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Submitted by:
Asif khan
&
Waleed Subhan
(BS Physics Students)
DEPARTMENT OF PHYSICS
UNIVERSITY OF PESHAWAR
CHAPTER II
LITRATURE REVIEW
1.1
Chromite ore:
The chemical formula of chromite ore is FeO.Cr 2O3 with Cr/Fe ratio as 2:1.Chromite ores are
basically classified on the basis of Cr2O3 content and Cr to Fe ratio. Naturally occurring chromite
minerals tends to have a spinel structure, which is characterized by the partial substitution of
Mg2+, Ca2+ or Mn2+ for Fe2+ and Al3+ or Fe3+ for Cr3+ with the general formula (Fe2+, Mg2+, Ca2+)O.
(Cr3+, Al3+,Fe3+)2O3 [1]. Highest-grade chromite have Cr/Fe ratio more than 2 containing
minimum of 46 to 48 wt% Cr2O3. Chemical and refractory-grade chromite typically have Cr/Fe
ratios ranging from 1.4 to 2.0. Chemical-grade (high-iron) chromite contain large amounts of
iron often results in Cr/Fe ratios of close to 1, absolute amount of contained chromium ranges
from 40 to 46 wt % Cr203. Low-grade chromite have low Cr/Fe ratios and contain relatively
small amounts of chromium. Refractory-grade chromite contain relatively large quantities of
Al203 (greater than 20 wt %) and have Cr203+ Al203 level more than 60 wt % [2].
1.2
Knowledge about particle size and distribution is essential for a wide variety of industrial
processes. To recover minerals in the mineral processing industry, an ore must be ground to
produce liberated grains within the size range defined. Mineral recoveries from a concentrator
can often be improved by utilizing mineralogical studies that affect mineral beneficiation. In
order to improve metal recovery of economic minerals in beneficiation, the necessary
quantitative mineralogical data can be obtained by developed image analyzer [3], cone beam Xray microtomography system has been used for the quantitative analysis of multiphase minerals,
including grain size distribution, interfacial area, textural information [4]. The use of an image
analyzer in mineral processing involves analyzing unbroken ore pieces to predict how the
minerals might behave during grinding and processing, and analyzing ground ores and
concentrated products to determine how the minerals respond to processing [3]. The first step in
studying the unbroken ore is to identify minerals and their quantitative appraisal in the ore. The
second and the most important step is size analysis for establishing size distribution.
2
Higher value of Cr content increases the significance of ore, but due to the presence of impurities
in the form of silicates, oxides, hydroxides which reduces the value of the ore. To analyze the
impurities present in chromite ore was collected from Prangghar (Mohmand agency), Pakistan
[5]. Table 1 shows the minerals of different sorts present in chromite ores [6].
1.3
Phase analysis:
The XRD data for the sample showed mainly 3 major peaks as shown in Figure 1. The EDX
analysis carried out were in agreement with XRD for the major compound, but some impurity
phases were also detected [5]. The pattern was matched with magnesio-chromite-ferroan ((Mg,
Fe) (Cr, Al)2 O4) ICDD card # 09-0353.According to the ICDD card data the spinel under
investigation has a cubic structure and almost all the iron is in form of Fe 2+ [6] however, a slight
difference between the d-values of the first peak and that of the database was observed. The
difference could be attributed to the change in the geological location of specimen used in
ICDD database, as it has been reported to be from Cribou Canada having the composition:
Cr2O3= 55.51%, Al2O3= 14.03%, Fe2O3= 3.79%, FeO= 11.35%, MgO= 14.83% and minor Si, Ti,
Ca and Mn related compounds.[7]
Figure 1.
The XRD pattern of the Mohmand agency chromite, the data has possible match
1.4
Microstructural analysis:
MMI showed four different type of grain morphologies marked with G, H, I & J showing a
different phase for each. Figures 3(b,d) and 3(a,c) show the metallurgical microscopy images and
SEIs of the same area respectively. MMI of samples when compared with SEM/EDX analysis
revealed that both G and H represented the same phase. The difference in grain morphology
(grain G being more continuous than H) might be due to over etching of one region with respect
to other. EDX of grains I and J showed them as impurities but of different sort, this could also be
seen in color contrast of SEIs Figure 2(a, b) as I was darker and J had whitish touch. EDX
analyses of each grain in Figure 2(a, b) are given in Table 2 . From XRD, but based on
SEM/EDX the impurities could be mainly attributed to silicates family with one of them being
uvarovite [5].
Figure 2 (a,c) and (b,d) showing the SEI and MMI of the same regions respectively. EDX analysis
suggested that the grains G and H represent chromite ore and I represent silicate impurities
5
The chemical analysis of chromite ore samples exploited from Philippines obtained from
Bluestar Yima Chrome Chemical Materials PR China is shown in table 3. The sample was
crushed and dry-sieved to four particle-size fractions (0.0450.063, 0.0630.075, 0.0750.090,
0.0900.150 mm), and then dried overnight at 80 C. The Cr2O3 and Fe2O3 content of each size is
given in table 4. All experiments were performed with the 0.0450.063 mm. The potassium
hydroxide used in this work is of analytical grade and commercial pure oxygen is used in this
experiment [8].
