CHAPTER TWO LITERATURE REVIEW ON IRONMAKING

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 welldescribed. The industrially proven smelting reduction processes

arepresented/explained.

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 direct smelting 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.
Table 2.1 Principal Iron Bearing Materials Parameter Hematite Magnetite Goethite (Limonite) Chemical Name Ferric Oxide FerrousFerric Oxide Chemical Formula Iron, wt% Color 69.94 Steel gray to red 72.36 Dark gray to black 62.85 Yellow or brown to nearly black 48.2 White to greenish gray to black Crystal Structure Specific Gravity 5.24 5.18 3.3-4.3 3.83-3.88 4.72 4.955.1 Hexagonal Cubic Orthorhombic Hexagonal Hexagonal Cubic 36.8 Ironblack 46.55 Pale brassyellow Fe2O3 Fe3O4 HFeO2 FeCO3 Hydrous Iron Oxide Iron Carbonate IronTitanium Oxide FeTiO3 FeS2 Iron Sulfide
[7]

Siderite

Ilmenite

Pyrite

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. Moreover, Magnetite is denser than other ores, thus it is
2

considered a resistance to the reducing gases. Thus, most of the reduction takes place by the solid carbon. The latter causes higher time needed for complete reduction. To treat this, high fuel consumption is needed. [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 is to be used. Thus, direct reduction technologies have big constraints on the purity of iron ore. The following table shows the composition 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 minesgreatly differ from each other. It is also apparent that the iron percentage in the Egyptian mine is low, and thus it isnt a suitable raw material for the production of DRI.
Table 2.2 Iron Ore composition from 2 different mines Composition Fe Al2O3 CaO K2 O MgO MnO Na2O P2O5 S SiO2 TiO2 Swedish Ore[8] 66.74 0.25 0.47 0.035 1.45 0.085 0.041 0.021 0.0005 2 0.195
3

Egyptian Ore[9] 58 2 0.7 0.3 0.02 3.5 0.3 0.2 0.1 8 0.02

V2O5 BaO

0.21 1.5

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. Iron ores can be also classified as manganiferous, siliceous, high-Phosphorous, lowphosphorous, etc. [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. 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. 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 grinded and cleaned. [10] The ground ore is mixed with the proper amount of water and binder, normally bentonite, hydrated lime, or organic material, and then is rolled into small balls 915 mm in diameter in a balling drum or disk. These green (wet) pellets are dried, then are heated to 1200 1375oC to bond the small particles, and finally are 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
4

a rotary kiln (grate kiln). The traveling grate and grate kiln are the most commonly used pelletizing processes.[1]

Figure 2.1 Iron Ore Pellets

Figure 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 cokefines on a traveling grate to produce a clinker-like aggregate (sinter) suitable for use in
5

the blast furnace. The iron-bearing fines can include iron ore fines, flue dust, or other steel mill wastes. 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 Depot

Discharge Water

Water Treatment

Slag Immobilisation

Figure 2.3 Flow Sheet of Iron Ore Sintering [ 1 4 ]

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, blast furnace is a steel reactor standing approximately the height of a 10-story building. It has a refractory brick lining to enable it to withstand the intense heat generated within. As shown in Figure 2.5, 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. The charge consists of alternating loads of coke and a mixtureof iron bearing materials (iron ore, pellets, sinter) and flux (mainly limestone, and dolomite).[3] These solids form a column that descends through the furnace with a total residence time of about eight hours. [15] 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 by the process, and to provide reducing gases that removes oxygen from the ore.
[16]

The reducing gases rapidly ascend through the column and are
[3]

expelled through a pair of stacks at the top in less than 20 seconds.

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.

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.

Figure 2.4 Blast Furnace

Figure 2.5 Double Bell System Used in Blast Furnaces

2.3.2 Blast Furnace Tapping

In the terminology of blast furnace, getting the hot metal and slag from the furnaces bottom is called tapping. As stated before, tapping takes plac e in batches. The latter range from 3 to 5 hours. Every product has a tapholewhere the product emerges from. A taphole is built into the refractory lining of the blast furnace. To get each product, a tapping machine is used as shown in figure 2.6. The latter utilizes a tapholedrill to drill a hole through the taphole material as shown in figure 2.7. After getting the product, and to close the holes again, the same tapping

machine utilizes a mud gun is used to plug the holes with a quick-hardening clay.[1]

Figure 2.6 Tapping MachineFigure 2.7 Blast Furnace Directly After Tapping

The slags hole is about 1.4 meters above the hot metals hole. From the operating experiences, the slag is tapped before the hot metal.
[17]

As shown in figure 2.8, Hot metal is poured into refractory-lined railcars. The latter are used for transportation to the steelmaking section. Slag is either transferred as a liquid in inverted bell-shaped rail cars, or poureddirectly into a slag pit adjacent to the blast furnace. After solidification, slag have multiple uses. The slag can be crushed, sized and sold for road ballast. In addition, the slag may be granulated using a water spray to make a by-product suitable for cement industry. Finally, it can also be used for the production of rock wool insulation. [1]

10

Figure 2.8 ARailcar Used for Transporting Hot Metal to the Steelmaking Facilities

2.3.3 Blast Furnace Gas Cycle

As shown in figure 2.9, Off-gases (top gas) leave the top of the furnace through uptake pipes,reverse direction in the downcomer, and enter the dust catcher. In the latter, dust is separated from the gases. The dust is emptiedinto a rail car for transport to a sinter plant for recycle or to a landfill.

Figure 2.9 Downcomer and Dust Catcher Used in the BF Gas Cycle

11

Afterleaving 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 cleanedgas can be utilized in different ways: a)Steam generation and Power generation (as shown in figure 2.10) b) Firingsteelmaking furnaces c) Firing of coke ovens in the coke-processing nearby plant. d) Firing the blast furnacestoves. 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 ofthe blast furnace off-gas and releasing heat to the cold blast air as it passesdown through the stove.After leaving the stoves, the hot blast enters a large refractory-lined bustlepipe which distributes the air on thetuyeres.[1] Figures 2.11, 2.12, and 2.13 show the air system in the blast furnace.

Figure 2.10 Blast Furnace Gas Utilized in Power Generation

12

Figure 2.11 TuyeresAround the Blast Furnace

Figure 2.12 Large Air Pipe Connected to Tuyeres

13

Figure 2.13 Stoves Used for Preheating the Air

2.3.4 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. The heating of the coal is done in narrow, rectangular, silica brick ovens. The ovens stand in groups of 10 to 100 or more, called batteries.Many of the organicsubstances inside the coal volatize at thattemperature, leaving the coke behind. The volatilized gas is then subjected to sequentiallylower temperature direct contact condensing chambers, which capture tar (amixture of many relatively heavy organic com-pounds), oils, light oils, and finally lowmolecular-weight gases. Coke is pushed into a quenching car that transports it
14

to quenching towers. Here, the coke is sprayed with water to lower the temperature. About 35% of this water evaporates. The remaining water drains to a settling basin, where the coke fines are removed.[19] Because of the direct contact of water with the coke oven gases, wastewater streams from the coking plant contain high concentrations of ammonia, phenol, sulfides, thiocyanates, and cyanides. Moreover, airborne emissions also include SO x, NOx, ammonia, and particulate matters. [20] The process of transforming coal into coke is a very complex process which isnt fully understood. The most known theory is: The more fusible components soften, the more volatile vaporize, and the less thermally stable decompose. The decomposition of other components, with the deposition of the decomposition products within the pores of the mass contributes to the strength of the coke.
[21]

2.3.5 Iron Ore Properties (1st Raw Material)

As stated before, the ores of iron occur exclusively as its oxides where hematite is the most famous form. Iron ore is charged into the blast furnace in the form of pellets, sinter, orlump ore. Total iron content in the iron oxides normally ranges from 60 to 66%,but may be as low as 50% in low quality ores or in sinter using high quantitiesof recycled materials. The impurities that can accompany iron oxide has been previously stated in Table 2.2. Size control is important in order to guarantee appropriate bed permeability inside the blast furnace,so fines (_6 mm) should be kept less than 2%. [1]

