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Danielly Da Silva Quaresma1 Jos Antnio da Silva Souza1, Joo Nazareno Nonato Quaresma1. Universidade Federal do Par - PRODERNA Rua Augusto Correia 01, Guam, Belm, Par, CEP 66075-110, Brazil Keywords: Bayer process, Red Mud, leaching. 1-Abstract The production of alumina from bauxite using the Bayer process generates the residue known by red mud. This material can be used as a source for concentration and recovery of valuable metals such as titanium. The greatest difficulty of concentrating titanium compounds is the large amount of iron oxide present in red mud > 30% by weight. This paper shows the extraction of the iron oxide, increasing the concentration of the titanium compounds. The red mud is leached with H2SO4 at 30% concentration and temperature range of 60C, 80C and 90C. Analysis of the leached and concentrated was made to verify the effectiveness of the iron oxide extracting process and the titanium compounds concentration viability.
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2- Introduction In the state of Para is located the Industrial Unit Alumina of North of the Brazil S/A (Alunorte), created to produce and commercialize alumina, aluminum oxide, Al2O3. The ALUNORTE with Aluminum Brasileiro S/A (Albras) and Mining Rio do Norte S/A (MRN) complete the production cycle of aluminum in the state. Although the production of alumina has a importance great for the socio-economic status, as in any area other, generates a amount large of waste, thus causing environmental impacts. Par State has produced 25 million tons of bauxite (Pinto, 2010), of which 60% were transformed into alumina plant in Par and Maranho by ALUNORTE by ALCOA, generating approximately 9,000,000 tons of waste known as Red Mud (RM). Due to the high reactivity this material is considered dangerous, and currently there is no operating process capable of reuse all the material produced at any refinery. The search for industrial processes in order to reuse these wastes can contribute to reducing the overall impact of the production process of alumina. In this context, this paper estudied, within the research line of Solid Waste valorization the mining industry and metallurgy, a process that makes possible the red mud as a source of raw material, in other words, seeks to maximize the use of red mud as raw material for concentration and or recovery of titanium compounds in both the crystalline form of anatase, rutile and ilmenite, avoiding the predatory extraction of natural resources of these materials. Applying definitely the concept of self-sustainability of the mining industry and metallurgy.
3- The Bayer process and generation of Red Mud The Bayer process was developed by the Austrian chemist Karl Joseph Bayer (1888-1892). According to Souza et al. (2010), the basics points of the Bayer process are essential according to Figure 2.1.
NaOH bauxita
DIGESTO
CLARIFICAO
Lama vermelha
PRECIPITAO
CALCINAO
alumina
Generally, the red mud containing hydroxides and oxides of iron and aluminum as major constituents, while the oxides V, Ga, P, Mn, Mg, Zn, Zr, Th, Cr, Nb, are present as traces in the waste. Thus the exact chemical composition of red mud varies widely depending on the current source (bauxite). major mineral phases identified include hematite, boehmite, gibbsite, goethite, calcite and sodalite group mineral. The red mud is typically alkaline and has very fine solid particles. 4 - Experimental Methodology The raw material was subjected to a treatment before carrying out the leaching experiments, which consisted of a process of sintering of red mud at a temperature of 900C. The sintering is performed for the oxides of iron present in red mud undergo a transformation to the magnetic phase of iron oxide, that have greater solubility in sulfuric acid, thus there will be a greater efficiency in the leaching process. The variables used are in the process according to table 4.1. To carry out the leaching process was made a leaching reactor, details of the reactor can be seen in Figure 4.1.
Tabela 4. 1- Leaching Process Variables Temperature 60C 80C 90C S/L 1/10 1/10 1/10 CH2SO4 20%-30% 20%-30% 20%-30% MLV 100g 100g 100g
The steps of the methodology used in the leaching process are presented in Figure 3.2, and a simplified scheme for obtaining the red mud generated from the Bayer process.
Figure 4.1-Leaching Reactor :(1) Condenser, (2) Mechanical Agitator, (3) Temperature Regulator , (4) Flask , (5) Heater Blanket, (6) Energy source.
