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JOURNAL OF IRON AND STEEL RESEARCH, INTERNATIONAL. 2006, 13(2): 06-09

Beneficiation of Titanium Oxides From Ilmenite by Self-Reduction of Coal Bearing Pellets

XU Meng ,
G U O Ming-wei, ZHANG Jian-liang

WAN Tian-ji,

KONG Ling-tan

(School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing , Beijing 100083, China)

Abstract: T h e study on the beneficiation of titanium oxides from Panzhihua ilmenites by reduction of coal bearing pellets was carried out. The iron oxides in pellets were efficiently reduced to metal iron, and titanium oxide slag beneficiated was separated from metal iron. The effect of temperature, flux and coal blending ratio on the reduction and separation was investigated, and rational parameters were determined. A new process for the beneficiation of titanium oxides by rotary hearth furnace (RHF) was proposed. Key words: ilmenite ; pyrometallurgy ; reduction; separation; titaniferous slag; coal bearing pellet

T o produce 1 t pigment from ilmenite (containing TiO, about 5 0 % ) , about 8 t waste sulphuric acid and 3 t FeS04 7 H , O waste slag are produced. Many large-scale producers of pigment are facing the pressure of environmental protection and forced t o increase the investment for treatment of these wastes. T h e replacement of ilmenite by acid soluble titaniferous slag of high grade and low impurity will eliminate the reduction of iron fines and FeS04 residuals with reduction of concentration of titanium solution and increase acidolysis productivity. T h u s , much attention has been paid to acid soluble titaniferous slag abroad. T h e slow development of acid soluble titaniferous slag production in China may be explained by two reasons. First, the acidolysis technology of acid soluble titaniferous slag is just under development domestically. Second, the technology of smelting titaniferous slag in electric arc furnace is still immature in China. Acid soluble titaniferous slag is mainly produced on large sealed submerged arc furnace with six electrodes abroad, but in China, it is on open and small-submerged arc furnace with three electrodes. T h e latter is featured by high power consumption, high cost and severe environmental pollution. Based on Itmk3 technique developed by a new
Biography:XU Meng(1973-), Male, Doctor;

process for smelting titaniferous slag by rotary hearth furnace (RHF) will be proposed. This process feeds powder materials or pellets containing ilmenite fines, coal fines and one or more than one flux. A t high temperature, FeTiOs in ilmenite is reduced by coal in RHF. T h e main factors affecting the reduction and separation of composites have been studied by present experiments, and rational process parameters have been determined.

Experimental Equipment and Method

Experiments were carried out in an electric resistance furnace heated by Si-Mo heating unit. Green pellets composed of ilmenite fines, coal fines and fluxes were put on the carbonaceous fines with size of 0 - 3 mm in a graphite box, as shown in Fig. 1. T h e graphite box with pellets was heated to 1 450 'C for 25-30 min. After being cooled, pellets were crushed and iron shots were picked out by hand. Tiny iron grains in slag were sorted out by magnet. T h e composition of Panzhihua ilmenite in mass percent (%) is TFe 31. 60, FeO 29. 25, TiO, 47.76, SiO, 1.45, Al,O, 1 . 3 3 , CaO 0.68, MgO 5.60, V 2 0 50.067, MnO 0 . 6 3 , S 0.22 and P 0.005. T h e compostion of Taixi coal in mass percent ( % ) is moisture 0. 30, volatile 8. 05, ash 2. 4 , fixed carbon
Revised Date: November 17, 2004

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No. 2

Beneficiation of T i t a n i u m Oxides F r o m Ilmenite by Self-Reduction of Coal Bearing Pellets

- 7 .

Fig. 1 Green pellets in graphite box

From Table 2 , it is clear that when Na,SO, and Li2C0, are used as fluxes, the separation is easier. Na2CO, deteriorates the separation. After cooling, most of iron was agglomerated into one or several iron shots in the size of 3-8 mm, gathered on the lower part of pellet or at the edge of pellet probably due to unevenness of hearth layer material. After the pellets were crushed, these iron shots could be picked out easily and the amount was defined as the yield of iron. But some iron still remained in slag as tiny particles and it was difficult to sort out. But in mass production, iron can be separated from slag by crushing and magnetic dressing. T h e morphology of reduced pellets is shown in Fig. 2.

89. 1 and S 0. 12. All raw materials were crushed and milled to about 0. 154 mm. T h e effects of fluxes, temperature and coal blending ratio on reduction and separation of pellets were investigated.