15

2.3.6 Coke Properties (2nd Raw material)

Coke has 3 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. If coal is used instead of coke, the volatile matter inside the coal will rapidly plug the bed once being volatilized. [2]Moreover, the coke has higher mechanical strength than coal, and hence promotes stable operation. [1] The composition of coke is known by conducting proximate analysis where 4 parameters are measured: Fixed Carbon, volatiles, ash content, and moisture. Mainly Ash, phosphorous, and sulphur are the major impurities in coke.Sulphur is the most undesirable impurity in this industry. Despite being partially removed during coking, still coke can contain about 1% sulphur. [6] Size control is important in order to guarantee appropriate bed permeability, so the minimum used size is about 15 mm. [17] Through continuous research, and as an attempt to reduce the coke consumption in the blast furnace, it is customary now to see solid, liquid, or gaseous fuels, eg, coal, fuel oil, ornatural gas, may be added to the hot air blast at the tuyeres to replace some of thecoke. [1]

16

2.3.7 Flux Properties (3rd Raw Material)

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 than iron. The coke forms ash when burnt in the furnace. The ash formed is composed largely of silica and alumina like the impurities of the iron ore. Flux also reacts with coke ash. Flux also reacts with sulphur, and thereby reducesits concentration in the hot metal. Most of the sulphur originates from coke, and it has the ability to transfer from the coke to the iron product if no flux is available. All the products of the flux reactions form the slag phase which is also tapped from the blast furnace. However, high temperatures are preferred as the slag will more desulphurize iron at high temperatures. [6] Fluxes are usually added in the form of either limestone or dolomite. Thefluxes provide the basic constituents (CaO and MgO) needed to balance theacid constituents (SiO 2 and Al2O3) from the coke and ore. [1] The main flux impurities are silica, alumina, sulphur, and phosphorous. The presence these impurities will reduce the % of lime and magnesia, and this will require additional amount of flux to get rid of them. The use of impure flux material will cause the formation of more slag, which need more heat to be melted, and thus the fuel consumption increases. Mainly sulphur and phosphorous arent found in high percentages in fluxes. However, if they are high, they will be detrimental to the quality of the iron produced. Thus, in this case the use of low grade fluxing material isnt possible.[6]

17

2.3.8 Air Properties (4th Raw Material)

Air may also be considered a raw material. Over 1.5 ton of air is required to produce 1 ton of hot metal. [1] 2.3.8.1 Modifications in temperature and composition of the air The air supply to the tuyeres has been greatly modified all over the years. It was known that preheating the air will lead to less coke consumption, so it was always a research objective. Long time ago, and when the researchers first think about preheating the air, higher temperatures were really produced in the combustion zones, but it was apparent that the heat transfer to the charge wasnt rapid enough to use this heat. Consequently, the idea of preheating th e air wasnt advan tageous in this period. After more research, the researchers pointed out that this poor performance might be caused by the undesirable melting of unreduced burden materials and subsequent resolidification during reduction by solid carbon. Moreover, the use of well-sized dense ores will cause more rapid heat transfer. Between the years of 1950 to 1955, it becomes apparent to the operators that if the moisture content of the air was 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. The coke is consumed by air through combustion, and by steam through water gas reaction, and thus the rate of heat transfer and rate of reduction were improved. After further research, and as stated above, 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, and after reaching good understanding of the process, and good control on the
18

temperature in the combustion zone, 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 between 900 and 1300o C, and is mainly associated with moisture, oxygen, and auxiliary fuels. 2.3.8.2 Modifications in the blast furnace stoves As stated above, the blast furnace stoves (also known as cawpers) are used for preheating the air used in the blast furnace. They are considered regenerative heat exchangers that convert the chemical energy of the blast furnace exiting gases into sensible heat of the entering air. Before discovering how to reach high air temperatures without causing problems in the combustion zone, most blast furnaces had more stove capacity than required. However, after getting more experience, and discovering that high air moisture can lead to better utilization of high air temperatures, many operators used the highest hot blast temperature that the stoves could produce. However, this has caused a control problem. If the furnace suddenly becomes cold, they couldnt use the stoves as a control parameter. The solution to this problem was the control of the airs moisture content. So, if the furnace becomes suddenly cold, the airs moisture content was decreased and vice versa. However, the stoves always suffer from the problem of dust and alkali attack on the refractories. Some reports stated that 60% of the dust and 80% of the alkalis from the gas remain in the stove. [22]

19

2.3.9 Blast Furnace Reactions

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. Equation1, however, is actually the combination of coke combustion (equation 2) and cokegasification (equation3, 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 oxygenis no longer available to completely combust the CO to CO 2. This reaction goesessentially to completion at temperatures between 1500 to 2100oC. The net heateffect 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 moisturein the hot blast.

b) Melting (fusion) zone and final reduction of wustite:

20

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)

The iron absorbs carbon through contact with the coke, and melts owing to itsdecreased melting point. Equations 3 and4 combine with equations 5 and 6 in a cyclewhich effectively regenerates CO. Owing to the highly endothermic nature ofequation 3, the gases cool as they rise in the furnace.

c) Thermal reserve zone: Once the gases have cooled toabout 925 oC, the thermodynamics for equation 3 are no longer favorable. Becausethe predominant reaction is now equation 5 which is slightly exothermic, andbecause the mildly endothermic equation 6 occurs to a much lesser extent, thegases do not cool appreciably, resulting in a thermal reserve zone. The net relativeamounts of CO 2 and H2O produced by reduction are determined by equilibrium of the water gas reaction (Equation 4).

d) Reduction of hematite to wustite (upper shaft): Only the slightest amounts of CO or H 2 are required to reduce hematite to Wustite.

CO + Fe2O3

CO2 + FeO
21

(7)

H2 + Fe2O3

H2O + FeO

(8)

Moreover, calcination and magnesium carbonate decomposition (from the flux) takes place in this zone:

CaCO3 MgCO3

CaO + CO2 MgO + CO2

(9) (9)

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

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 (10)

Reduction of other metallic oxides, MnO + C SiO2 + C P2O5 + 5 C Mn + CO Si + 2 CO 2 P + 5 CO (11) (12) (13)

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

Finally, it is to be noted that factors affecting the rate of reactions in the blast furnace are the reactivity of the reductant (fuel), particle size of the ore
22

and the reductant, and the intimate contact between the ore and the reductant. Reactivity of the fuel is the form of the carbon which reacts faster than another at any given temperature. High reactivity of the fuel is not always necessary because of the high temperatures already available in the furnace. So, the reactions will mainly depend at the rate of transfer of oxygen. [21]

2.3.10 Role of Computerized Programs in the Blast Furnace

Inside the blast furnace, many different unit operationsoccur simultaneously including heat and mass transfer, reduction by gases, reduction by solid carbon, high temperature gas generation, and finally smelting and 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] Moreover, the packed bed created by coke in the blast furnace differ than the common packing features in the chemical engineering applications as follows: - The superficial velocities of molten slag and metal in the furnace are very low, about 0.08 mm/s, compared with those in chemical processes. - The packing material in the furnace is crushed coke while artificial packings with much higher porosity are commonly used in chemical processes. - The liquids are more than 2.5 times as heavy as the packing, coke, in the furnace while the packings are usually heavier than the liquids in chemical processes.[25]

Thus, the blast furnace is a very complex reactor which needs rigorous control in order to reach smooth operation. The accumulating experiences in operating the blast furnace have resulted in the increased dependence on computerized control. Modern furnaces rely on computerized controls for weighing and chargingthe raw materials. The ore and coke are charged in alternating
23

batches, so asto create distinct layers within the furnace which promote permeability for therising gases. Computer controls are also used for stove operation, to control deliveryof the hot air. High air temperatures are generally desirable, as thesereduce the coke rate. Control of the flame temperature in the raceway is effectedby controlled additions to the hot blast, primarily of moisture. The effect of adding auxiliary fuels should be well covered in the computerized control. Moreover, Controlling slag chemistry is crucial in operating the furnace. In general, increasing the basicity of the slag promotes sulfur removal but decreases alkali removal.
[1]

Increasing the basicity preserves the refractories,

but increases the slag's viscosity, and thus results in lower fluidity. [17] So, all these factors should be balanced by proper control on the amounts of limestone and dolomite added.

2.3.11 The Challenge of Coal Injection

Among all the ironmaking processes, the blast furnace still holds the dominant position. Despite that the new technologies have already started competing with the blast furnace; experts believe that the blast furnace will remain the principal method for iron making. This is essentially because of the developments that have taken place over the years in the technology, and the engineering aspects.
[26]

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 coke rates of 300 kg/THM (Ton Hot Metal) with 190-200 kg/THM of coal injection have already been achieved.
[27]

It is also foreseen that coal injection

of 250 280 kg / THM should be possible.

