranges of lump ore, pellets, and non-coking coal are respectively 4-20 mm, 9-20 mm, and 6-20 mm. This coal is referred to as co-current coal, and it acts as a reducing agent, and as a major heat supplier to the kiln. A finer

31

fraction of coal (-6 mm) is also injected from the discharge end of the kiln using primary air as the carrier gas. This coal is called countercurrent coal, and it helps in completing the reduction, and supplying heat. A fluxing material like limestone or dolomite should also be added in order to control the sulfur pick up by the reduced materials from the coal ash. The flux is mainly in fine form (-4 mm), and is added with the countercurrent coal. In these processes, optimizing the temperature of the bed charge is crucial. At the inlet end, the temperature should be high enough so that the reduction reactions proceed rapidly. On the other hand, the temperature should be low enough to prevent the fusion of the coal ash. This is achieved by conserving a balance between the solid-bed temperature, and the temperature in the atmosphere above the bed (normally at least 100-150oC higher).
[30]

This is

mainly achieved by burning combustibles released from the bed using secondary air. The latter is blown by fans through burner tube space uniformly along the length of the kiln.
[34]

The product from the kiln is mainly a mixture of DRI and char. The product's temperature is about 950-1000oC, and it is cooled in an indirectly water-cooled rotary cooler to about 120 oC. After that, the DRI is separated from the coal char using magnetic separators, and finally screening is performed. The separated char is mainly recycled as a feed material. Waste gases leaving the kiln at the inlet end pass through a dust chamber and a post-combustion chamber, before being cooled and cleaned in electrostatic precipitators, scrubbers, or bag filters. Alternatively, the clean kiln gases can be used in waste heat boilers to utilize the sensible heat in producing steam.
[5]

Figure 2.13 shows a schematic representation of DRI

[30]

production in rotary kilns.

32

13 Figure

2.13 A schematic representation of DRI production in rotary kilns

2.6.2 Encountered Reactions during coal-based DR Processes

The main reactions that take place within the rotary kiln are the frequent reduction reactions. CO + Fe2O3 CO + FeO CO2 + 2 FeO CO2 + Fe (1) (2)

Reaction 2 takes place in the last 30% of the kiln's length.

The carbon monoxide results from combustion of coal in the presence of controlled amounts of air C + 0.5 O2 CO (3)

The produced carbon dioxide resulting from the reduction reacts quickly with the carbon present in coal to produce carbon monoxide according to the famous boudouard reaction

33

C + CO2

2 CO

(4)

This cycle continues to maintain the reducing conditions prevailing in the kiln. Moreover, coal pyrolysis takes place inside the kiln, where volatiles tend to evolve till about 600 oC. However, it is to be noted that most of these volatiles don't have real contribution to the actual process of reduction. Part of these volatiles is being combusted by the secondary air injected to the kiln. This combustion transfers heat to the charge directly by radiation, and also by conduction from the kiln lining. [16]

2.6.3 Comparison between Different Rotary Kiln DR Processes in Commercial Use

The coal-based DR processes are similar to great extent. The main industrially applied processes are SL/RN, Codir, DRC, Jindal, and SIIL. The main differences between them are in the tolerable size of raw materials, and energy consumption. However, it worth noting that SL/RN process is the mother of all the other coal-based DR processes, and it is the most widely applied. [30]

2.6.4 Advantages of Rotary Kiln Processes

Rotary Kiln can effectively mix the solid charge as it undergoes simultaneous heating and reduction. Intimate mixing of the charge helps in diluting CO2 formed around the iron ore particles, and this helps the reduction reactions to proceed. Since large freeboard space is available above the solid charge in any kiln, the gas phase can tolerate the presence of heavily dust-laden gases. In gasbased processes, generation of dust can lead to channeling. Rotary kilns are commercially proven, and there is a lot of operating experiences with it especially in cement industry.

34

 The temperature of iron oxide reduction is much lower than that of blast furnace (1000oC against 1300-1600oC). As a result, less energy is required for reduction. [30]

2.6.5 Disadvantages of Rotary Kiln Processes

The productivity is very low compared to shaft furnaces in gas-based DR processes. In the latter, yield is up to 5 times more than the rotary kilns for the same inner volume. Thus, for large capacity plants, multiple rotary kilns are needed. The reactor rotates at 0.4-0.5 rpm which makes it difficult to incorporate process control and quality control systems. Moreover, the engineering of such kilns is difficult. The fact of cooling the product in order to perform magnetic separation is a huge source of energy losses. Thus, these processes exhibit very low energy efficiency. Because of the repeated fall and rise of the charge during rotation, the solids undergo size degradation. Thus, the coarser particles tend to float on the top of the charge, and the fines tend to settle at the bottom, and thereby increasing the tendency of adhering to refractory lining. The latter gives rise to ring formation. Once rings are formed, uniform movement of the charge becomes difficult, and shutdown of the kiln becomes a must. [30]

2.7 Smelting Reduction

As stated before, smelting reduction (SR) is the third route of ironmaking after the blast furnace, and direct reduction. Smelting reduction produces pig iron like the blast furnace; however, it has different features. The gradual world shift from the integrated steel plants using the blast furnace basic

35

oxygen furnace route to smaller mini-mills essentially based on EAF was the main driving force for research and development in the field of SR.
[35]

2.7.1 Advantages of SR with respect to Blast Furnace

SR processes use non-coking coal as fuel and reductant instead of the scarce coal used in blast furnace. SR processes are viable at lower production capacities, and this copes with the gradual world shift from the integrated steel plants to smaller mini-mills essentially based on EAF. SR processes are more environmentally friendly compared to blast furnace. Some SR processes use un-agglomerated ore over 8 mm in size as the ferrous feedstock. This wasn't possible in blast furnace.
[38]

In SR, the same phenomena taking place in the blast furnace occurs; however, they can take place separately in 2 or 3 units, and this assures better process control.
[5] [39]

In SR, the dependence on pure oxygen instead of air prevents the formation of cyanides.

