Carbothermic Reduction Kinetics of Ilmenite Concentrates Catalyzed by Sodium Silicate and Microwave- Absorbing Characteristics O
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Available on line at Association of the Chemical Engineers of Serbia AChE www.ache.org.rs/CICEQ Chemical Industry & Chemical Engineering Quarterly 19 (3) 423−433 (2013) CI&CEQ WEI LI1,2 CARBOTHERMIC REDUCTION KINETICS OF JINHUI PENG1 1 ILMENITE CONCENTRATES CATALYZED BY SHENGHUI GUO SODIUM SILICATE AND MICROWAVE- LIBO ZHANG1 GUO CHEN1 ABSORBING CHARACTERISTICS OF HONGYING XIA1 REDUCTIVE PRODUCTS 1 Key Laboratory of Unconventional Carbothermic reduction kinetics of ilmenite concentrates catalyzed by sodium Metallurgy, Ministry of Education, silicate were investigated; the reduction degree of ilmenite concentrates Kunming University of Science and reduction reaction was determined as R = 4/7(16y + 56x)(ΔWΣ - f W)/(16y + Technology, Yunnan, China A-P 2Faculty of Science, Kunming + 56x + 112). The results show that the reaction activation energy of initial University of Science and stage and later stage is 36.45 and 135.14 kJ/mol, respectively. There is a great Technology, Yunnan, China change in the reduction rate at temperatures of 1100 and 1150 °C; the catal- ysis effect and change of reduction rate were evaluated by TG and DSC curves SCIENTIFIC PAPER of sodium silicate. Microwave-absorbing characteristics of reduction products were measured by the method of microwave cavity perturbation. It was found UDC 544.47/.478 that microwave absorbing characteristics of reduction products obtained at ° DOI 10.2298/CICEQ120421077L temperatures of 900, 1100 and 1150 C have significant differences. XRD characterization results explained the formation and accumulation of reduction product Fe, and pronounced changes of microwave absorbing characteristics due to the decrease of the content of ilmenite concentrates. Keywords: sodium silicate; ilmenite concentrates; catalytic reduction; kinetics; microwave absorbing characteristics. The mineral ilmenite (FeTiO3) is the main source Researches have shown that carbothermic reduction of titanium dioxide which is widely used as a white of ilmenite at temperatures below 1200 °C produces pigment. The common treatment method is thermal metallic iron and reduced form of oxides (TinO2n-1) reduction of ilmenite to form TiO2 and elemental iron [4,5]. Carbothermic reduction of ilmenite and rutile followed by a leach to remove the iron. The reduction was investigated by Welham and Williams [6] at tem- of ilmenite concentrate plays an important role in the peratures up to 1500 °C, indicating that the reduction titanium industry. It has been well documented that of rutile was found to proceed through a series of ilmenite concentrate usually needs high reductive oxides TinO2n-1 until the formation of Ti3O5. Kucuk- temperature or needs additives to improve its reac- karagoz [7] investigated the reduction of ilmenite tivity when it is directly reduced [1,2]. Over the past concentrate with graphite under argon gas between several decades, many research studies have been 1250 and 1350 °C, showing that reduction rates done on the mechanism and kinetics of the reduction increased with increasing temperature and decreas- of different ilmenite. Wouterlood [3] investigated the ing particle size. Dewan [8] studied carbothermal reduction of ilmenite with carbon at temperatures of reduction of ilmenites of different grades and synthe- 900 to 1200 °C and found the reaction consisted of tic rutile in different gas atmospheres. The carbother- two stages: the fast first stage indicating the reduction mal reduction of primary ilmenite concentrate was of ferric to ferrous iron, and a slower second stage in faster in hydrogen and occurred at a lower tempe- which ferrous iron was reduced to metallic iron. rature than in argon and helium. The reduction in argon and helium had about the same rate and extent Correspondence: J. Peng, Faculty of Science, Kunming Univer- [8]. Eungyeul [9,10] researched the reduction of tita- sity of Science and Technology, Yunnan,650093, China. nia-ferrous ore by H2 and CO; Satoshi [11] also inves- E-mail: [email protected] tigated the reduction kinetics of natural ilmenite ore Paper received: 21 April, 2012 Paper revised: 10 August, 2012 with carbon monoxide and found the reduction rate Paper accepted: 13 August, 2012 423 W. Li et al.: CARBOTHERMIC REDUCTION KINETICS OF ILMENITE… CI&CEQ 19 (3) 423−433 (2013) increased with increasing temperature, the rate and making and activated carbon production, and micro- the degree of reduction depended on the formation of wave assisted waste management, etc. [22-31]. a metallic shell of iron [9-11]. The reactivity of ilmenite For microwave processing of ilmenite, Itoh et al. can also be improved by using a pre-oxidization described the microwave oxidation of