24

The coal injection is adopted till the maximum possible extent ensuring stable operation of the furnace. The important aspects of coal injection include coal quality, granulometry of coal, and influence of hot air temperature. However, still more research is needed to decrease the consumption of coke for the technology to be sustainable. The recent research trend is to increase the oxygen enrichment in the entering hot air.
[5]

2.3.12 Operational Features of Large Blast Furnaces in the World

The following table compares the size, productivity, iron ore form, and the auxiliary fuel used in different blast furnaces. The hearth diameter is equivalent to the bottom diameter.
Table 2.3 Comparison of different blast furnaces in terms of size, productivity, iron ore form, and the auxiliary fuel used [5]
Hearth Diameter, m

Country

Furnace

Productivity t/m3/d

Auxiliary Burden Form Injected Fuel Sinter Oil

Finland

Rautaruukki BF1, BF2 SSAB Trunplat BF2 Dofasco BF4 Rouge C Sidmar BF A Nisshin Kure BF1 BHP Port Kembla BF5 Wuhan BF5

7.2

3.4

Sweden Canada USA Belgium Japan

8.5 8.5 8.6 10 10.5

3.5 2.9 3.1 2.9 2.4

Pellets Pellets Pellets Sinter Sinter

Coal Oil Gas Coal Coal

Australia China

12 12.2

2.5 2

Sinter Sinter

Gas Coal

25

Hoogovens Netherlands BF7 Hoogovens BF6

13.8

2.7

Sinter + Pellets

Coal

11

2.9

Sinter + Pellets

Coal

The following table compares the top pressure, oxygen enrichment, coke rate, auxiliary fuel rate, slag rate, and hot air temperature in different blast furnaces. PCI refers to pulverized coal injection.
Table 2.4 Comparison of different blast furnaces in terms of top pressure, oxygen enrichment, coke rate, auxiliary fuel rate, slag rate, and hot air temperature [5] Posco (Korea) BF6 Hoogovens (Netherlands) BF7 2.9 Kimitusu 3 (Japan) Nippon steel (Japan)

Parameter

Productivity, t/m3/d Top Pressure, kg/cm2 % oxygen enrichment Burden Coke rate, / THM PCI rate, kg / THM Slag rate, kg / THM Blast Temperature o C kg

2.66

2.7

2.47

2.5

1.67

2.25

2.2

1.6 / 2 85% Sinter 15% Lump 390

4.9 50% Sinter 50% Pellets 339

4 50% Sinter 50% Pellets 365

2.4 93% Sinter 7% Pellets 392

100

161

125

71 (Oil)

320

236

236

286

1200

1180

1180

1278

26

Moreover, it has become customary to use the slag resulting from the steelmaking section in the blast furnace. This slag contains iron, manganese, and an excess of calcined basic oxides with a ratio of bases to acids of 2 or 3 to 1. If this slag isn't used in the blast furnace, an additional cost will be required to dispose of it. However, this slag also contains phosphorous, so the added amount of this slag is often limited by the allowable phosphorous content in the pig iron product. [22]

2.3.13 Environmental Analysis for the Blast Furnace Technology

The blast furnace route for steel production is always criticized by the experts for its bad environmental impacts. As the environmental awareness in the world is enhanced, the pressures on the blast furnace route are increased. The pollutants are mainly generated from the sintering plant, and coking plants. 2.3.13.1 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, CO 2, SOx, and NOx, together with particulate matter. The concentrations of these substances vary with the quality of the fuel and raw materials used and combustion conditions. Atmospheric emissions also include volatile organic compounds (VOCs) formed from volatile material in the coke breeze, dioxins and furans, formed from organic material under certain operating conditions, and oily mill scale.Iron sintering has been identified as a source of polychlorinated dibenzoparadioxins (PCDD) and polychlorinated dibenzofurans (PCDF).

27

Combustion gases are most often cleaned in electrostatic precipitators (ESPs), which significantly reduce dust emissions but have minimal effect on the gaseous emissions. Water scrubbers, which are sometimes used for sinter plants, may have lower particulate collection efficiency than ESPs but higher collection efficiency for gaseous emissions. Significant amounts of oil in the raw material feed may create explosive conditions in the ESP. Sinter crushing and screening emissions are usually controlled by ESPs or fabric filters. Wastewater discharges, including runoff from the materials storage areas, are treated in a wastewater treatment plant that may also be used to treat blast furnace wastewater. [28] 2.3.13.2 Coking Plant Pollutants The coke oven is a major source of fugitive air emissions. Table 2.5 shows the approximate amounts of emissions resulting for every ton of coke producedif there is no vapor recovery system. Most of these emissions are released from doors during coking and when the coke is pushed from the oven on the way to the quench tower.
[1]

Table 2.5Approximate amounts of emissions resulting for every ton of coke produced in the absence of vapor recovery system [20] 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)

As shown above in the process description of the coke processing, the plant also produces rich wastewater streams. Wastewater is generated at an average rate ranging from 0.3 to 4 cubic meters per ton of coke processed. [1] Table
28

2.6shows the approximate wastewater concentration resulting from the plant. PAH stands for polycyclic aromatic hydrocarbons.
Table 2.6Approximate wastewater concentration resulting from the coking plant [20] Pollutant BOD 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

2.3.13.3 Blast Furnace Pollutants As mentioned above, blast furnace gas is scrubbed before being used as a fuel. Thewastewater 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, SO x and NO x result from the combustion. 2.3.13.4Greenhouse Gas Emissions for the Whole Industry Generally, the largest future environmental problem facing the worlds steel industryis that of greenhouse gas emission, specifically carbon dioxide.

29

The preparationof sinter fines or pellets uses a large amount of electricity. The production of electricity is primarily based on coal and oil, whichends up as CO2 and water. The reduction of iron ore is largely based on the use ofcarbon, which ultimately ends up as CO 2. Limestone used ultimately dissociatesinto CaO and CO2. Thus, the industry produces a tremendous amount of carbondioxide. The blast furnace route followed by the basic oxygen furnace (BOF) used for steelmaking results in emission of about one ton of CO 2 per ton of steel.Thus, the industry is one of the largest contributors to greenhousegas emissions. Unfortunately, currently there is no economic substitute for thereductant and energy requirements of the industry. So the only choice to reduce these emissions is to improvethe energy efficiency of the existing plants and processes. [1]

2.3.14 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: There is continuing restructuring of the industry. In 1985, less than 50% of the steel industry was in private hands. This percentage increases gradually, resulting in increased competitive pressures. The capital cost of a conventional integrated iron and steelmaking complex is very high, and

30

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 blast furnace process on the scarce coking coal is a great disadvantage for the process.[5] Blast Furnaces are relatively inflexible in terms of output and any reduction in production 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] Coke ovens and sinter plants required for blast furnace operation are major sources of environmental pollutants, and there are currently a lot of pressures against the use of this route in iron production.[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 gasesous 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. 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.
31

Direct reduced iron (DRI) can be produced in pellet, lump, or briquette form. When produced in pellets or lumps, 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 92% and a metallic iron content of 85% has 92.4% metallization. 100

% =

Although it is theoretically possible to convert all of the iron oxide in iron ore to metallic iron, it is not economically feasible. The reduction reaction slows significantly in the last stages and low production rates would result in case of reaching complete metallization. Moreover, in practice, it is advantageous to retain a small amount of iron oxide in the DRI. During melting in an electric arc furnace (used for steelmaking), the iron oxide in DRI reacts with carbon in the DRI to form metallic iron and carbon monoxide. The carbon monoxide foams the slag during steelmaking, and this improves the operation of the electric furnace. [1] 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

32

Basic Oxygen Furnace for steel production) to mini-mills. The latter mainly use electric arc furnace (EAF) for steelmaking. With advantages of lower investment costs coupled with better flexibility towardsthe input raw materials, energy inputs and steel grade mix, the world steelproduction through EAF route is projected to touch the magic figure of 50% soon.[29] EAF-based plants currently represent about one third of global steelmaking capacity. Theirshare has been growing at 5% year on year, and will systematically increase in the future, asnearly all new steel production outside China is through the EAF process. [30] Over 95% of the world s DRI production is consumed in electric arc furnace steelmaking. The primary use of DRI is as a clean supplement or replacement for the ferrousscrap charge in EAF.The desired portion of DRI used in the EAF charge depends on economics, thetype of steel being produced, and the available scrap quality.[1]

2.4.3 Use of DRI in Blast Furnace

DRI can be added to the blast furnace burden to increase furnace productivity and reduce coke requirements. It can be used for short-term increases in blast furnace output when a facility is short of hot metal during times of high steel demand, or when one of several blast furnaces is down for maintenance.[1]

2.4.4 DRI Oxidation

The removal of oxygen from the iron oxide during direct reduction leaves voids, giving the DRI a spongy appearance when viewed through a microscope as shown in figure 2.14. This is why DRI is also called sponge iron. The latter is characterized by having very small size of grains.
[31]

Thus, DRI in these

33

forms tends to have lower apparent density, greater porosity, and more specific surface area than iron ore.