2.2

of temperature on reduction and Separation The effect of temperature on yield of iron is shown in Fig. 3. At 1 500 "c, while Na2SO.i and LizcO, are
Table 1 Composition of fluxes in mass percent
Flux content
10

%
LipCOs
2. 5 2. 5 2. 5 2. 5
3.0

2
2. 1

Experimental Results and Analysis

Choice of fluxes

Flux No.

NaZSOI

NazCOa
2. 5

1
2
3 4
3

5. 0
0

Table 1 shows N a 2 S 0 , , Na2C0, and Li2C0, contents in fluxes. T h e degree of separation of iron from slag after reduction of pellets at 1 450 shown in Table 2.
Table 2
Flux No. Flux content/%
10

10
10 10

7. 5
5. 0
0
0

2. 5 7. 5
9. 0

"C is

12

Degree of separation of iron from slag

Total slag mass/g Mass of iron shots/g Magnetic substance Non-magnetic substance
4. 0
3. 0
8. 0

Mass of dry pellet/g 24. 0

24. 0 24. 0 24. 0 24. 4

1
2

8. 2
7. 3
-

10

11.1
-

3
4 5

10
10

5. 0 5. 1

2. 6
3. 3

12. 2 11. 6

12

Fig. 2 Morphology of iron particles separated from slag (a) and reduced pellets (b)

Journal of Iron and Steel Research, International

Vol. 13

100

Na,SO, and Li,C0,3as fluxes

90

2
3

.r-

80

Na,SO,, Na,CO, and Li,CO, as fluxes

F 70

60 1450

1460

1470 1480 Temperature/"c

1490

I 1500

Fig. 3

Effect of temperature on reduction and separation

used as fluxes, the yield of iron reaches 9 8 % , and the content of magnetic substance in slag is the least, so the reduction rate is not the dominant factor for yield of iron. At high temperature, iron and slag are melted quickly, and the viscosity of slag is lower, so the fluidity is higher, and iron droplets are easier to aggregate and form iron shots. But, the partial replacement of Na2SO, with NaZCo3 decreases the yield of iron.

is generally believed that LizC03behaves as a catalyst in the reduction of ferriferous oxides. The melting point of C LizC03is 726 O , so it may be thoughtc5]that the alkali metal infiltrates into carbon particles and reacts with carbon: Li2C03(1)+C(s)=LizO(1)+2CO(g), L i z O ( l ) + C O z ( g ) = L i 2 C 0 3( l ) , promoting the gasification of carbon. At the same time, the addition of Li2C03 also promotes the reaction of FeO -+ Fe. However, at the experimental temperature, the gasification of carbon and the reduction of ferriferous oxides both go on very rapidly, and the catalysis is weakened greatly with highlighted fluxing action. In TiOz-Liz0 binary phase diagramC6', TiOz and Lip0 firstly form congruent melting phase LizO 3 T i o 2 C with congruent melting point at about 1 220 ' between L i 2 0 * 3 T i o 2 and Ti02. It can be seen from the phase diagram that small quantity of L i 2 0 plays a fluxing action for TiO, remarkably. And there is an optimal value for L i z O , beyond or below which the melting temperature of the binary mixture is increased. All of these are in good agreement with the experiment results.
2.4

Effect of coal blending ratio on reduction and separation of pellets

2 . 3 Effect of Li,C03 content on reduction and separation T h e displayed results in Fig. 4 are obtained at 1 450 "C with total content of Na,SO, and Li2C0, of
10%. It is shown that small quantity of L i z C 0 3can increase the yield of iron and decrease magnetic substance in slag. When the amount of LizC03is 2 % 3 % , the yield of iron is the highest. Beyond 3 % , the yield of iron is decreased, and correspondingly the content of magnetic substance in slag is higher. It

Coal in a pellet mainly plays two roles: one is the reductant, and the other is the carburizing agent of iron that decreases the melting point of iron alloy. But too much carbon particles in the pellet will retard the aggregation of iron and slag, especially iron. Accordingly, they will make the separation of iron and slag more difficult. This has been proved by the results shown in Fig. 5 . When the coal blending ratio is 8 % , the yield of iron is the highest. When it is beyond 1 2 % , the yield of iron decreases dramatically because the tiny

2 3 4 Li2C0, contenl in one pelleWo

"'

10 12 14 Coal blending ratio in one pellet!??