rutile extraction process, increasing the rate of ilmenite reduction and process, in which rutile is extracted from a natural the rate of leaching [12-15]. Zhang and Ostrovski [15] ilmenite ore by oxidation and magnetic separation investigated the effects of pre-oxidation and sintering followed by leaching with diluted acid [32]. Kelly and on the phase composition, specific surface area, mor- Rowson investigated microwave reduction of oxidized phology and reducibility of ilmenite concentrates. It ilimenite concentrate [33]. Tong et al. evaluated the was demonstrated that both pre-oxidation and sinte- economic values of industrial applications of carbo- ring increased the temperature required to reduce thermic reduction of metals oxide by microwave heat- titanium oxides. Pre-oxidization is now a broadly ing, showing that the cost is lowered about 15-50% adopted practice in the processing of ilmenite ore for compared to that of conventional method [34]. Cut- production of TiO2 pigment and metallic titanium. more et al. investigated dielectric properties of some Wang and Yuang [16] described the reduction degree minerals [35]. Microwave absorbing characteristics of and rate of Bama ilmenite concentrate by graphite at ilmenite concentrate with different proportions of car- temperatures from 850 to 1400 °C. The reduction bonaceous reduction agents were investigated by the degree and reaction rate of the ilmenite increased authors’ group [20], which further confirms the feasi- with increasing temperature. The higher the tempe- bility of microwave reduction of ilmenite concentrate. rature was, the faster the reaction rate was. The All of these investigations present encouraging results. reduction degree of the ilmenite decreased due to the However, to the best of our knowledge, there is presence of impurities. little information about carbothermic reduction kinetics The ilmenite deposit in Panzhihua region, of ilmenite concentrate by using catalyst and micro- Sichuan, China accounts for 35% of the titanium wave absorbing characteristics of reactants and pro- resource in the world, and for approximately of 92% in ducts during microwave irradiation, resulting in diffi- China [17]. So, it is very important to utilize the ilme- culty of investigations on the interaction mechanism nite resources efficiently for the development of the between microwaves and materials, which limits the titanium industry. However, due to the higher contents application of microwave heating technology in indus- of CaO and MgO and complex mineralogy in ilmenite try. So, there is an urgent need to investigate micro- in Panzhihua region, it is very difficult to upgrade the wave-absorbing characteristics of materials and accu- ilmenite to titanium-rich slag, which limits the develop- mulation of data of dielectric properties, in order to ment and utilization of ilmenite deposit in Panzhihua prompt applications of microwave heating in all diffe- region; it is urgent to develop new processing techno- rent kind of fields. logies of ilmenite concentrates [13,18-20]. The objective of the present study is to inves- In recent years there has been a growing inte- tigate carbothermic reduction kinetics of ilmenite con- rest in microwave heating in mineral treatment. centrate synergistic catalyzed by sodium silicate and Advantages in utilizing microwave technologies for microwave-absorbing characteristics of reductive pro- processing materials include penetrating radiation, ducts measured by the method of microwave cavity controlled electric field distribution and selective and perturbation. volumetric heating [21]. Because of these advan- tages, a number of potential applications of micro- EXPERIMENTAL wave processing materials have been investigated, such as microwave assisted ore grinding, microwave Materials assisted carbothermic reduction of metal oxides, mic- The raw material, ilmenite, was obtained from rowave assisted drying and anhydration, microwave Panzhihua (Sichuan province, PR China). The chemi- assisted mineral leaching, microwave assisted roast- cal compositions of ilmenite and proximate analysis of ing and smelting of sulphide concentrate, microwave coke were listed in Tables 1 and 2, respectively. assisted pretreatment of refractory gold concentrate, It can be seen from Tables 1 and 2 that both microwave assisted spent carbon regeneration, coke ilmenite and coke contain volatiles; especially for Table 1. Chemical compositions of ilmenite concentrate Component TFe TiO2 CaO MgO SiO2 Al2O3 S Content, mass% 32.18 47.85 1.56 6.56 5.6 3.16 ≤0.1 424 W. Li et al.: CARBOTHERMIC REDUCTION KINETICS OF ILMENITE… CI&CEQ 19 (3) 423−433 (2013) Table 2. Proximate analysis of coke Water content Ash Volatile Fixed carbon Total sulfur Calorific value 1.93% 27.80% 1.41% 70.80% 2.68% 23.64 MJ/Kg coke, the amount content of volatile, sulfur and water