Figure 2.14 Micrograph of sponge iron

Because of the high porosity, and specific surface area, DRI is subjected to oxidation during transportation. In general, oxidation of DRI takes place in two forms: Reoxidation andCorrosion. [32] Reoxidation occurs when the metallic iron in hot DRI reacts with oxygen inthe air to form either Fe 3O4 or Fe2O3. The reaction continues as long as the DRIremains hot and sufficient oxygen is available. Because reoxidation reactions areexothermic and DRI is a good insulator, it is possible that once reoxidation beginsinside a pile, the DRI temperature increases and accelerates the reoxidation rate.Although the inner core of the pile may reach temperatures up to the fusion pointof iron, the maximum temperature of the outer parts of the pile will be muchlower because of heat dissipation. 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. The corrosion reactionscontinue as long as water is present. Because water evaporates at approximately100oC, corrosion reactions have a low temperature limit even though thereactions are exothermic. Small amounts of hydrogen may be
34

generated whenDRI reacts with water. it is stored in closed environment. [30]

[1]

This can form an explosive mixture if

Allowing DRI to become wet does not necessarily cause it to overheat.Whenlarge piles of DRI are wetted with rain, the corrosion reactions are limited to theouter surface area of the pile and the resultant heat from the corrosion reactionsis dissipated into the atmosphere. However, if water penetrates into the pilefrom the bottom, or if wet DRI is covered with dry DRI, the heat from corrosionreactions can build up inside the pile to the point where rapid reoxidationbegins. DRI saturated with water can cause steam explosions if it is batch chargedinto an electric arc furnace. Thus, the key to avoid oxidation is simply keeping the material cool and dry. [1]

2.4.5 DRI Briquetting

Several methods of passivating DRI to make it more resistant to reoxidation and corrosion have been developed, but none has been as effective as hot briquetting. When DRI is hot briquetted, it is called HBI. HBI is produced by molding hot (700oC) DRI into pillow-shaped briquettesusing roll press. HBI has the following advantages: It is almost twice as dense as non-briquettedDRI and it has substantially less surface area, which makes it 100 times moreresistant to reoxidation. It is stronger and more massive, making it more resistantto fines generation. It takes up less volume for storage and shippingowing to its high bulk density.[1] Figure 2.15 shows the difference between the HBI and Pellet DRI.

35

Figure 2.15 HBI and Pellet DRI

2.4.6 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 2.7 shows a comparison between gas-based and coal-based DR processes.
Table 2.7 Comparison between Gas-based and Coal-based DR Processes Parameter Reaction Kinetics Temperatures Needed Product's Purity Energy Consumption Raw Materials[31] Capital Cost[33] Gas-Based Faster Lower Higher Lower Natural Gas and Pellets Higher Coal-Based Slower Higher Lower Higher Non-coking coal and Lump ore Lower

36

2.4.7 Global DRI Production

As stated before, the blast furnace share in ironmaking decreases with time. The following curve shows the growth of DRI production globally from 1975 to 2007.[31]

Figure 2.16 Growth of global DRI production from 1975 to 2007

The DRI production isn't localized in certain part in the world; however, it is divided between the different regions as shown in figure 2.17.
[34]

Figure 2.17 2008 World DRI production by region (Mt)

37

2.5 Gas-Based DR Processes

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

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. The reducing gas is produced by reformation of natural gas. [35]

2.5.1 HYL I Process

The process was first developed in Mexico, and the first industrial scale unit was built in Monterrey (Mexico) in 1957 in a capacity of 200 metric tons per day. After that, the process has undergone several modifications. By 1980, fifteen HYL plants with a total capacity of about 10 million metric ton (11 million net ton) per year of DRI were scheduled to be in operation in world wide.[35] 2.5.1.1 Main Reactions Taking Place Steam Reforming: CH4 + H2O CO+ 3 H2 (1)

Iron Ore Reduction: H2 + Fe2O3 CO + Fe2O3 H2 +FeO CO + FeO H2O + 2 FeO CO2 + 2 FeO H2O + Fe CO2 + Fe (5) (2) (3) (4)

2.5.1.2 Process Description As shown in figure 2.18, the reducing section consists of a set of four reactors, three of which are in operation while the fourth is in the turn-around
38

position. The HYL process is a cyclical batch operation, and three on line reactors operates in series. The reduction of the charge is performed in two stages, an initial reduction stage and main reduction stage. Cooling and carbonization (Fe 3C) and the final adjustment of metallization are performed in the third stage. Each stage of operation takes about three hours. A rigorous system of valves permits the reactors to be connected in any desired order so that inside any reactor, initial reduction or main reduction or cooling and carburization can take place.[35] Natural gas is reformed using excess steam in the presence of catalyst. The resulting reducing gases are quenched so as to condense water, and increase the calorific value. [36] The flow of reducing gas is counter-current of the iron oxide reduction stage. The quenched fresh gas from the reformer is used first in the reactor where cooling and carburization takes place (in which DRI will be produced). The gas then flow through the reactor that is in the main reduction stage, and finally through the reactor that has most recently been charged for the initial reduction stage. Reduction is accomplished according to reduction (2) to (5). Because water is produced during reduction, the reducing gas is quenched when it leaves each reactor to condense the water and enhance the reduction potential of the gas. Before entering the reactors in the reduction stage, the quenched process gas is heated to about 815C in an indirectly heated gas fired furnace. The gas is further heated to about 1050 oC by the combustion of residuals unreformed hydrocarbons with the controlled injection of air at t he entrance to the reactor. The reducing temperature in the HYL process is above 980oC.[35]

39

2.5.1.3 Current Status At present, 3 HYL I plants (Located in Venezuela, Indonesia, and Iran) having 9 modules with total plant capacities varying from 1 to 2 Mtpa, are in operation. However, and because of being a batch process, the process is no longer attractive, and is now contributing by less than 1% of the global DRI production despite contributing by about 40% in the early eighties. [36]

Figure 2.18 Flow Sheet of HYL I process for DRI production

2.5.2 MIDREX Process

Surface combustion division of Midland developed the Midrex Process. In the mid-1960s the Midrex division became a subsidiary of Korf industries. The first commercial Midrex plant was installed near Portland Oregon and started
40

production in 1969. The plant included two shaft reduction furnaces of 3.4 m (11.2 feet) inside diameter and had a total capacity of 300000 metric tons per year. The average energy consumption of this plant was about 15 million kilojoules per metric ton (12.9 million BTU per ton of DRI). Many difficult engineering and operating problems were solved during the first several years of operation of this plant. By 1983, more than twenty Midrex modules were installed having a total capacity of about 9 million metric ton per year (9.9 million net ton per year). [35] 2.5.2.1 Main Reactions Taking Place Reforming: CH4 + H2O CH4 + CO2 CO+ 3 H2 2 CO+ 2 H2 (1) (2)

Iron Ore Reduction: H2 + Fe2O3 CO + Fe2O3 H2 +FeO CO + FeO H2O + 2 FeO CO2 + 2 FeO H2O + Fe CO2 + Fe (3) (4) (5) (6)

2.5.2.2 Process Description As shown in figure 2.19, reducing process gas, about 95% combined hydrogen and carbon monoxide, enters the reducing furnace through a bustle pipe and ports located at the bottom of the reduction zone. The reducing gas temperature ranges between 760 & 950 oC. The reducing gas flows countercurrent to the descending solids.
[35]

The latter may be lump ore or

pellets; however, pellets are preferred owing to their superior physicochemical

41

characteristics.

