NATIONAL INSTITUTE OF TECHNOLOGY

JAMSHEDPUR

Category: Mitigate the detrimental effect of alkali in iron ore

sinter through sinter making route
Proposal: Produce low alkali sinter (<0.1%) for blast furnace

Under the guidance of-

Ms. Moni Sinha
Principal Scientist
Agglomeration Research Group (R&D)
TATA Steel

Submitted by-
Aashi
2014UGMM002
B.Tech (Hons.), 7th Semester
Metallurgical and Materials Engineering
NIT Jamshedpur

**This research is a copyright of TATA Steel Limited and is performed in accordance with
its norms. Use by any third party is restricted.
1. Introduction
Sintering is a process by which a mixture of iron ores, fluxes and coke, with a particle size of
-8mm, is agglomerated in a sinter plant to manufacture a sinter product of a suitable
composition, quality and size (12-35 mm) to be used as burden material in the blast furnace.
Sinter Composition-

Component Fe SiO Al2O3 CaO Mg Na2O + K2O

2 O

Content 60-65 4-5 1.8- 7.5-8.5 1.6- 0.2-0.5

(%) 2.5 2

The average alkali content (Na2O + K2O) in the final sinter is about 0.2-0.5%, K2O being in
higher amount, which is undesirable in blast furnace.

1.1. Effect of alkali in Blast Furnace

 Increased alkali Recirculation
 Decreased hearth temperature and increased top gas temperature
 Reduced refractory life
 Decreased bed permeability
 Scaffold formation
 Deteriorated slag properties
 Catalyses coke gasification

Recommended alkali that can be input in blast furnace is <0.1%

2. Literature Review

Methods Description Benefits Limitations

Beneficiation Mixing of ores ~20% removal of alkali. Expensive

Leaching with NH4Cl, Time Consuming
citric acid

Biological Leaching with ~20% K2O removal Inefficient in

Method Aspergillus niger Eco-friendly alkali removal
Time consuming

Use of CaCl2 Volatilization of NaCl, ~90% K2O and ~60% Corrosive for
KCl vapours by CaCl2 Na2O removal refractories
addition.
 Olivine Alkali removal through Increased alkali content Partial removal
addition with BF slag by using olivine in BF slag of alkali
BF charge (dunite/pyroxenite in Reduced CO2 emission
India) as fluxing agent. Reduced coke rate

3. Challenges
3.1. Alkali as oxides
 Increasing the vaporization rate of Na2O and K2O during sintering process
 Higher reducing atmosphere, compared to normal sintering process, required for
formation of Na and K vapours
3.2. Alkali as silicates
 Removal of alkali as silicates not feasible at sintering temperature
 Inhibit the formation of stable sodium and potassium silicates or other stable
phases in presence of carbon

Hence, the main challenge is to maintain a reducing atmosphere without excessive melting of
mix, as fusion will result in the formation of stable silicate phases.

4. Aim
 Leaching of iron ore using citric acid
 Formation of (K)Na2O.B2O3 and (K)Na2O.SiO2.B2O3 phases having lower vaporization
temperatures (1100-12500C)
 Alkali reduction using CO gas

5. Theory
 Leaching
o Citric acid contains 3 carboxyl groups.
o C6H8O7 = 3H+ + C6H5O73-
o C6H5O73- forms stable complexes with K+ and Na+ cations.
 Alkali silicates
o Stable at sintering temperatures (1100-13000C).
o Reduction by carbon alone not feasible.
Na2SiO3 + C  2Na + SiO2 + CO (17000C)
K2SiO3 + C  2K + SiO2+ CO (>1550"C)
 B2O3
o Formation of K/Na, K/NaBO2, (K/NaBO2)2 vapours from Na2O-SiO2-B2O3
melts
Na2O(l) + B2O3(l)  NaBO2(l)  NaBO2(g) or (NaBO2)2(g)
Na2O(l) + K2O(l) + 2B2O3(l)  2NaK(BO2)2(l)  2NaKBO2(g)
o Temperature range: 1100-12500C
o Molar ratio, (K)Na2O/B2O3>1, else HBO2 vapour forms instead of (K)NaBO2.
 Pre-Reduction using CO gas circulation
 Na2O + C  2Na + CO (at 10200C)
K2O + C  2K + CO (at 8150C)
Na2O + CO  2Na + CO2 (900-11000C)
K2O + CO  2K + CO2 (7600C)

6. Hydrometallurgy
6.1. Experimental
 Material Preparation
o Ore (-1+0.5mm, -0.5+0.25mm)
o Citric acid (1M, 1.25M, 1.5M)
 Solution preparation
o 100g ore in 100 ml citric acid solution.
o Incubation
o Temperature- 250C
o Duration- 5 days
o Occasional stirring.
 Ore Extraction
o Filtration
o Washing with water (4 times)
o Drying (1500C, 1h)

6.2. Results
Final total alkali concentration (Na2O + K2O) as low as 0.07% was achieved.
Limitations:
 Time consuming (~5days).
 Expensive (~₹1.5lakh/tonne of iron ore).
 Increase pollution load in water resources.
 Stable phase formation, not recyclable.
 Not efficient for coarser particles.