16

Fig. 4

Effect of Li2C03content on reduction and separation

Fig. 5

Effect of coal blending ratio on yield of iron

No. 2

Beneficiation of T i t a n i u m Oxides F r o m Ilmenite by Self-Reduction of Coal Bearing Pellets

- 9 .

iron particles are remained in slag and it is difficult to pick out.

2.5

Beneficiation rate of titanium oxides and components of slag phase The beneficiation rate of titanium oxides is 70 % 7 6 % obtained by chemical analysis, which is in good agreement with theoretical estimation. T h e X-ray diffraction of the slag phase is shown in Fig. 6. By contrast, the titaniferous slag is composed of the solid solution phase of M, O5 type ( pseudobrookite, M = T i , F e , Mg, Al, M n , Li and so on) and small amount of silicate phase. In accordance with the Ref. [7], when iron and titanium are extracted from all kinds of titaniferous and ferriferous oxide ores by reduction, the main phase of slag is usually anosvite n ( M ; + O 3 TiO, 11, which is [m(MZf 0 2Ti02 simplified as M30; type, enriched with TiOz and is easily dissolved in acid. While in existence of excess carbon, the following reaction occurred between FeO 2TiO2 and carbon in titaniferous metallized pellet : z ( F e 0 2TiO2)+5(z-2)C=2(Fe,-, Ti,05)+ 3 (5- 2 ) Fe+ 5 (z- 2 ) CO (2<z<3)

iron n u g g e t s similar t o pig iron in composition a t 1 400-1 450 "C. As long as the furnace temperaC ture can be raised to 1 450 ' or higher, R H F will be able to meet the technical requirements of smelting the titaniferous slag.

Summary

(1) T h e optimal parameters of reduction and separation of coal bearing ilmenite pellets are: adding Li,CO, of 2%-3% and Na,SO, of 7%-8% as fluxes, coal blending ratio 8% - 12 % and temperature 1 450 ' or higher. T h e beneficiation rate of C titanium oxide slag can be up t o 70%-76%. ( 2 ) T h e fluxes play critical role for separation of iron from slag. Especially, adding Li,CO, by 2 % - 3% can decrease the separation temperature by about 100 "C. (3) T h e main phase of beneficiation slag is the solid solution phase of M,Oj type called as anosvite.
References:
Osamu Tsuge, Shoichi Kikuchi, Koji Tokuda, et al. Successful Iron Nuggets Production a t Itmk3 Pilot Plant [A]. 2002 Ironmaking Conference Proceedings [C]. USA: Iron and Steel Society, 2002. 511-519. Larry Lehtinen, Steven D Rutherford. T h e Mesabi Nugget Project-New Iron Making Technology of the Future [A]. ISSTech 2003 Conference Proceedings CC]. USA: Iron and Steel Society, 2003. 1043-1048. Meissner S , Kobayashi I , Tanigaki Y , et al. Reduction and Melting Model of Carbon Composite Ore Pellets [J]. ISIJ Int, 2003, 3 0 ( 2 ) : 170.176. Yoshitaka SAWA, Tetsuya YAMAMOTO, Kanji TAKEDA, et al. New Coal-Based Process to Produce High Quality DRI for the E A F [J]. ISIJ Int, 2001, 41(Supplement) : S17-S21. GUO Xing-min, T A N G Hong-fu, ZHANG Bi-sheng, et al. Study on the Catalysis Mechanism of LizC03 for Reduction of Iron Ore Pellet With Carbon [J]. Acta Metallurgica Sinica, 2000, 3 6 ( 6 ) : 638-641 (in Chinese). Ernest M Levin, Carl R Robbins, Howard F McMurdie. Phase Diagrams for Ceramists [MI. Ohio: T h e American Ceramic Society, 1964. CUI Shu-xian, LI Ji-zhong. Effect of the Constituents of the Electric Arc Furnace Slags Containing Titania on Their AcidSolubility [J]. Iron Steel Vanadium Titanium, 1995, 16(3) : 57-63 (in Chinese).

Propose of Developing RHF Smelting Titaniferous Slag Process

R H F has been successfully applied to production of direct reduction iron domestically and abroad. Moreover, Itmk3 process has passed the pilot experiment in Japan and America, which produces pebble iron or

8000

6000

t t
10

Fig. 6

X-ray diffraction pattern of titaniferous slag phase