[36]

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 above. The hot reformed gas (over 900 oC) which has been restored to 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 in the heat recuperates to reheat combustion air for the reformer burners and also to preheat the process gas before reforming. The addition of heat recuperates to these gas streams has enhanced process efficiency, helping to decrease 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. [35] When incorporating hot briquetting in the MIDREX process, the cooling gascircuit is eliminated, and the hot DRI is continuously discharged from the shaftfurnace into a hopper and directly fed into a hot briquetting machine. The resultingHBI is continuously discharged from the hot briquetting machine, separatedinto individual briquettes, and cooled. [1]

42

Figure 2.19 Flow Sheet of MIDREX Process for DRI Production

2.5.3 HYL III Process

The HYL-III process of Hylsa of Monterrey, Mexico evolved from the original HYL process by retaining the catalytic reformer, the gas reheater, and the off gas handling system which condenses water and remove particulates. 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. [35] 2.5.3.1 Main Reactions Taking Place Steam Reforming: CH4 + H2O CO+ 3 H2 (1)

Iron Ore Reduction: H2 + Fe2O3 CO + Fe2O3 H2 +FeO CO + FeO H2O + 2 FeO CO2 + 2 FeO H2O + Fe CO2 + Fe
43

(2) (3) (4) (5)

2.5.3.2 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 2.20, sized iron ore (pellet or lump) is charged via lock hoppersinto a pressurized shaft furnace wherein the ore is heated, reduced, carburized,and cooled as it descends by gravity. The cooled

productisdischarged via a rotary valve and lock hoppers onto a conveyor belt. In thecase of hot briquetting, the cooling gas circuit is eliminated and the hot DRI isdischarged through lock hoppers into the hot briquetting units. Fresh reducing gas is generated by reforming natural gas with steam. Thenatural gas is preheated in the reformer's stack, desulfurized to less than 1 ppm sulfur. It is thenmixed with superheated steam, further preheated to 620 oC in the reformer's stack, andthen reformed in alloy tubes filled with nickelbased catalyst at a temperatureof 830 oC. The reformed gas is quenched to remove water vapor, mixed withclean recycled top gas from the shaft furnace, reheated to 925 oC in an indirectfired heater, and injected into the shaft furnace. For high (above 92%) metallizationa CO 2 removal unit is added in the top gas recycle line in order to upgradethe quality of the recycled top gas and reducing gas.[1]

2.5.3.3 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 degree of metallization and/or carbon content of the final product.
44

 The higher gas pressure system reduces the tendency for bed fluidization, and thus permits higher capacity. Selective elimination of H2O and CO2 from the reducing gas circuit allows maximum recycle of reducing gases to the furnace High pressure steam generated in the reformer is mainly used for generating electric power for the plant.[16]

Figure 2.20 Flow Sheet of HYL III Process for DRI Production

2.5.4 ENERGIRON Process

45

For more than 50 years, HYL (now Tenova HYL) has developed technologiesdesigned to improve steelmaking competitiveness and productivity for steelfacilities. [37] ENERGIRON brings the combined support of two premier companies Tenova and Danieli to the world iron and steel industry. ENERGIRON is the innovative HYL direct reduction technology jointly developed by Tenova and Danieli.[38] 2.5.4.1 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 2 H2O CO+ 3 H2 CO+ H2O CO + 2 H2

Iron Ore Reduction: H2 + Fe2O3 CO + Fe2O3 H2 +FeO CO + FeO H2O + 2 FeO CO2 + 2 FeO H2O + Fe CO2 + Fe (2) (3) (4) (5)

2.5.4.2 Process Description

46

As shown in figure 2.21, 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. Since all reducing gases are generated in the reduction section, takingadvantage of the catalytic effect of the metallic iron inside the shaft furnace,optimum reduction efficiency is attained, and thus an external reducing gasreformer is not required. This is called zero-reformer process (ZR). The basic scheme can also use the conventional steam-natural gas reformingequipment, which has long characterized the process. Other reducing agentssuch as hydrogen, gases from gasification of coal, petroleum coke and similar fossilfuels and coke-oven gas, among others, are also potential sources ofreducing gas depending on the particular situation and availability. [37]

Figure 2.21 Flow Sheet of ENERGIRON process for DRI production

47

2.5.4.3 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 asthe sulfur is eliminated along with the CO2 in the CO2 absorption system,which is part of the reduction circuit. Mixtures of pellets and lump ores can be processed in ratios ranging from100% pellets to 100% lump ores, depending on the ore characteristics. Plantsin Brazil (Usiba) and In India (VikramIspat) are operating with 100% lump ore. Additionally, the low gas velocity inside the shaft, due to the high operationpressure, diminishes fines carry over, and thus reducing ore losses from the plant. For the production of high quality DRI,i.e. 94% metallization, 3.5% carbon anddischarged at 700C, the thermal energyconsumption is only 9.15 million BTU per ton of DRI which is lower than other technologies. A remarkable advantage of this processscheme is the wider flexibility for DRIcarburization, which allows attainingcarbon levels up to 5.5%. The effect of increasing carbon content on the energy consumption in the subsequent EAF is shown in figure 2.22. For the ENERGIRON plant, the NOx is below environmental limits as there is no need for huge air preheating. This is because of the very high energy integration available in the process. [37]

48

Figure 2.22 Effect of increasing carbon content and temperature of DRI

on the energy consumption in EAF

2.5.5 Global Gas-Based DRI Production

As stated above, 75% of the DRI productionin 2008 was from the gas-based processes. As shown in figure 2.23, MIDREX technology is the dominating, followed by HYL/Energiron. [34]

Figure 2.23 2008 World Gas-based DRI Production by Process

49

2.6 Coal-Based DR Processes

In 2008, 25% of the DRI production was from the coal-based processes.
[34]

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 2.24.

Figure 2.24 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. Historically, this is true and shown in figure 2.25.
[23]

50

Figure 2.25 Fluctuations of crude oil and coking coal historically

In coal-based processes, rotary kilns are used as the reducing reactor. The basic principle of all rotary kiln processes is to reduce iron ore (lump or pellets) in a rotary kiln where coal is fed from both ends to produce the reducing conditions and generate the heat required for reduction along the kiln's length. The main differences in the individual processes are related to the control system especially for temperature. [31]

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 owing to its combustion. A finer 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
51

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).
[31]

This is

mainly achieved by burning combustibles released form the bed using secondary air. The latter is blown by fansthrough burner tube space uniformly along the length of the kiln. [35] 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 2.26 shows a schematic representation of DRI production in rotary kilns. Figure 2.27 shows an approximate material balance for DRI production in rotary kilns. [31]

52

Figure 2.26 A schematic representation of DRI production in rotary kilns

Figure 2.27 An approximate material balance for DRI production in rotary kilns.

53

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

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]

54

Figure 2.28 shows a schematic cross section area of rotary kiln together with the encountered reactions.[31]

Figure 2.28 A schematic cross section area of a rotary kiln t ogether with the encountered reactions

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. Before discussing every process separately, the main differences between them are shown in table 2.8.[31]

55

Table 2.8 Main differences between commercial rotary kiln DR processes Parameter % P in Ore Size range of ironbearing materials, mm Energy Requirements,Gj/t DRI Flux, kg/t DRI 50-70 50-90 40 40 20 15 16.5-18.5 17.5-19 SL/RN As low as possible 10-30 (Lump) 10-16 (Pellets) Codir As low as possible Wide size range acceptable DRC As low as possible Jindal Up to 0.04

5-25

6-18

2.6.4 SL/RN Process

RN process (for Republic Steel Company and Nations Lead Corporation) was developed originally in Norway, primarily to recover TiO 2 from titanium bearing ore for the production of paint pigments. However, further development showed that other iron bearing ores could also be treated successfully to produce iron. Subsequently, a pilot plant was built in the United States, and in 1964 LurgiChemie acquired the RN patents and developed the technology further with the Steel Company of Canada Ltd. (Stelco) to the SL/RN process.Currently, the process is also known as Lurgi (Outokumpo) process. [35] The process description is the same as that shown in section 2.6.1. The main features of this process are: Flexibility to the type of iron bearing materials which can be used such as lump ore, pellets, ilmenite, iron sands, and steel plant wastes

56

 Use of wide variety of solid fuels ranging from anthraciteto lignite including charcoal. [5] Finally, it worth noting that this process is the mother of all the other coalbased DR processes, and it is the most widely applied. [31]

2.6.5 DRC Process

The DRC process of the DAVY Reduction Corporation (DRC)was developed on the basis of the Hockin process of synthetic titanium production. The first commercial furnace was constructed for Scaw Metals in Germiston, South Africa. Operations at Scaw Metals started in July of 1983. [35] The process description is the same as that shown in section 2.6.1. The main features of this process are: The direction of the opening in the secondary air tubes in the kiln's preheating zone ensures co-current flow with respect to the kiln gases. On the other hand, the openings in the reduction zone are positioned to give countercurrent flow with respect to the kiln gases. It is claimed that this method for air injection inside the kiln insures optimum heat transfer. The trajectory of the fine coal injection can be altered by changing the inclination of the delivery pipe.[31]

2.6.6 CODIR Process

The CODIR (Coal Ore Direct Reduction) process was developed in Germany. Commercial operation of the process began in 1974 when a 120,000 tpa plant was commissioned at the Dunswart iron and steel works, South Africa.