2.7.2 Advantages of SR with respect to DR

SR processes are characterized by operating at high temperatures so as to produce molten iron. These high temperatures ensure faster rates of reaction, and prevention of sticking problems associated with solid state reactions in DR Processes. Having liquid phase in the reactor ensures increased transport rates owing to convection, and remarkable increase in the conversion rate because of the higher contact area resulting from the dispersed nature of phases. Another advantage is the lower energy consumption when used in EAF (This is discussed in the next section).
[5]

36

2.7.3 Use of Hot Metal in Electric Arc Furnaces (EAF)

In mini-mills, DRI or hot metal (HM) can be used as scrap substitutes in EAF. As shown in figure 2.14, charging of HM as a scrap substitute leads to great decrease in energy consumption, whereas, DRI causes slight increase.
[5]

14Figure 2.14 Effect of different scrap substitutes on EAF energy consumption

2.7.4 General Features of SR

Figure 2.15 shows a schematic diagram of SR processes. The phenomena taking place in the blast furnace are mainly divided on 2 stages. Moreover, the reactants aren't introduced together. Thermal non-coking coal is used as a fuel and reductant instead of coke. As stated before, liquid phase formation helps in having higher reaction rates. The SR processes are characterized by reduction of molten FeO by CO. It has been concluded that the controlling step for this reaction is mass transfer. The overall reaction rate is proportional to the square root of the gas flow rate. Therefore, for SR processes, one of the objectives is to increase the amount of gas available for reduction. This will be mainly achieved by increasing the amount of used coal.
[35]

Post combustion mainly refers to the

37

secondary oxygen or air introduced in the process for combusting volatiles for heat production and volatiles cracking.

15Figure 2.15 Schematic representation of SR technology

2.7.5 Reaction Encountered in SR Processes

2.7.5.1 Reactions Encountered in Pre-reduction Stage Iron Ore Reduction: H2 + Fe2O3 CO + Fe2O3 H2 + FeO CO + FeO H2O + 2 FeO CO2 + 2 FeO H2O + Fe CO2 + Fe (1) (2) (3) (4)

Carburization: 3 Fe + 2 CO 3 Fe + CO + H2 Fe 3C + CO 2 Fe3C + H2 O (5) (6)

38

2.7.5.2 Reactions Encountered in Smelting Stage C + 0.5 O2 C + O2 C + CO2 C + H2O 2 H2 + O2 CO + H2O H2 + Fe2O3 CO + Fe2O3 H2 + FeO CO + FeO C in HM + FeO in slag CO + FeO in slag
[39]

CO CO2 2 CO CO + H2 2 H2O CO2 + H2 H2O + 2 FeO CO2 + 2 FeO H2O + Fe CO2 + Fe Fe in HM + CO Fe in HM + CO 2

(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12)

In addition, pyrolysis of coal, volatiles decomposition, and evaporation of moisture takes place.

2.7.6 COREX Process

Among the newly developed SR processes, COREX is the leader both in terms of capacity and number of plants using this technology.
[39]

COREX

produces a high quality HM using non-coking coal and pure oxygen in an environmentally-friendly process. 2.7.6.1 History of COREX The COREX process is a technology developed by Voest Alpine, Austria (Now Siemens VAI) and Korf Engineering, Germany. The success achieved in the early experiments led to the commissioning of a pilot plant at Kehl in Germany in 1981 with a capacity of 60,000 tpa. The pilot plant was operated

39

for six years, during which various grades of different iron ore forms as well as different types of coal were tested. Successful performance of the pilot plant encouraged the process developers to set up a commercial unit. It was felt that a maximum scale up factor of 5 will be successful. Thus, a COREX unit was installed in 1988 in South Africa in Iscor's Pretoria Works with a capacity of 300, 000 tpa. 2.7.6.2 COREX Process Description As shown in figure 2.16, the COREX process is based upon a reduction shaft for iron ore reduction, and a melter-gasifier for coal gasification and iron melting. In the reduction shaft, the iron oxide feed is in the form of lump ore or pellets. As in blast furnace, the reduction gas (originated from the meltergasifier as will be shown below) moves counter-currently to the descending burden. In the reduction shaft, about 75-95% metallization is achieved. The off-gases are cleaned and then used as high caloric export gas. The solid product from the reduction shaft is discharged via screw conveyors, and transported via feed legs into the melter-gasifier. [16] In the melter-gasifier, the pre-reduced iron is further heated and melted to separate iron from slag. Hot metal is tapped at a temperature of approximately 1400-1500oC in a manner similar to the blast furnace. Inside the meltergasifier, the non-coking coal is introduced at room temperature, and it is dried and devolatilized along the reactor. In the bottom, it is combusted using pure oxygen in order to generate carbon monoxide essential for reduction. The evolved coal volatiles are cracked in the top of the reactor, and thus huge environmental problems are prevented. The reducing gases exit the meltergasifier at about 1000-1100oC. They are cooled to 800-900oC, dedusted in a hot dust cyclone, and conveyed back to the reduction shaft.
[39] [39]

40

16

Figure 2.16 Flow Sheet of COREX process for HM Production

2.7.6.3 Commercial Production Currently, 4 plants are utilizing COREX process for pig iron production. These plants are Saldanha Steel Works in South Africa (0.8 mtpa), Jindal South West Steel in India (2 * 0.8 mtpa), Posco in Korea (0.8 mtpa), and Baosteel in China (1.2 mtpa).

2.7.7 FINEX Process

As shown in figure 2.17, FINEX is an SR process that uses ore fines in a series of fluidized bed reactors for initial pre-reduction followed by a meltergasifier to produce pig iron.
[35]

Since 1992, Siemens VAI and the Korean steel producer Posco have been jointly developing the FINEX process.
[40]

The objective of the process was

mainly utilizing the ore and coal fines generated during processing of the feed required by the COREX unit in Posco.
[35]

A commercial unit of 1.5 mtpa at

[41]

Pohang, Korea was commissioned in 2007 and is in operation since then. This is the only operating FINEX process till now.

41

The generated FINEX export gas is a highly valuable product and can be further used for DRI/HBI production, electric energy generation or heating purposes. The hot metal and slag produced in the melter-gasifier is frequently tapped from the hearth as in blast furnace or COREX process. [40]

17

Figure 2.17 Flow Sheet of FINEX process for HM Production

2.8 COREX Process for Pig Iron Production

As this thesis deals with optimization and modeling of COREX process, the following section aims to zoom into the process from different view points.

2.8.1 Detailed Process Description

As mentioned previously, COREX consists of 2 reactors, the reduction shaft and the melter-gasifier. The reduction shaft (RS) is placed above the meltergasifier (MG). The process operates at high pressure of about 3.5 bar which ensures lowering the dimensions, and having high conversions for the different reactions especially in the absence of nitrogen because of using pure oxygen.