7. Pyrometallurgy
7.1. Raw Materials
Khondbond iron ore: Fe (t)- 62%, Na2O + K2O ~ 0.3%
Coke breeze: Na2O + K2O ~ 0.1%
7.2. Lab Scale
Experimental
  Experiments were conducted in tube furnace at specified CO flow rates for a
few hours.
 The Coke and Colemanite content was varied at two different temperatures.
 The initial and final samples were sent for chemical analysis and compared.
 The samples were also analysed using SEM and XRD.

Observations

 Addition of Colemanite didn’t have any appreciable effect on alkali content.

 For high coke content (>2%), the process was not efficient.
 Alkali was found to go into stable silicate phases upon excessive melting at
higher temperatures.

7.3. Bench Scale

Experimental
 Experiments were conducted in sinter pots using the best results from the lab
scale experiments.
 Iron ore and coke (10 kg total) were mixed in mixed drum with 8-9% moisture
 The sample was charged in sinter pot and ignited.
 Duration of combustion was ~5 mins, in between which CO gas was
circulated.
 Negative pressure was 1500 mmwc.
 The process was repeated for sinter base mix.
 All the samples were sent for chemical analysis and compared.
 The samples were also sent for SEM and XRD analysis.

Observations

 The reduction trend observed in bench scale experiments was the same as in
lab scale experiments.
 There was no appreciable decrease in alkali content when sinter base mix was
used.
 The reason for the above could be the high coke content, causing excessive
melting, or high flux content, facilitating alkali silicate formation.

7.4. Result
 The alkali content was brought down to as low as 0.03% from 0.3%.
 Efficiency ~ 90%
 The process was not effective for sinter base mix.

8. Conclusion
 Dealkalization by leaching can be done, but is time consuming and expensive.
 Sinter flue gas can be used as source of CO gas.
 Reuse of reducing gas can bring down the alkali to 0.0328% (from 0.3%).
 High alkali containing iron ores can thus be utilized.
9. Benefits
 Decreased overall coke consumption.
 Reduction in CO and CO2 emissions.
 Effective heat utilization of sinter flue gas.
 Reuse of flue gas >> Environmentally sustainable.

10. Further Work

 Plant scale trials and process optimization using flue gas
 Study the impact of boron on sinter phases

11. References
 Method for estimation of na2o and k2o in ores, fluxes, coal and coke ash by inductively
coupled plasma-atomic emission spectroscopy. S. Sarkar1 and v.v.v. Subrahmanyam2
 Alkaline carbonates in blast furnace process. P. Besta, a. Samolejova, r. Lenort, k.
Janovska, j. Kutač, a. Sikorova.
 The softening properties of alkali-containing iron oxide briquettes under reducing
conditions by C. A. Pickles.
 The kinetics of gasification of alkalis from the gangue in iron ores by calcium chloride,
w. Lapkowsky and w.-K. Lv.
 Appropriate technology parameters of iron ore sintering process with flue gas
recirculation. Xiaohui fan, zhiyuan yu,* min gan, xuling chen, tao jiang and hongli
wen.
 Development of the process for producing pre-reduced agglomerates. Machida
satoshi*1 sato hideaki*2 takeda kanji*
 Agglomerates containing olivine for use in blast furnace, Ellenbaum et al.
 Process of using olivine in a blast furnace, inventors: frank h. Ellenbaum, hinsdale,
Richard ciesco, grifith, ind.
 Usus rationis ad sinistram cerebri media est nobis vertebrate
 Value-in-use analysis of using olivine flux for agglomerate in iron-making processes,
Wang chuan, he zhijun, mousa elsayed, sundqvist lena, Wikström jan-olov.
 Iron ore sintering. Part 1. Theory and practice of the sintering process.
 The effect of harmeful elements in production of iron in relation to input and output
material balance. P. Besta, a. Samolejová, k. Janovská, r. Lenort, j. Haverland
 Effect of alkalies on the performance of blast furnace. By a. A. El-geassy, k. A.
Shehata, M. I. Nasr and S. S. Fakhoury.
 An investigation on the removal of alkali from sinter mix with the chlorinating
evaporation method. Mustafa boyrazli.
 The influence of simultaneous adsorption of Potassium and sodium vapours on coke
structure and performance. J. Zhong, j. Zhang, k. Li, z. Liu, C. Wang, D. Zhao & H.
Zhang.
 The removal of alkalis from iron ores by chloride volatilization, Suheyla aydin and
feridun dike
 S Afr J Sci. 2010; 106(3/4), Art. #158, 5 pages
 Canadian Metallurgical Quarterly, Vol. 29, No.3, pp. 213-216, 1990.
 Ellenbaum et al.: Patent US3966456