57

The process description is the same as that shown in section 2.6.1. The main features of this process are: Countercurrent injection of coarse coal in the size range of 6-25 mm, going up even to 35 mm using highly reactive coals (rather than below 6 or 10 mm in other rotary kiln processes). In this process, most of the coal is injected from the discharge end of the kiln (which is completely opposite to the other rotary kiln processes) The coarse coal particles which settle in high temperature zone of the kiln are mixed with the burden while releasing volatiles. As a result, the volatiles in the countercurrent injected coal participate to reduction, and thus amount of coal needed becomes lower. CODIR coolers use a direct mist of water inside the rotary cooler rather than indirect water sprays on the cooler shell. The water mist is controlled in such a manner that the hot sponge iron is cooled without significant loss in metallization. This has led to significant reduction in amount of cooling water required. The energy consumption in case of course coal injection is only15 Gj/t compared to 20 Gj/t with finer coal injection.

Because of these modifications, the flow sheet has slightly been changed to be as shown in figure 2.29. [31]

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Figure 2.29 General Flow Sheet of the CODIR process for DRI production

2.6.7 Jindal Process

The Jindal process for DRI production was developed by Jindal strips Ltd.in a 15,000 tpa pilot plant. Based on that, Jindal strips installed a commercial plant which started production in March 1991. Today, Jindal Steel and Power has six kilns of 300 tpd and four kilns of 500 tpd (total capacity 1.37 tpa). Thus, it is the largest coal based DRI plant in the world.

The process description is the same as that shown in section 2.6.1. The main features of this process are: 55-60% of the total coal is injected from the discharge end. It is claimed that as a result, the C/Fe ration in the feed end is as low as 0.42-0.44 which is well below the normal figures in the other coal-based DR processes (0.46-0.48).
59

 Coal up to 30% ash can be used successfully. The placement of secondary air tubes within the kiln is completely different from the other technologies (no details are available). For the first time in the world, the blast furnace gas has been used in this process, and has resulted in better reduction, and reduction on specific coal consumption.[31]

2.6.8 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. 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 [31]

2.6.9 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.
60

 The fact that the reactor rotates at 0.4-0.5 rpm 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.[31]

2.6.10 Share of Different Processes in Global DRI Production

The coal-based DR processes are growing gradually. In 2003, their contribution in the global DRI production was only 10.1%. The corresponding figures for 2004, 2005, 2006, 2007, and 2008 were 12.1%, 15%, 19.7%, 22.6% and 25.3% respectively. The breakup of production in different coal-based rotary kiln processes in 2006 is shown in the following table.
[31]

Table 2.9 Share of different coal-based processes in global 2006 DRI production Process SL/RN DRC CODIR Jindal Production in Mt 1.83 0.63 0.52 1.32

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2.7 Smelting Reduction

As stated before, smelting reduction (SR) is the 3 rd 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 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. [36]

2.7.1 Advantages of SR with respect to Blast Furnace

SR processes use non-coking coal as fuel and reductant instead of the scare 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 8mmin size as the ferrousfeedstock. This wasn't possible in blast furnace.
[39]

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.
[40]

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 have the following advantages: Faster rates of reaction
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 Prevention of sticking problems associated with solid state reactions in DR Processes

Having liquid phase in the reactor has the following advantages: Increased transport rates owing to convection Remarkable increase in the conversion rate because of the higher contact area resulting from the dispersed nature of phases.[5]

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 2.30, charging of HM as a scrap substitute leads to great decrease in energy consumption, whereas, DRI causes a slight increase. However, a maximum of 50% replacement is specified for the HM, as the energy content will be too large for EAF steelmaking. As shown in figure 2.31, at higher percentages, productivity decreases, as the decarburization of HM will be the dominant operation in the EAF. [5] Thus, this can be considered anther advantage of SR with respect to DR.

Figure 2.30 Effect of different scrap substitutes on EAF energy consumption

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Figure 2.31 Effect of different scrap substitutes on EAF productivity

2.7.4 Raw Materials for SR Processes

In both blast furnace and SR, the cost of raw materials constitutes about 60% of the total cost of producing hit metal. Thus, efforts have been made and will continue to utilize less expensive raw materials. However, already the quality specifications for raw materials used in SR processes are less stringent than those used in blast furnace. Most SR processes therefore use low grade fine ores, iron bearing wastes, and cheap thermal coals.[36]

2.7.5General Features of SR
Figure 2.32 shows a schematic diagram of SR. The phenomena taking place in the blast furnace are mainly divided on 2 stages. Moreover, the reactants

64

aren't introduced together. Thermal non-coking coal is used as a fuel and reductant. 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.[36] Post combustion mainly refers to the secondary oxygen or air introduced in the process for combusting volatiles for heat production and volatiles cracking.

Figure 2.31 Schematic representation of SR technology

2.7.6 Single Stage SR

In an ideal single SR reactor, all the reduction reaction should take place together in the liquid state in a single step as shown in figure 2.32. Since the reactor is fed with iron ore without any pre-reduction, the energy consumptionin single stage SR is higher. The energy consumed is translated
65

into coal, and thus high amounts of oxygen will also be required to react with coal. Consequently, single stage SR processes are often in efficient and economically unattractive despite having low capital cost. In actual practice, most SR processes utilize at least 2 reactors for effective process control. [36]

Figure 2.32 Block Diagram for single stage SR

2.7.7 Two-Stage SR
2.7.7.1 General Idea Here 2 separate reactors are involved, one for pre-reduction and the other for smelting and the rest of the reduction as shown in figure 2.33. The off-gas from the smelting stage is utilized for pre-reduction. Hence, there must be a close match between these 2 stages to assure efficient operation. [36]

Figure 2.33 Block Diagram for two-stage SR

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2.7.7.2 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)

2.7.7.3 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 2 H2O CO2 + H2 H2O + 2 FeO CO2 + 2 FeO H2O + Fe CO2 + Fe Fe in HM + CO Fe in HM + CO 2 (9) (10) (11) (12) CO CO2 2 CO CO + H2 (5) (6) (7) (8) (1) (2) (3) (4)

In addition, pyrolysis of coal, volatiles composition, and evaporation of moisture takes place.
[40]

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2.7.8 COREX Process

Among the newly developed SR processes, COREX is the leader both in terms of capacity and number of plants across the world which has adopted this technology. [40] COREX produces a high quality HM using non-coking coal and pure oxygen in an environmentally-friendly process. 2.7.8.1 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 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. [40] 2.7.8.2 COREX Process Description As shown in figure 2.34, the COREX process is based upon areduction shaft for iron ore reduction, and a meltergasifier 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 meltergasifier.
68
[16]

In the meltergasifier,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. [40]

Figure 2.34 Flow Sheet of COREX process for HM Production

2.7.8.3 Limitations for Economic Production The export gas from the reduction shaft is produced in large amountstypically 1650 1700 Nm3/THM. Efficient utilization of COREX export gas is the only way that hot metal production can be made techno-economically

69

feasible. The export gas can be used in different ways including heating processes in steel plants, and power generation. [40] 2.7.8.4 Commercial Production Currently, 4 plants are utilizing COREX process for pig iron production. These plants are: (i) (ii) (iii) (iv) Saldanha Steel Works, South Africa (0.8 mtpa); Jindal South West Steel, Toranagallu Works, India (2 *0.8 mtpa); Posco, Pohang Works, Korea (0.8 mtpa); Baosteel, China (1.2 mtpa).