42

2.8.1.1 RS Process Description Iron ore, pellets and additives (limestone and dolomite) are continuously charged into RS via lock hopper system located on the top of the shaft. Some amount of coke is also added to the shaft to avoid clustering of the burden inside the shaft due to sticking of ore/pellets and to maintain adequate bed permeability. The reduction gas is injected through the bustle located about 5 meters above the bottom of the shaft at about 850 oC and over 3-bar pressure. The gas moves in the counter current direction to the top of the shaft and exits from the shaft at around 250 oC. Percentage metallization ranges from 75% to 95%, and the solid product is termed as DRI. Subsequently, six screws discharge the DRI from the RS into the MG. 2.8.1.2 MG Process Description As shown in figure 2.18, the MG can be divided into 3 main reaction zones namely: Gaseous free board zone (Dome), moving bed (middle part above oxygen tuyeres) also called char bed, and fluidized bed (in the transition area between the moving bed and the free board zone). The Hearth zone which is the lower part below oxygen tuyeres can also be considered as the fourth zone. The hot DRI at around 600-800oC along with partially calcined limestone and dolomite are continuously fed into the MG through DRI down pipes. The DRI down pipes are uniformly distributed along the circumference near the top of the melter-gasifier so as to ensure uniform distribution of material over the char bed. Additionally non-coking coal, iron ore fines, flux fines and some coke are continuously charged by means of lock hopper system. Oxygen plays a vital role in COREX process for generation of heat and reduction gases. It is injected through the tuyeres, which gasifies the coal char generating CO. The hot gases ascend upward through the char bed.
[42]

It is to
[39]

be noted that the gas velocity in the lower part of the gasifier is adjusted to maintain a stable fluidized bed before the secondary oxygen injection. The

43

sensible heat of the gases is transferred to the char bed, which is utilized for melting iron and slag and other metallurgical reactions. The hot metal and slag are collected in the hearth and tapped in a manner similar to the blast furnace. The dome temperature is maintained between 1000oC to 1100 oC, and this assures cracking of all the volatile matter released from the coal. The gas generated inside the MG contains fine dust particles, which are separated in hot gas cyclones. The dust collected in the cyclones is recycled back to the MG through the dust burners, where the dust is combusted with secondary oxygen. There are four of these dust burners located around the circumference of the melter-gasifier above the char bed. The gas from the MG is cooled to the reduction gas temperature (850 oC) through the addition of cooling gas. A major part of this gas is subsequently fed to the RS. The excess gas is used to control the plant pressure. This excess gas and the RS top gas are mixed and termed as COREX export gas. [42]

18Figure 2.18 Zones in the Melter -Gasifier

2.8.2 Dimensions of the Encountered Reactors

COREX process can operate economically at small module sizes. Figure 2.19 shows the different modules currently available for the process. C-1000 stands for 1000 tpd, C-2000 stands for 2000 tpd, and similarly C-3000 stands for 3000 tpd.

44

19 Figure 2.19 Different modules available for the reactors of COREX process

The hearth diameter in the melter gasifier is the main dimension that characterizes the reactor as shown in figure 2.19. As C-2000 is the module used in most of the operating plants, it is important to know more about its dimensions. As shown in figure 2.18, the free board is the dome shaped zone inside the melter gasifier. Its diameter is about 14 meters, and its height is about 8 meters. The whole melter gasifiers height is about 22 meters.

2.8.3 COREX Export Gas

Unless export gas is well-utilized, the process won't be cheaper than the blast furnace route.
[35]

Large volumes of export gas are generated from the process-

typically 1650 1700 Nm3/THM. The gas mainly consists of CO, H2, CO2, and small amounts of CH4. The export gas can be utilized in heating purposes in a steel

45

plant (in rolling mills), power generation (as shown in figure 2.20 a), the production of oxygen used in MG (as shown in figure 2.20 a), synthesis gas in the chemical industry, reductant to produce DRI in any gas-based DR processes (as shown in figure 2.20 b), and finally can be used internally in the process as reducing gas after CO2 removal. The latter results in appreciable reduction in the consumption of coal and oxygen (as shown in figure 2.21). [39]

20Figure 2.20 Export gas from 3000 tpd COREX plant used in: a) combined cycle power plant (th: thermal, el: electrical) and b) DRI production

21

Figure 2.21 In-Process utilization of COREX export gas

46

2.8.4 Raw Material Requirements for COREX Process

To achieve reliable operation, there are specifications for the different raw materials to be used in COREX process. 2.8.4.1 General Requirements Table 2.6 summarizes the preferred and tolerable grain size, and some chemical properties of the raw materials used in COREX process.
6Table 2.6 Raw materials requirements for COREX process Specification Coal a) % Volatile Matter b) % Ash c) % Sulfur d) Grain size, mm Lump Ore a) Fe% b) Grain size, mm Pellets a) Fe% b) Grain size, mm Sinter a) Fe% b) Grain size, mm Limestone, dolomite Grain size, mm Limestone, dolomite fines Grain size, mm 4 - 10 8 16 50 - 55 10 - 30 45 - 50 (min.) 6 - 45 62 - 65 8 - 16 58 (min.) 6 - 30 62 - 65 8 - 20 55 (min.) 6 - 30 20 - 30 (Water free) 5 - 12 (Water free) 0.4 - 0.6 5 - 40 (50% should be +10) 15 - 36 (Water free) 10 - 25 (Water free) 0.5 - 1.5 Preferred Tolerable

47

2.8.4.2 COREX Insensitivity to Alkali Content One of the most attractive features of COREX is its insensitivity to the alkali content of the raw materials, so there is no buildup of alkalis as is the case in the blast furnace. Since pure oxygen is used, no cyanides are formed at the tuyere level, rather K 2CO3 and Na2CO3 vapors are formed from the reaction with CO 2. These vapors are non toxic and are discharged via the cooling gas scrubbers at the same input quantity. Moreover, if some alkali dust emerges from the MG, the water used in the scrubbers dissolve them, and thereby prevents accumulation.
[5]

2.8.4.3 Use of Coke in COREX Process Despite announcing in the beginning that COREX can operate totally without coke, the actual practice has shown that coke quantities in the operating plants are in the range of approximately 2-10 % of the coal charge. Whereas POSCO plant in South Korea showed that it is possible to operate the COREX plant at zero coke for long periods (coke consumption in total 1999 was in average 19 kg/t HM) by a careful operation and treatment of the raw materials. However, SALDANHA plant of South Africa and JINDAL plant of India could not reach that. Another important aspect has to be taken into account regarding to the required coke quality: In case coke is charged to the COREX plant, only low quality coke is required. Consequently, coke can be seen as an "additive" for the process as to the most extent thermal coal is directly used. Moreover, coke will be of minor economic impact.
[43]

2.8.5 Factors Affecting the Efficiency of COREX Process

In the reduction shaft, the metallization degree of the DRI and the calcination of the additives are strongly dependent on the following parameters: [42]

48

Amount and quality of the reduction gas flow Temperature of the reduction gas Reducibility of the iron bearing burden Average particle size and the distribution of the solids charged

The efficiency of the whole process depends on the following parameters:

Size and chemical analysis of the raw materials especially the coal % Metallization of the DRI in the RS Optimum distribution of oxygen between the tuyeres and dust burners Permeability of the char bed

2.8.6 Environmental Analysis for COREX Process

The elimination of coke-making operations and sintering has made COREX process a very environmentally friendly process. The latter is one of the most salient features for this process. Table 2.7 shows the differences between the gaseous emissions and aqueous effluents between a modern blast furnace, and an operating COREX unit.
[5]

It is apparent that COREX is a very clean

technology with respect to the blast furnace.

