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This presentation will show the logic and experimental techniques which revealed the mechanism of Reduction Swelling of Iron Ores in a ground breaking research work done in Germany and created a sensation some years ago . Many of its results have been published, and it has been quoted extensively. But some important observations and new questions which came up with it remain a mystery and continue to challenge our imagination even today. They are topics for advanced research for developing new technologies of huge economic importance.
The accepted limit in DR and Bf grade pellet is 20% ( ISO 4698 free swelling test method ). So , we can imagine what will happen with 150 % or 400% swelling in DR and Blast Furnace Process !
Reducing Gases
CVRD 6th DR Seminar 26-30/11/2007 Belo Horizonte
Ore/ Pellet
Hot Blast
Electrical furnace heats the alumina tube which holds the pellet sample. One end of tube has quartz glass window and inlet for gases. Other end has thermocouple and exit for gases.
CO, CO2, H2, N2 from gas cylinders via Rotameter , set of valves and safety devices supply gases to alumina tube. Hartmann Brown URAS continuous CO2 gas analyzer plotted CO2 in exit gases indicating progress and end of reduction reaction.
Thermocouple touching the pellet measured isothermal reduction temperature. A camera was used to take images of pellet through the quartz glass window at close time intervals. After each test , diameter was read from images and volumes calculated . % Swelling = [(V2-V1)/V1]x 100.
Test Series 2
Now that we know how to make this phenomenon manifest itself in highest form , i.e. the highest swelling conditions, we can investigate the reason for swelling . This makes observations easier compared with a low swelling sample where everything is in smaller dimensions and so is difficult to observe accurately whats going on inside . The same logic is applied for studying other phenomenon- example : sun-spots are studied when solar activity peaks in the 11 year cycle!
find out during which step of Hematite reduction to Iron , swelling happens.
We know that in practice, reduction proceeds Topochemically. That means , when CO molecules hit the pellet , reduction happens from surface to center of pellet . There are 3 transformations . 1. Hematite to Magnetite . 2.Magnetite to Wustite 3. Wustite to Iron .
Topochemical Reduction
If we stop reduction mid-way and look at the cross section- we see 4 layers: outer layer of Iron, next is Wustite, then Magnetite and a core of un-reduced Hematite. All 4 layers happen same time till whole pellet is completely reduced to Iron.
Fe FeO Fe3O4 Fe2O3
CO 850 C
So the Question is: Which reduction step is causing Swelling ? 1, 2 , 3 or all 3 steps.
Fe2O3 1
Fe3O4 2
FeO
Fe
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How to do Step-reduction ?
Bauer Glaessner Diagram shows equilibrium between Iron, Carbon and Oxygen . Read CO/CO2 ratios from it and make each step of reduction happen on command .
to Fe
Fe2O3
Fe3O4
FeO
Fe
Pellet
Pellet
Pellet
DRI
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reduction step.
Result: No swelling in first 2 steps. Abnormal Swelling happened when Wustite was reduced to Iron in the 3rd Step.
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Hematite to Wustite
Wustite to Iron
After flushing system including URAS with N2, 100% CO sent in to reduce Wustite to Iron.
Camera took images in both Steps. CO2 plot showed End of each step .
Swelling happens from point 1 to 2 of the bend. Why ? What is happening there?
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Question 1: Why does it happen? Question 2: When does it happen? Question 2 was answered with Step Reduction.
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Recap of Findings
Ore X has Maximum Swelling tendency
Maximum Swelling is with 100% CO at 850 C reduction. Ore Y has least swelling tendency H2 reduction does not cause abnormal swelling
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Consider 3 oxide particles inside a pellet. After reduction , iron separates as whiskers and pushes particles from each other increasing diameter d1 of pellet to d2 of DRI. DRI Swells abnormally(100 to 400%) , is highly porous, spongy, soft .
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X /CO/1000 C
X /H2/ 850 C
it was modified . A Leitz Hot-Stage Type 850 was modified to pass CO/H2 through it. A 5mm by 3 mm thick piece of ore was chipped from X and Y as samples. Surface of sample is unpolished , rough. Monocular-microscope has low depth of focus, will give blurred image. So, a Stereo microscope was used to , observe surface changes , the maximum magnification possible was only 300 .
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CVRD 6th DR Seminar 26-30/11/2007 Belo Horizonte
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This is the first time in Ferrous Metallurgy a live observation of iron ore reduction was done . The record of events and images of iron formation on Wustite surface made a sensation in the research circle and triggered a number of research in this direction.
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Solar prominences are loops of plasma anchored to the solar surface . Magnetic fields are thought to be causing solar prominences. Exact reason is not known. Why iron whiskers form loops anchored to Wustite surface? We dont know. Can a strong magnetic field affect morphology of iron formation ? These are unsolved Mysteries !
CVRD 6th DR Seminar 26-30/11/2007 Belo Horizonte
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Questions
In Science , when one question is solved , many New Questions come up with it. Questions which surfaced in this research work are : 1. Is abnormal swelling really bad? When outer iron layer is full of whiskers , it opens up, helps rapid gas-solid contact to unreduced layers - rate of reduction is faster. If iron layer is sintered and continuous , gas-solid contact is via cracks, open pores or by slow diffusion process through the compact iron layer reduction rate is slow-more unreduced core.
CO
2 . In DR , can we use 850 C instead of 950 C and save energy / t DRI ? 3. Can we invent a process to take advantage of Abnormal Swelling phenomenon ?
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More Questions !
4 . Highly swollen DRI is very reactive , it can be good catalyst for self-reforming inside DR reactor, in Haber-Bosch process for nitrogen extraction from air for artificial fertilizer . Can we develop better catalyst promoting iron formation in the form of whiskers? 5. Highly swollen DRI is soft and spongy and so easy to make good HBI . Can we commercially produce highly swollen DRI to produce highly compacted HBI briquetts with less energy.
6 .Whisker is believed to be single crystal free of dislocations, possess high strength. Can we grow long iron whiskers to make high strength composite materials ?
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0.2mm
CVRD 6th DR Seminar 26-30/11/2007 Belo Horizonte
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Author :Mukundan Ponthenkandath from Kerala State, India, based on his PhD Thesis at RWTH-Aachen, Germany, July 1971
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