Figure 2.35 COREX plant in Saldanha Steel Works, South Africa

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2.7.9 FINEX Process

FINEX is a 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.[36] 2.7.9.1 History of FINEX Since 1992, Siemens VAI and the Korean steel producer Posco have been jointly developing the FINEX process. [41] 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.[36] A 150 ton/day pilot plant was installed after the success achieved with smaller 15ton/day unit.
[16]

After that,

commercial unit of 1.5 mtpa at Pohang, Korea was commissioned in 2007 and is in operation since then. [42]This is the only operating FINEX process till now. 2.7.9.2 FINEX Process Description As shown in figure 2.36, fine iron ore is preheated and reduced to fine direct reduced iron (DRI) in a three or four stage fluidized bed reactor system. The upper reactor stage serves primarilyas a preheating stage. In the succeeding stages the iron ore is progressively reduced to fine DRI. The fine DRI will be compacted and then charged in the form of hot compacted iron (HCI) intothe meltergasifier. The charged HCI is subsequently reduced to metallic iron and melted. The heat needed for reduction and melting is supplied by coal gasification with oxygen. The reduction gas, also produced by the coal gasification, ispassed through the fluidized bed reactors in a similar idea to COREX process.

71

The generated FINEX export gas is ahighly valuable product and can befurther used for DRI/HBI production,electric energy generation or heatingpurposes. The hot metal and slagproduced in the meltergasifier isfrequently tapped from the hearth as inblast furnace or COREX process. [41]

Figure 2.36 Flow Sheet of FINEX process for HM Production

Figure 2.37 FINEX plant, Posco, Pohang Works, Korea

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2.8 Groupings of Ironmaking processes

To summarize the previous part, different groupings of the process will be presented according to different points of comparison. [16]

2.8.1 According to Reduction Process Type

2.8.2 According to Reduction Agent Type

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2.8.3 According to Production Capacity

2.8.4 According to Product Type

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2.9 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 point of views.

2.9.1 Detailed Process Description

As shown in figure 2.38, COREX consists of two reactors, the reduction shaft and the melter-gasifier. The reduction shaft is placed above the meltergasifier. 2.9.1.1 Reduction Shaft Process Description Iron ore, pellets and additives (limestone and dolomite) are continuously charged into the reduction shaft 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 specific reduction gas flow is about 1200Nm 3/ton of iron bearing burden charged to the shaft. 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 reduction shaft into the melter-gasifier. 2.9.1.2 Melter-Gasifier Process Description As shown in figure 2.39, the melter-gasifier can be divided into three main reaction zones: Gaseous free board zone (upper part or dome)

75

 Moving bed (middle part above oxygen tuyeres). It is also called char bed. 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 melter-gasifier 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. The operating pressure, in the melter-gasifier is in excess of 3 bars. 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. [43] It is to 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.
[40]

The

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 releases from the coal. The gas generated inside the melter-gasifier contains fine dust particles, which are separated in hot gas cyclones. The dust collected in the cyclones is recycled back to the melter-gasifier 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 melter-gasifier is cooled to the reduction gas temperature
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(850oC) through the addition of cooling gas. A major part of this gas is subsequently fed to the reduction shaft. The excess gas is used to control the plant pressure. This excess gas and the reduction shaft top gas are mixed and termed as COREX export gas.[43]

Figure 2.38 Flow Sheet of COREX Process for HM Production

Figure 2.39 Zones in the Melter-Gasifier

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2.9.2 Gas Cycle and Specifications in COREX Process

Figure 2.40 shows the gas flow diagram in COREX process. [40] Stream number 3 refers to the cooling gas. It appears from the table attached that the amount of dust is greatly reduced in the process due to the presence of the hot gas cyclone, and the water scrubbers. By comparing the compositions of stream 4 and stream 5, it is also apparent that the water scrubbers help in increasing the calorific value of the gas by condensing the water vapor.

Figure 2.40 Gas Cycle and Specifications in COREX Process

2.9.3 COREX Export Gas

Unless export gas is well-utilized, the process won't be cheaper than the blast furnace route.
[36]

Large volumes of export gas are generated from the process-

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typically 1650 1700 Nm3/THM. The export gas can be utilized in the following ways: Heating purposes is a steel plant (in rolling mills) Power Generation (as shown in figure 2.41 a) The production of oxygen needed in COREX plant (as shown in figure 2.41 a) Synthesis gas in the chemical industry Reductant to produce DRI in any gas-based DR processes (as shown in figure 2.41 b) Can be used internally in the process as reducing gas after carbon dioxide removal. This results in appreciable reduction in the consumption of coal and oxygen (as shown in figure 2.42)[40]

Figure 2.41 Export gas from 3000 tpd C OREX plant used in: a) combined cycle power plant (th: thermal, el: electrical) and b) DRI production

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Figure 2.42 In-Process utilization of COREX export gas

2.9.4 Raw Material Requirements for COREX Process

To achieve reliable operation, there are specifications for the different raw materials to be used in COREX process. 2.9.4.1 General Requirements Table 2.10 summarizes the preferred and tolerable grain size, and some chemical properties of the raw materials used in COREX process.
Table 2.10 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% 62 - 65
80

Preferred

Tolerable

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

62 - 65 8 - 20

55 (min.) 6 - 30

58 (min.)

b) Grain size, mm Sinter a) Fe% b) Grain size, mm Limestone, dolomite Grain size, mm Limestone, dolomite fines Grain size, mm

8 - 16

6 - 30

50 - 55 10 - 30 8 16

45 - 50 (min.) 6 - 45

4 - 10

The chemical requirements of coal can also be illustrated in figure 2.42. The figure defines the regions where the coal can be used safely, and the regions where blending should be performed to ensure safe operation. The numbers shown are for various tested coals. [5]

Figure 2.43 classification of coal according to their ash and volatile matter content

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2.9.4.2 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 melter-gasifier, the water used in the scrubbers dissolve them, and thereby prevents accumulation.[5] 2.9.4.3 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 JINDALplant 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, the coke quality is different to the coke qualities being typically used in the blast furnace. In terms of blast furnace operation, only low quality coke is required for COREX, which has also a big effect to the specific coke price. It is equal to coke breeze. Finally, coke can be seen as an "additive" for the processas to the most extent thermal coal is directly used. Moreover, coke will be of minor economic impact.[44]

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2.9.5 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:[43]

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 Low CO2 percentage in the reduction gas so as to ensure higher metallization of the DRI Optimum distribution of oxygen between the tuyeres and dust burners Permeability of the char bed High system pressure

2.9.6 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 2.11 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.

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Table 2.11 Comparison between pollutants emerging from a blast furnace and a COREX unit Blast Furnace 1) Aqueous Effluents in mg/THM a) Ammonia b) Phenol c) Sulphide d) Cyanide 2) Gaseous Emissions in mg/THM a) NOx b) SOx c) Dust 1900 1600 427 21 26 39 590 80 60 20 50 0-1 7 1 COREX Process

Table 2.12 compares the sulfur input and output balance in blast furnace and COREX unit.
(45)

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 hot metal is similar to that ofthe blast furnace. This is because during the gasification of coal in the melter-gasifier, sulfur is converted predominantly to H2S. Moreover, small amount of SO x is formed by the combustion of H 2S with the oxygen in the dust burner region.The above H 2S and SOx along with reducing gases enter the reduction shaft furnace 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 melter-gasifier and finally dissolves into a molten-slag phase.[46]

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Table 2.12 Comparison between sulfur balance in a blast furnace and a COREX unit Sulfur input / output 1) Inputsin kg sulfur/THM a) Ore b) Fuel Total 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 0.15 2.6 2.75 0.035 4.682 4.717 Blast Furnace COREX Process

2.9.7 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 non-coking coal.[40] 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. [39] 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.