7Table 2.7 Comparison between pollutants emerging from a blast furnace and a COREX unit Blast Furnace 1) Aqueous Effluents in mg/THM 590 80 60 20 50 0-1 7 1 COREX Process

a) Ammonia b) Phenol c) Sulphide d) Cyanide

49

2) Gaseous Emissions in mg/THM a) NOx b) SOx c) Dust 1900 1600 427 21 26 39

Table 2.8 compares the sulfur input and output balance in blast furnace and COREX unit located in the same facility.
[44]

It is apparent that despite that

COREX can sustain an input amount of sulfur twice as high as a blast furnace, the sulfur content in the HM is similar to that of blast furnace. This is because during the gasification of coal in the MG, sulfur is converted predominantly to H2S. Moreover, small amount of SOx is formed by the combustion of H 2S with the oxygen in the dust burner region. The above H2S and SOx along with reducing gases enter the RS where the following reactions take place: CaO + H2S (Ca,Mg)O + H 2S 4 CaO + 4 SO2 CaS + H2O (Ca, Mg)S + H 2O 3 CaSO4 + CaS

Through these reactions, sulfur is captured in the calcined additives and then is fed into the MG and finally dissolves into the molten-slag phase. [45]
8Table 2.8 Comparison between sulfur balance in a blast furnace and a COREX unit Sulfur input / output 1) Inputs in kg sulfur/THM a) Ore 0.15 2.6 2.75 0.035 4.682 4.717 Blast Furnace COREX Process

b) Fuel

Total

50

2) Outputs in kg sulfur/THM a) Slag b) HM c) Sludge/ Dust Total 2.42 0.18 0.15 2.75 4.051 0.19 0.476 4.717

2.8.7 Advantages of COREX Process

COREX process holds a lot of advantages, and this is why more than one steel plant in the world uses this process in ironmaking. This is also why this process is nearly the only competent to the blast furnace in the field of pig iron production. The advantages can be summarized in the following points: The dependence on thermal coal instead of coke allows conserving of the scarce coking coal. [39] The process is viable at lower production capacities, and this copes with the gradual world shift from the integrated steel plants to smaller mini-mills essentially based on EAF. [38] The process is very environmentally friendly (as proved above). The raw material requirement is not as stringent as in blast furnace, and despite that the quality of the produced hot metal is not affected. [46] Insensitivity to the alkali contents of the raw materials. [5] Correction of hot metal and slag composition is easier and faster in COREX than in blast furnace as additions can be made through the melter-gasifier. The calorific value of COREX gas is 2.6 - .27 times higher than that of blast furnace. The start of the COREX furnace is easier after a shut down, and can reach the rated capacity in one hour.

51

 Specific melting capacity of COREX is about twice that of the blast furnace. [46] The cost advantage of COREX process with respect to the blast furnace (after utilizing the export gas) varies from 10-20%. It is 10% at POSCO in South Korea, and 19% at Jindal in India. [39] COREX is suitable for two different steelmaking routes, the EAF route at Saldanha Steel, South Africa, and the basic oxygen furnace (BOF) route at Jindal, India. [4] COREX is suitable for mini-mills and integrated steel plants. [5]

2.8.8 Disadvantages of COREX Process

Beside the various advantages of COREX, the process has also some drawbacks which can be summarized in the following points: The process can only have a maximum of 15.5% ore fines in the charge. High volatile coals can't be used directly, and they must be blended with low volatile ones. The process won't be economically viable if the export gas isn't well utilized. [41]

2.8.9 Case Study Jindal

Jindal Vijayanagar Steel Limited (JVSL) is a great example of COREX process success. The company started its integrated steel operation in 1999, based on COREX with a capacity of 0.8 mtpa. After success of the first Corex unit, JVSL added the second module in 2001. After that, the company further increased the production capacity to 3.8 mtpa by the commissioning of 2 blast furnaces. Thus, the company utilizes the advantages of both COREX and the blast furnace in a great synergetic way.
[46]

52

2.8.9.1 COREX Export Gas The export gas from both COREX units is used in the generation of electrical energy in two adjacent power plants each of 130 MW capacity, as well as for the production of pellets in a pelletising plant of 3 mtpa. About 50% of these pellets is processed in COREX plants, while the rest is sold to third parties. Using 70% pellets instead of 100 % lump ore increased the metal output. [5] During the decision making process of installing COREX modules in the company, it was deduced that buying electricity from the state grid would have meant paying Rs 4.32 per unit. On the other hand, generating power from a COREX unit cost only Rs 2.60 per unit. This meant power costs reduced by almost 40 per cent. On the other hand, and during the decision making process of increasing the production capacity, it was deduced that there will be surplus amount of export gas if COREX is to be applied. Since no feasible application was found for this surplus gas, the decision was to use blast furnace instead. The chief executive officer of JVSL says that setting up a plant using COREX involves an assumption that theres an assured buyer for the excess power produ ced. This shows that the decision of returning back to blast furnace doesn't necessarily mean that blast furnace is better than COREX. [47] 2.8.9.2 Using Iron Ore Fines Undersized iron ore (size 6-12 mm) is being charged directly into the COREX MG. It was realized that the surplus heat available in the free board could be utilized for reduction of iron ore fines. Addition of fines via the coal line increases the hot metal productivity, generates extra reduction gas for the shaft and helps in controlling the process parameters more uniformly. On a monthly average basis, maximum 15.5% of the total iron bearing material has been substituted by iron ore fines addition.
[42]

53

2.8.9.3 Recycling of various by products and plant wastes The drive towards reduction in hot metal price has prompted JVSL to adopt innovative measures for recycling of various by products and plant wastes. Some of these are the use of BOF Slag, mill scale, and Limestone and Dolomite fines. [42] 2.8.9.4 Improvement in Plant Operation Through continuous research, and by gaining more operating experiences, the plant's performance was greatly enhanced as shown in Table 2.9.
9Table 2.9 Progress of COREX performance in JVSL Year 1999-2000 2000-2001 2001-2002 2002 - 2003 2003-2004 Production, mtpa 0.4 0.77 1.52 1.46 1.36 Fuel Consumption, kg / THM 1163 1071 1082 1041 1000 Hot Metal Temperature, oC 1491 1503 1497 1497 1487 % S in HM 0.06 0.037 0.037 0.029 0.027
[42]

2.8.9.5 Synergetic Combination of COREX and Blast Furnace JVSL has initiated a great engineering trend of having both COREX and blast furnace operating in one integrated steel plant. The synergy of COREX and blast furnace has helped JVSL to maximize the utilization of solid waste and thereby reduced production cost of pig iron. As shown in figure 2.22, the non-coking coal used in COREX is screened so that the lump coal is fed to COREX, and the coal fines (- 6 mm) are fed to the blast furnace as pulverized coal injection. Moreover, out of the total coke produced, the lump coke is fed to the blast furnace, nut coke (6-25 mm) is fed to COREX, and the coke breeze (-6 mm) is fed to the sinter plant.