Figure 4.2 - Flowchart of the experimental methodology for the leaching process.
5.1 - Analysis of Solubility Curves The leaching process carried out in this work was aimed at obtaining the solubility behavior of iron metal in solutions of sulfuric acid. Below are presented and discussed the results (solubility curves) based on the effects of the main relevant variables considered here, which are: leaching temperature and concentration of sulfuric acid. The leaching experiments were performed using sulfuric acid with concentrations ranging from 20% to 30% for 8 h with the ratio L/S of 10/1 at temperatures of 60C, 80C and 90C. It is noteworthy that the results are presented in relation to the average data of each experiment, since they were performed in triplicate.
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% Fe2O3
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0 0 30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 480
tem (m po in)
Figure 5.1-solubility curves of iron leaching with temperatures of 60C, 80C and 90C to sulfuric acid concentration of 30%.
The Figure 5.2 shows the evolution in the extraction of iron with time of leaching as a function of temperature in the range of 60C, 80C and 90C for an sulfuric acid concentration of 20%. The temperature remains the main factor for the extraction of iron, and analyzing the three solubility curves is possible to observe that the greater efficiency of the leaching process occurs at a temperature of 90C which is around 80%, to temperatures of 80C and 60 C, the efficiencies achieved are 65% and 23% respectively. Here is also observed an optimum leaching time of four hours for the experiment carried out at 90C.
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% Fe 2O 3
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tempo (m in)
Figure 5.2- Solubility curves of iron leaching with temperatures of 60C, 80C and 90C to sulfuric acid concentration of 20%.
60 55 50 45 40
% Fe2O3
35 30 25 20 15 10 5 0 0 30 60 90
TL = 90C e CH2SO4 = 30% TL = 90C e CH2SO4 = 20% TL = da LV 80C e CH2SO4 = 30% TL = 80C e CH2SO4 = 20% TL = 60C e CH2SO4 = 30% TL = 60C e CH2SO4 = 20%
120 150 180 210 240 270 300 330 360 390 420 450 480
tempo (min)
Figure 5.3-solubility curves of iron leaching with temperatures 60C 80C and 90C to sulfuric acid concentration of 20% and 30%.
Chemical analysis of red mud after leaching it is necessary to verify there was a concentration of titanium compounds in red mud. The best results of extraction of iron occurred at 90C and sulfuric acid concentration of 20% and 30%, we present only the results of chemical analysis performed for these conditions, these results can be seen in table 4.1. It can be seen in the table for the experiments performed with a constant temperature of leaching and varying the concentration of sulfuric acid (20% and 30%) the best results for the extraction of iron are those made with the highest concentration of acid (30%), providing a higher concentration of Titanium compounds in red mud, which is around 9.66% by weight.
Table 5.1-Chemical composition of red mud after leaching Red Mud (%) weight
constituents
Red Mud (%) weight CA= 20%; T= 90C 6,36 9,57 0,10 56,48 9,45 0,85 15,31
CA= 30%; T= 90C Fe2O3 TiO2 CaO SiO2 Al2O3 Na2O PF 3,24 9,66 < 0,10 62,63 7,53 0,53 14,02
6 CONCLUSIONS The application of the Bayer process waste, generated by ALUNORTE, consisting mainly of iron oxides and an appreciable amount of titanium oxide, showed a great potential to be used as a raw material alternative to titanium compounds concentration, primarily because consists in a low cost material and generated in large quantities in grain sizes and compositions defined. The red mud, Bayer process waste, generated by industry ALUNORTE, can not be used alone in the sintering process aimed at transformation of hematite to magnetite, and was not possible to
obtain compounds of iron and titanium ilmenite possibly, would allow the solubilization of titanium in sulfuric acid solution.
The leaching experiments allow us to say, based on the overall objective of this work, the optimal variables to carry out the leaching process are: Leaching temperature of 90 C and concentration of sulfuric acid 30%, and for these conditions the iron oxide present in greater amounts in the residue showed a percentage of solubility of 90% which contributed to a concentration of titanium compounds in the mud red around 9.66% by weight. The tests also show by analyzing the solubility curves that the optimum time of leaching was about four hours.
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