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 Correction of hot metal and slag composition is easier and faster in COREX than in blast furnace as additions can be made through the meltergasifier. 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. Specific melting capacity of COREX is about twice that of the blast furnace. [47] 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 Jindalin India.[40] 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]

2.9.8 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 10% 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.[42]

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2.9.9 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 into 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.
[47]

2.9.9.1 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 will be processed in Corex plants, and the rest will be 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, they have 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, they have deduced that there will be surplus amount of export gas if COREX is to be applied. In that case, they didn't find a feasible application for this surplus gas, and thus, 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 produced. This shows that the decision of returning back to blast furnace doesn't necessarily mean that blast furnace is better than COREX.[48]
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2.9.9.2 Using Iron Ore Fines Undersized iron ore (size 6-12 mm) is being charged directly into the COREX melter-gasifier. 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. [43] 2.9.9.3 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:

Use of BOF Slag Mill scale Limestone and Dolomite fines [43]

2.9.9.4 Improvement in Plant Operation Through continuous research, and by gaining more operating experiences, the plant's performance was greatly enhanced as shown in Table 2.13.[43]
Table 2.13 Progress of COREX performance in JVSL Year 1999-2000 2000-2001 2001-2002 2002 - 2003 2003-2004 Production, mt 0.4 0.77 1.52 1.46 1.36 Fuel Consumption, kg / THM 1163 1071 1082 1041 1000 Hot Metal Temperature, C 1491 1503 1497 1497 1487
o

% S in HM 0.06 0.037 0.037 0.029 0.027

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2.9.9.5 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 2,44, 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 us 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. 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.
[49]

Figure 2.44 Synergy of COREX and Blast Furnace

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2.9.10 Case Study SALDANHA

An Integrated Compact Mill (ICM), 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, on the west coast of South Africa. Export gas from the COREX plant is used for the production of direct reduced iron (DRI) in an adjacent DR plant using a MIDREX shaft furnace and LINDE Vacuum Pressure Swing Absorption plant (VPSA) for the removal of CO2. The DR plant is operated with a mixture of about 65 per cent lump ore and 35 per cent pellets. The COREX plant at SALDANHA STEEL was started up on December 1998 and 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. [44]

2.10 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 parameters so as to be able to optimize it.

2.10.1 Reduction Shaft

The most important parameter is the permeability of the burden inside the shaft. To ensure good permeability, the particle size of the iron bearing materials, and the amount of fines generated before and after reduction should be adjusted. 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.
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As this parameter decreases, the pellets crumble and decreases the bed voidage, 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.[50]

Figure 2.45 Influence of CCS on the reduction shaft's pressure drop

2.10.2 MelterGasifier
Most of the research focus on the melter-gasifier as it is the place where coal pyrolysis, and combustion takes place. Moreover, it is the place where the products are tapped. 2.10.2.1 Effect of Coal Size

91

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 2.46. undersize faster, and of the
[50]

Moreover, the combusts

coal

thus a proportion combustion heat used in melting; raises the dome's temperature. This

is not fully however, it

results fuel

in rate

increasing

the

and raising the

silicon percentage in hot metal. [51] . It was deduced that the optimum mean particle size is 20-22 mm.[50]

Figure 2.46 Influence of the mean particle size on the meltergasifier's pressure drop

2.10.2.2 Fuel Rate Regression analysis using multiple variables was used to get an equation for the fuel rate (coal + coke) in COREX process

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 = 1712 8.1 + 12.1 1.28 + 0.21 + 2.45 + 1.1 (4.1 ) Where FR is the fuel rate (kg/THM), MR is melting rate (t/h), Moist is % moisture in coal, Metln is % metallization, SR is slag rate (kg/THM), US is % undersize coal (-6 mm), VM is % 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. [50] 2.10.2.3 Factors Affecting Coke Addition Heat stability is also an important index of coal forCOREX

processoptimisation. Usually the higher thevalue, the better the process as high stability coal candecrease coke consumption in the meltergasifier. [52] The heat stability is measured using the following experiment. One kilogram of coal is put into drying oven. Thiscoal should have a grain size between 5 and 15 mm. Thisoven is heated to 1100 oC where the coal will bemaintained in the furnace for 0.5 h without air. Afterthat, the coal is taken out and screened using 6 mmscreen. RW+6 is the percentage of coal bigger than 6 mmobtained after this process. [53] 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. [52] In another study, statistical analysis of daily plant performance data using more than 500 points has been carried out, and the following regression equation was the result:
= 409.3 + 13.56 0.11 + 0.21 3.08 5.15 23 4.18 (1.14 )

Where Mcoke is the % 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
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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. [54] 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 charstrength after reaction (CSR) and char reactivity index (CRI). Their significance can be explained as follows: During coal descent in the fixedbed, char is gasified with CO 2, where CO is produced from the famous Boudouard reaction. Ifthe latter occurs quickly in thechar bed, carbon consumption increases in intensity toform a small combustion area, which leads to unevengas distribution and poor heat balance of the char bed.[55] The quick consumption can be attributed to particle size of char (CSR), and char reactivity (CRI). It is apparent from figure 2.47 that with increasing CSR thecoke rate decreases. Thus, CSR of char above 45 and CRI below 30% are recommended. [54]

Figure 2.47Effect of coal's CSR on coke rate

2.10.2.4 Effect of amount of volatile matter in coal If the coalvolatile matter is low as seen from figure 2.48, the gasesgenerated from such coal would be insufficientfor carrying out the reduction ofiron bearing materials in the shaft. On the other hand, if volatile matteris high, it would increase the heat demand inside themelter gasifier dome and cause
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problems such as highfuel rate and more tarry material like CH 4would begreater than2% as shown in figure 2.49. High amount of tarry materialcreates problem in the gas cleaning system.[54]

Figure 2.48 Effect of coal's VM on reduction gas and fuel rate

Figure 2.49 Effect of coal's VM on % CH 4 in the reduction gas

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2.10.2.5 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.[54] Figure 2.50 shows the effect of moisture on the dry fuel rate.

Figure 2.50 Effect of coal's moisture on the dry fuel rate

2.10.2.6 Minimization of Energy Consumption To minimize energy consumption, amount of gases produced in the meltergasifiershould be the same amount needed in the reduction shaft. It was found that % Metallization of 85-95% is the optimum for minimized energy consumption. [52] 2.10.2.7 Effect of %MgO and %Al2O3 on the slag Experiments have proved thatthe viscosity ofslag decreases with increasing level of MgO and hencewhen Al2O3in slag is to be increased to reduce slag
96

ratewhich also tends to increase viscosity, MgO in slag needs to be increased. to counter balance this effect. [56] The following figures also show that increasing % MgO in the slag tends to reduce the slag rate and fuel rate.
[54]

Figure 2.51 Effect of %MgO and % Al 2 O 3 on the slag rate

97

Figure 2.52 Effect of %MgO and % Al 2 O 3 on the dry fuel rate

2.10.2.8 Modeling of COREX process for optimisation ofoperational parameters One of the most important studies was conducted 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 2.53. The model has been validated for slag rate and %CO inthe generator gas.

Figure 2.53Block diagram showing a macroscopic mod el for COREX

2.11 COREX Microscopic Analysis

Due to the enclosed process and the limitations of measuringinstruments, it is difficult to directly study the different velocity, temperature and composition profiles inside each part of the process.
98
[57]

Thus, to reach the

previous objective, microscopic modeling was performed for both the reduction shaft and melter-gasifier.

2.11.1 Reduction Shaft

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 temperaturereducing gas brings more energy along the pathway, thus helping to increase the reductionreaction rate and enhance DRI average metallization level. [57]

2.11.2 MelterGasifier
The firstdeveloped model for the melter-gasifier was one-dimensional (1D), and focused on coal pyrolysis. The reactor was classified into 3 zones which are the freeboard, fluidized bed, and moving bed.
[39]

After that, and in

another paper, the model was used to studythe effect of operational parameters like the bed height,C/O ratio, top pressure, and steam injection on the processperformance. [58] This model hasassumed that combustion took place instantaneously at the tuyere plane (zero-dimensionalmodel was assumed for the tuyere region). This reduces thecombustion-zone height to zero. But, the combustion zonecould be
99

quite large, since pureoxygen is used for combustion. Thereby, the simplifyingassumption ignores one of the important aspects of the process. The modelfurther assumed that the ore and flux arenonreactive and gases in the free board are in equilibrium.However, their resultsshow general agreement with the plant data for the temperature of the hot metal and composition and temperature of the top gas. [39] The most recent model has modified the modeling of the tuyere level by using twodimensional(2-D) modeling of the combustion zone. The 2-D zone extends fromthe tuyere region to 0.5 m above that, and the remainingpart is 1D as shown in figure 2.54.The model is based on multiphase conservation of mass, momentum, and heat. The fluidized bed has been treatedas 1-D. Partial equilibrium is calculated for the free board. The calculated temperature of the hotmetal, chemistry with The the of the modelhas top gas, and the the top gas agree reported plant data. been used to study bed impure O2, height, coal the

the effects of injection of

chemistry, and process

reactivityon performance. [59]

100

Figure 2.54 Schematic diagram of the computational domains in the melter gasifier

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