54

More than 70% of the plant wastes such as flux fines, mill scale, and BOF slag are recycled into COREX either directly or indirectly through the pellet and sinter plants. Moreover, the COREX export gas is used as a backup in the blast furnace stoves, boilers, and in sinter and pellet plant. [48]

22

Figure 2.22 Synergy of COREX and Blast Furnace

2.8.10 Case Study SALDANHA

An Integrated Compact Mill, based on a COREX C-2000 (2000 tpd) unit in combination with a COREX gas based direct reduction (DR) plant, was started-up in 1999 at SALDANHA STEEL, South Africa. Export gas from the COREX plant is used for the production of DRI in an adjacent plant using a MIDREX shaft furnace and LINDE Vacuum Pressure Swing Absorption plant (VPSA) for the removal of CO 2. The DR plant is operated with a mixture of about 65 % lump ore and 35 % pellets.

55

The COREX plant is operated with mainly local iron ores comprising lump ore (80 - 100%), pellets (0 - 20%) and local coal. All of the required additives are also supplied locally.
[43]

2.9 COREX Macroscopic Analysis

Because of having a multi-component multi-phase system, the macroscopic analysis is very important to reach better understanding of the process, and assess the effect of different process parameters.

2.9.1 Reduction Shaft Macroscopic Analysis

The most important parameter is the permeability of the burden inside the shaft. Despite having better strength than lump, the particle size of pellets decreases along the shaft because of attrition, and reaction. The cold crushing strength (CCS) is the parameter which measures the pellets' strength. As this parameter decreases, the pellets crumble and decrease the bed permeability, and consequently pressure drop increases. The latter will cause channeling, and low metallization. Statistical analysis has been used to study this phenomenon, and the following curve results.
[49]

23 Figure 2.23 Influence of CCS on the reduction shaft's pressure drop

56

2.9.2 Melter-Gasifier Macroscopic Analysis

Most of the research focus on the MG as it is the place where coal pyrolysis, and combustion takes place. Moreover, it is the place where the products are tapped. 2.9.2.1 Effect of Coal Size A decrease in the mean particle size of the coal decreases the permeability of the bed causing gas channeling and high pressure drop as shown in figure 2.24.
[49]

Moreover, the undersize coal combusts faster, and thus a proportion

of the combustion heat is not fully used in melting; however, it raises the dome's temperature. This results in increasing the fuel rate and raising the silicon percentage in hot metal. particle size is 20-22 mm. [49]
[50]

It was deduced that the optimum mean

24Figure 2.24 Influence of the mean particle size on the melter-gasifier's pressure drop

2.9.2.2 Fuel Rate Kumar et al. developed a regression analysis using multiple variables to get an equation for the fuel rate (coal + coke) in COREX process
[49]

= 1712 8.1 + 12.1 1.28 + 0.21 + 2.45 + 1.1 (4.1 )

57

Where FR is the fuel rate (kg/THM), MR is melting rate (t/h), Moist is %age moisture in coal, Metln is %age metallization, SR is slag rate (kg/THM), US is %age undersize coal (-6 mm), VM is %age volatiles in coal, and CCSR is coal char strength after reaction. CCSR is an important factor in characterizing coal, and it determines to great extent the amount of coke needed. 2.9.2.3 Factors Affecting Coke Addition Heat stability is also an important index of coal for COREX process optimization. Usually the higher the value, the better the process as high stability coal can decrease coke consumption in the MG.
[51] [49]

The heat stability is measured by putting one kilogram of coal having a grain size between 5 and 15 mm into a drying oven. The oven is heated to 1100oC where the coal will be maintained in the furnace for 0 .5 h without air. After that, the coal is taken out and screened using 6 mm screen. RW+6 is the percentage of coal bigger than 6 mm obtained after this process.
[51] [52]

For high

heat stability of smelting coal, its RW+6 reaches 98%, and this value can theoretically cancel the addition of coke to the process. In another study, Kumar et al. have conducted a statistical analysis of daily plant performance data using more than 500 points, and the following regression equation was the result:
[53]

= 409.3 + 13.56 0.11 + 0.21 3.08 5.15 23 4.18 (1.14 )

Where Mcoke is the %age moisture in coke, MR is the melting rate in t/h, SR is the slag rate in kg/THM, CSR is the char strength after reaction of the coal blend, PAl2O3 and PMgO are respectively the percentage of Al 2O3 and MgO in the slag, and P m is the percentage metallization from the reduction shaft.
[53]

58

Another study has discussed this issue from another point of view, where 2 factors for the used thermal coal will be able to assess the amount of coke to be added. These 2 factors are char strength after reaction (CSR) and char reactivity index (CRI). Their significance can be explained as follows: During coal descent in the fixed bed, char is gasified with CO 2, where CO is produced from the famous Boudouard reaction. If this occurs quickly in the char bed, carbon consumption will increase leading to uneven gas distribution and poor heat balance of the char bed.
[54]

The quick consumption can be attributed to low particle size of char (CSR), and high char reactivity (CRI). It is apparent from figure 2.25 that with increasing CSR the coke rate decreases. Thus, CSR of char above 45 and CRI below 30% are recommended. [53]

25Figure 2.25 Effect of coal's CSR on coke rate

2.9.2.4 Effect of amount of volatile matter in coal If the coal volatile matter is low (below 26%) as seen from figure 2.26, the gases generated from such coal would be insufficient for carrying out the reduction of iron bearing materials in the shaft (< 1800 Nm3/THM). On the other hand, if volatile matter is high, it would increase the heat demand inside the MG dome and cause problems such as high fuel rate and more tarry material like CH 4 would be greater than 2% as shown in figure 2.27. High amount of tarry material creates problem in the gas cleaning system.
[53]

59

26 Figure 2.26 Effect of coal's VM on reduction gas and fuel rate

27 Figure 2.27 Effect of coal's VM on % CH 4 in the reduction gas

2.9.2.5 Effect of Moisture As coal's moisture increases, fuel rate increases, oxygen used increases, and high reduction gas flow rate results. 1% increase in moisture may increase about 10 kg Carbon per THM. the dry fuel rate.
[53]

Figure 2.28 shows the effect of moisture on

60

28

Figure 2.28 Effect of coal's moisture on the dry fuel rate

2.9.2.6 Minimization of Energy Consumption To minimize energy consumption, amount of gases produced in the MG should be the same amount needed in the RS. It was found that metallization of 85-95% is optimum for minimized energy consumption. 2.9.2.7 Effect of %MgO and %Al2O3 on the slag Experiments have proved that the viscosity of slag decreases with increasing level of MgO. Thus, when Al2O3in slag is to be increased to reduce slag rate (but also tends to increase viscosity), MgO in slag needs to be increased to counter balance this effect.
[55] [51]

The following figures also show that increasing

[53]

% MgO in the slag tends to reduce the slag rate and fuel rate.

29

Figure 2.29 Effect of %MgO and % Al 2 O 3 on the slag rate

61

30Figure 2.30 Effect of %MgO and % Al 2 O 3 on the dry fuel rate

2.9.2.8 Modeling of COREX process for optimization of operational parameters Kumar et al. have conducted one of the most important studies to build a macroscopic model able to predict the changes taking place on altering any of the input variables. A complex mass and energy balance model has been developed as illustrated in figure 2.31. The model has been validated for slag rate and %age CO in the generator gas.
[56]

31Figure 2.31 Block diagram showing a macroscopic model for COREX

62

2.10 COREX Microscopic Analysis

Due to the enclosed process and the limitations of measuring instruments, it is difficult to directly study the different velocity, temperature and composition profiles inside the process.
[57]

Thus, to reach the previous

objective, some microscopic modeling attempts were found in the literature for both the RS and MG.

2.10.1 Reduction Shaft Microscopic Analysis

A two-dimensional mathematical model was developed to describe iron oxides reduction in the reduction shaft. Combined with mass, momentum and heat transfers between gas and solid phases in steady state, the model calculates and demonstrates the basic characteristics of the shaft furnace, such as velocity, pressure, temperature fields of relevant phases and species mass fraction distributions. It was proved that the reduction from magnetite (Fe 3O4) to wustite (FeO) occupies most part of the furnace, and the reduction degree of burden located near wall is comparatively higher than that close to center. The model has also been applied to determine the influences of down pipe gas on reduction behaviors. When flowing toward the center from DRI down pipe, the high temperature reducing gas brings more energy along the pathway, thus helping to increase the reduction reaction rate and enhance DRI average metallization level.
[57]

2.10.2 Melter-Gasifier Microscopic Analysis

Lee et al. have developed the first model for the MG. The model was onedimensional (1-D), and mainly focused on coal pyrolysis.
[38]

Following, was

another publication by Lee et al. where they developed the model to study the effect of operational parameters like the bed height, C/O ratio, top pressure, and steam injection on the process performance.
[58]

63

The

previous

model

has

assumed

that

combustion

took

place

instantaneously at the tuyere plane (zero-dimensional model was assumed for the tuyere region). This reduces the combustion-zone height to zero. In real case, the combustion zone will be quite large, since pure oxygen is used for combustion. Thereby, the simplifying assumption ignores one of the important aspects of the process. The model further assumed that the ore and flux are nonreactive and gases in the free board are in equilibrium. However, their results show general agreement with the plant data for the temperature of the HM and composition and temperature of the top gas.
[38]

In the most recent model, Pal et al. have modified the modeling of the tuyere level by using two dimensional (2-D) modeling of the combustion zone. The 2-D zone extends from the tuyere region to 0.5 m above that, and the remaining part is 1-D as shown in figure 2.32. Partial equilibrium was assumed for the free board, and preheating of solids through this zone was neglected. The calculated temperature of the HM, the top gas, and the chemistry of the top gas agree with the reported plant data. The model has been used to study the effects of bed height, injection of impure O 2, coal chemistry, and reactivity on the process performance.
[59]

32Figure 2.32 Schematic diagram of the computational domains in the MG

64

References
1. Kirk-Othmer Encyclopedia of Chemical Technology : John Wiley & Sons Inc. 2. 1999 Gasification Technologies Conference. San Francisco, california : 1999, Developments in Ironmaking opportunities for power generation. 3. The Iron Blast Furnace A Study in Chemical Thermodynamics. R.S. Treptow, L. Jean: Journal of Chemical Education, 1998, Vol. 75. 4. A. K. Jouhari, R. K. Galgali, Vibhuti N. Misra.Smelting Reduction for ironmaking: Allied Publishers, 2002. 5. A. Chatterjee, B. Pandey.Metallics for Steelmaking: Production and Use: Allied Publishers, 2001. 6. Roy P. Hudson. The Blast furnace: Chemical Publishing Co., Inc Brooklyn, N.Y, USA, 1942 7. W. T. Lankford, Jr. and co-workers.The Making, Shaping, and Treating of Steel, 10th ed. Pittsburgh : Association of Iron ans Steel Engineers, 1985. 8. A. Andersson. A Study on Selected Hot-Metal and Slag Components for Improved Blast Furnace Control. Licentiate Thesis. Stockholm, 2003. 9. Al Bahareya Oasis, Egypt : Al Gadeeda Mine. 10. Gupta.Theory And Laboratory Experiments In Ferrous Metallurgy : PHI Learning Pvt. Ltd., 2010. 11. Influence of Iron Ore Fines Feed Size on Microstructure, Productivity and Quality of Iron Ore Sinter. T. UMADEVI, A. BRAHMACHARYULU, A.K. ROY, P. C. MAHAPATRA, M. PRABHU and M. RANJAN. 6, India : ISIJ International, 2011, Vol. 51. 12. B. G. Ellis, C. E. Loo and D. Witchard: Ironmaking Steelmaking, 2007, Vol. 34. 13. T. Maeda, C. Fukumoto, T. Matsumara, K. Nishioka and M. Shimizu: ISIJ International, 2005, Vol. 45. 14. K.Hofstadler.Dioxin at Sinter Plants and Electric Arc Furnaces- Emission profiles and removal efficiency. sterreich : Institut fr Verfahrenstechnik des Industriellen Umweltschutzes, 2003. 15. G. R. Bashforth. The Manufacture of Iron and Steel, Volume 1. London : Chapman & Hall, 1948. 16. L.Greene. Ironmaking Process Alternatives Screening Study, Volume 2. USA : Department of Energy, 2000. 17. Helwan, Egypt : Egyptian Iron and Steel Company, 2009.

65

18. Blast furnace gas cleaning systems. A. Lajtonyi, D. Corus, London : MILLENNIUM STEEL, 2006. 19. H.U. Ross. Solid Fuels and Reductants for the Beneficiation and Reduction of Iron Ores. [book auth.] R. R. Rogers. Iron Ore Reduction: Pergamon Press, 1962. 20. F.Woodard. Industrial Waste Treatment Handbook. USA : ButterworthHeinemann, 2001. 21. Pollution Prevention and Abatement Handbook: World Bank Group, 1998. 22. J.H. Strassburger. Blast furnace-theory and practice, Volume 2 : Taylor & Francis, 1969. 23. A. Chatterjee. Beyond the Blast Furnace : CRC Press, 1993. 24. Blast Furnace Reactions. E.T. TURKDOGAN: METALLURGICAL TRANSACTIONS B, 1978, Vol. 9B. 25. Meeting of the IISI Technical Committee. S. Inaba. 1995. 26. Coal Injection into Blast Furnace in Western Europe. Scunthrope : British Steel. 27. Environmental Code of Practice for Integrated Seel Mills - CEPA 1999 Code of Practice. Canada : Public Works and Government Services, 2001. 28. Technologies for cost reduction in EAFs. B.V.R.Raja, N.Pal, P.L.Talwar, N.P.Jayaswal Alloy Steels Plant, Steel Authority of India Ltd. : Steelworld, 2005. 29. R. Leszczynski. http://www.bancosta.it/. [Online] May 9, 2007. 30. A. Chatterjee. Sponge Iron Production By Direct Reduction Of Iron Oxide: PHI Learning Pvt. Ltd., 2010. 31. J. A. Lepinski, D. C. Meissner, and T. J. Coyne: Steel Times, 1981. 32. Energiron Technology Flexibility For Adapting to Indian Conditions: Micro-Module and Gas Alternatives: Danieli & C.; HYL Technologies, 2007. 33. Statistics, 2008 World Direct Reduction. www.midrex.com. [Online] March 2009. 34. J. M. Mauskar. Comprehensive Industry Documents Series, Spone Iron Industry. Delhi : CENTRAL POLLUTION CONTROL BOARD, Ministry of Environment & Forests, Govt. of India, 2007. 35. A.Chatterjee, and A.Ghosh. Ironmaking And Steelmaking: Theory And Practice: PHI Learning Pvt. Ltd., 2008. 36. ENERGIRON Direct Reduction Technology - Economical, Flexible, Environmentally Friendly. P.E. Duarte, Rosario, Argentina : www.tenovagroup.com, 2007.

66

37. Innovative DR Technology for Innovative Steelmaking. T. Scarnati, Cairo-Egypt : MB North African Steel Conference, 2008. 38. A Development of Computer Model for Simulating the Transport Phenomenain COREX Melter-gasifier. S.C. LEE, M. K. SHIN, S. JOO, and J.K. YOON: ISIJ International,, 1999, Vol. 39. 39. A. Chatterjee. Hot Metal Production By Smelting Reduction Of Iron Oxide. New Delhi : PHI Learning Pvt. Ltd., 2010. 40. Competence in IronMaking. www.siemens-vai.com. [Online] 2007. 41. New Ironmaking Processes: Relevance to India., B. B. Agrawal and A S. Mathur, Ranchi, India : R & D Centre for Iron & Steel. Steel Authority of India Ltd., 2011. 42. S .K. Gupta. Corex Process - One of the dynamic routes for gel making with special reference to the success of JVSL. Kolkata : Joint Plant Committee (JPC), 2005. 43. K. Wieder, C. Bohm, and J .Wurn. VOEST ALPINE Industrieanlagenbau GmBH & Co (VAI).The COREX and FINEX Processes - reliable, environmental friendly and economical Hot Metal Production . Kolkata : Joint Plant Committee (JPC), 2005. 44. Internal Report. South Korea : POSCO, 1999. 45. Energy and Pollutants Reducing Technologies in New IronMaking Processes at POSCO. l.O. LEE, M.K. SHIN, M.CHO, H.G. KIM and H.G. LEE: ISIJ International, 2002, Vol. 42. 46. Operating experiences with Corex and blast furnace at JSW steel Ltd. P. Prachethan Kumar, P.K. Gupta, and M. Ranjan : Ironmaking & Steelmaking, 2008, Vol. 35. 47. G. Shukla & M. Kapur. Blast From the Past. [book auth.] Meenakshi RadhakrishnanSwami. Stratagem: cases on retail, products, services, and trends: Tata McGraw-Hill Education, 2007. 48. Paper 32. D. Gupta & T. K.Naha, Linz, Austria : Siemsns-VAI, 2006. 49. Raw materials for Corex and their influence on furnace performance. P. P. Kumar, S.C. Barman; B.M. Reddy; V.R. Sekhar: Ironmaking & Steelmaking, 2009, Vol. 36. 50. P.P. Kumar, A. V. R. P. Dasu, M. Ranjan and T. K. Naha. : Ironmaking & Steelmaking, 2008, Vol. 35. 51. Optimisation of COREX Process. P. S. Assis, L. Guo, J. Fang, T. R. Mankhand, and C. F. C. de Assis: Ironmaking & Steelmaking, 2008, Vol. 35. 52. Study on heat stability measuring method for industrial briquette. Z.Y.Pi. Beijing : Coal Technology/National Coal Quality Supervision Test Center, 2003, Vol. 31.

67

53. Factors Affecting fuel rate in Corex process. P. P. Kumar, D. Gupta, T. K. Naha and S. S. Gupta : Ironmaking & Steelmaking, 2006, Vol. 33. 54. Paper 20. J. K. Tandon, M. K. Mitra, R. Singh and D. Gupta. Beijing, China : Proc. Asia Steel Int. Conf., 2000. 55. S.Kim. Seo: Metallurgical Transcations, 1990, Vol. 30. 56. Modelling of Corex process for optimisation of operational parameters. P. P. Kumar, L. M. Garg, and S. S. Gupta : Ironmaking and Steelmaking, 2006, Vol. 33. 57. Basic Characteristics of the Shaft Furnace of COREX Smelting Reduction Process Based on Iron Oxides Reduction Simulation. W.U. Shengli, X.U. Jian, Y. Shidong, Q. ZHOU and L. ZHANG: ISIJ International, 2010, Vol. 50. 58. The Effects of Operational Parameters on the Transport Phenomena in COREX Melter Gasifier. S.C. LEE, M.K. SHIN, J. Sangahoon, and J.K. YOON: ISIJ International, 2000, Vol. 40. 59. Mathematical Model of COREX Melter Gasifier: Part I. Steady-State Model. S. PAL and A. K. LAHIRI: METALLURGICAL AND MATERIALS TRANSACTIONS B, 2003, Vol. 34. 60. COAL PYROLYSIS: EXPERIMENTS, KINETIC RATES AND MECHANISMS. P. R. SOLOMON, M.A. SERIO and E.M. SUUBERG. Great Britain : Prog. Energy Combust., 1992, Vol. 18. 61. K. Clark. Thermal Drying and Binderless Briquetting of Sub-bituminous Coals. Sydney, Australia : Binderless (Coal) Briquetting Company Pty Limited. 62. Silicon distribution between blast furnace slag and hot metal. M. Meraikib: Ironmaking & Steelmaking, 2000, Vol. 27. 63. Carburization rate into solid iron at CO-CO2 atmosphere. X. Zhang, R. Takahashi, T. Akiyama, J. Yagi: ISIJ, 1997, Vol. 83. 64. RETROSPECT ON TECHNOLOGY INNOVATIONS IN FERROUS PYROMETALLURGY. E.T. TURKDOGAN: CANADIAN METALLURGICAL QUARTERLY, 2001, Vol. 40. 65. E.T. Turkdogan, G.J.W. Kor and R.J. Fruehan : Ironmaking & Steelmaking, 1980, Vol. 7. 66. A Numerical Study on the Combustion of a Low Temperature Carbonized Semi-coke Particle. T. MORl, K. MIYAUCHI, Y.MAENO, H. AOKI and T. MIURA : ISIJ International, 1999, Vol. 39. 67. PERRYS' CHEMICAL ENGINEERS HANDBOOK, 8TH EDITION : McGraw-Hill, 2008. 68. P. PATNAIK & S.K. DUMPAWAR. AN ATTEMPT AT OPTIMIZING THE FLOW CHARACTERISTICS OF BLAST FURNACE SLAG BY INVESTIGATION WITH SLAG

68

OBTAINED FROM BLAST FURNACE OF ROURKELA STEEL PLANT, SAIL: Department of Metallurgical and Materials Engineering, Rourkela, 2010. 69. The thermodynamic properties of slags . J. W. Matousek: JOM Journal of the Minerals, Metals and Materials Society, 2008, Vol. 60. 70. http://webbook.nist.gov/chemistry/. [Online] [Cited: 7 22, 2011.] 71. S.C. Saxena: Prog. Energy Combust. Sci., 1990, Vol. 16. 72. F.E. Ndaji, I.M. Butterfield, K.M. Thomas: Fuel, 1997, Vol. 76. 73. Experimental and modelling of the thermal regions of activity during pyrolysis of bituminous coals. V. Strezov, J.A. Lucas , L. Strezov: Journal of Analytical and Applied Pyrolysis, 2004, Vol. 71. 74. Y. Yun, E.M. Suuberg: Fuel, 1993, Vol. 72. 75. A.J. Lopez-Peinado, P.J.J. Tromp, J.A. Moulijn: Fuel, 1989, Vol. 68. 76. Glass, H.D.: Fuel, 1955, Vol. 34. 77. N. Berkowitz, W. den Hertog: Fuel, 1962, Vol. 41. 78. Joo, et al. Method for injecting fine iron ore in smelting reducing process, 1997. 79. Trust Fund on Iron Ore Information, Iron Ore Market. Geneva : United Nations Conference on Trade and Development, 2009. 80. Board, CDM Executive.Use of waste gas use for electricity generation at JSW Energy Limited. PROJECT DESIGN DOCUMENT FORM (CDM-PDD). Karnataka : UNFCC, 2006. 81. http://www.oreteam.com/pricing.php?id=7852&l1=chL1_5&l2=chL2_16&l3=chL3_73&day=22 &month=7&year=2011. [Online] [Cited: 7 23, 2011.] 82. Cairo : Egyptian International Company for Petroleum Services Technology, 2011. 83. W.E. Ranz and W.R.Marshall: Chem. Eng. Progr, 1951, Vol. 48. 84. J, M. Coulson, J. F. Richardson, J. R. Backhurst and J. H. Marker.Coulson & Richardson's Chemical Engineering, Volume 1, Sixth edition. Oxford : Butterworth Heinemann, 1999. 85. N.N. Viswanathan, Ph.D. Thesis. Bangalore, India : Indian Institute of Science, 1997. 86. Muchi, J. Yagi: Trans. Iron Steel Inst. Jpn., 1970, Vol. 10. 87. Blast Furnace Phenomena and Modelling. New York : ISIJ, 1987.

69

88. I. Muchi: Trans. Iron Steel Inst. Jpn., 1967, Vol. 7. 89. M. Kunugi, H. Jinno, and H. Torii: J. Chem. Soc. Jpn., Ind. Chem. , 1953, Vol. 56. 90. Effect of Tuyere Blocking on Melter Gasifier Performance. S. PAL and A. K. LAHIRI: ISIJ International, 2006, Vol. 46. 91. The Modeling of Hematite Reduction with Hydrogen Plus Carbon Monoxide Mixtures Part I. The Behavior of Single Pellets. Q. T. TSAY, W. H. RAY and J. SZEKELY: AlChE Journal, 1976, Vol. 22. 92. J.M. Smith, H. C. Van Ness, M. M. Abbott.INTRODUCTION TO CHEMICAL ENGINEERING THERMODYNAMICS, Sixth Edition. New York : McGraw-Hill, 2001. 93. A. Kobayashi and M. Steinberg.THE THERMAL DECOMPOSITION OF METHANE IN A TUBULAR REACTOR. New York : Brookhaven National Laboratory, Department of Applied Science, 1992. 94. J.I. Morell and N.R. Amundson: Chem. Eng. Sci., 1990, Vol. 45. 95. Comparison of dolomite decomposition kinetics with related carbonates and the effect of procedural variables on its kinetic parameters. M. Samtani, D. Dollimore, K.S. Alexander : Thermochimica Acta, 2002. 96. J. Sestak, G. Berggren: Thermochim. Acta, 1971, Vol. 3. 97. Approximate modelling of coal pyrolysis. E. Donskoi, D.L.S. McElwain. Australia : Fuel, 1999, Vol. 78. 98. Smoot. L. D. and Smith, P. J.Pulverized-Coal Combustion and Gasification. New York : Plenum Press, 1979. 99. M. L. Radulovic, P. T.and Smoot, L. D.Hobbs: AIChE, 1992, Vol. 38. 100. K. Levy. Edward, N. Sarunac, and W. Zhang.USE OF COAL DRYING TO REDUCE WATER CONSUMED IN PULVERIZED COAL POWER PLANTS. Bethlehem, Pennsylvania : Energy Research Center, Lehigh University, 2004. 101. W.L. Mccabe, J.C. Smith, and P. Harriott.Unit Operations Of Chemical Engineering, Fifth Edition. New York : McGraw-Hill, 1993. 102. R.E. Treybal. Mass-Transfer Operations, Third Edition. New York : McGraw-Hill, 1981. 103. Direct Analogy Between Mass and Heat Transfer to Beds of Spheres . A. S. Gupta, and G. Thodos: AIChE, 1963, Vol. 9. 104. D.J. Gunn: Int. J. Heat Mass Transfer, 1978, Vol. 21.

70