Table 4 Cr2O3 and FeO content in different size of Philippine chromite ore.
The mineralogical analysis result of the Philippine chromite ore indicates that the sample mainly
consists of (Fe, Mg)(Cr, Fe)2O4 (Fig 3). The morphology of chromite ore was investigated by
scanning electron microscopy (SEM). Several important features can be observed. (1) The solid
particles have a compact surface (Fig. 4) and (2) The main elements including Cr, Fe and Al are
uniformly distributed in the chromite ore (Fig. 5), suggesting that chromite ore has homogeneous
structure [8].
Table 5 The Physical and Chemical Properties of South African Chromite Ores.
Figure 6. The XRD pattern of the South African chromite ore. The intensities are in
arbitrary units (AU).
9
Figure 7. The microstructure of the chromite ore. Light gray phases are the chromite
minerals
10
Figure 10.
Samples of chromite ores from South Africa (SA-1), India (ICO-1), and China (CCO-1) were
used for experiments. The main differences between the three types of ores are apparent from
their physical and chemical properties, summarized by comparing the chemical analysis in Table
7 and the X-ray diffraction (XRD) patterns shown in Figure 13. In the South African ore, the
chromite spinel is predominant and the silica content is less than 1 wt%. By comparison, the
Indian ore, in addition to chromite spinel, also consists of the gibbsite and Fe-rich sesquioxide
solid solutions, with silica at less than 1 wt%. The Chinese chromite, on the other hand, was
found to have approximately 6 wt% SiO2 in the form of pure SiO2 and forsterite (Mg2SiO4)
phases. Neither of these two phases are present in the Indian and South African ores. The
scanning electron microscopic examination of ores also revealed a considerable variation in the
chemical compositions of chromite grains in the Chinese ore, as compared to the average
compositional variation among the grains of the South African and Indian chromite spinels. The
overall chemical analysis of chromite ores was carried out using the X-ray fluorescence
spectrometric technique after the loss-on-ignition (LOI) measurements at 1298 K. When the
Chinese and South African ores were heated in air for LOI analysis, both samples gained weight
due to the oxidation of FeO to Fe 2O3, whereas a major weight loss was observed in the Indian ore
due to the release of water of crystallization during the thermal decomposition of gibbsite to
constituent oxides [11].
14
Table 7. Physical and Chemical Properties of South Africa (SA-1), India (ICO-1), and China
(CCO-1) Chromite Ores
Figure 13. The XRD patterns of the South Africa (SA-1), India (ICO-1), and China (CCO-1)
chromite ore samples.
15
1.5
16
Calcium carbonate is added to increase heat of the reaction some calcium chromate is formed
during the process and is mostly decomposed by excess soda. The red hot roasted product (frit) is
transferred to wash tanks where hot water is carefully added this flooding give rise to a strong
exothermic reaction, as a result sodium mono chromate is leached out and the liquor run off and
is treated according to special treatments. In order to obtain dichromate, the mono chromate
liquor is treated with dilute sulphuric acid (H 2SO4) in special tanks. The reaction proceeds as
[15].
4. 2 Na2CrO4 + H2SO4 Na2SO4 + Na2Cr2O7 + H2O
The sodium sulphate is less soluble then the dichromate and much of it separates out and is
removed more sodium sulphate separates and is removed. The final mother liquor contains the
dichromate which crystallizes out on concentration. In order to obtain potassium dichromate a
concentrated solution of potassium salt (e.g potassium chloride) is added to a concentrated
solution of sodium dichromate. Potassium dichromate is precipitated immediately. Another
chromium compound is chromic acid (CrO3) is prepared by adding strong sulphuric acid to a
concentrated solution of potassium dichromate, the reaction is given as [15].
17
Figure 14. Illustrate flow sheet of traditional production process for chromic oxide (Cr2O3)
18
1.6
A green manufacturing process for chromium compounds has been developed by the Institute of
Process Engineering, Chinese Academy of Sciences [17], with the design objective of eliminating
pollution [18] the green process includes continuous oxidization of chromite ore in a sub molten
salt medium at 300 C coupling of reaction and separation, recovery, and recycling of the
reaction medium and comprehensive use of the multiple components in chromite ore. The
essence of the green process is that traditional oxidation roasting of chromite ore with sodium
carbonate at 1200 C is replaced by continuous liquid-phase oxidation of chromite ore in the sub
molten salt medium at 300 C in a multiphase reactor. at the source The new cleaner process is
based on the principles of cleaner production and industrial ecology [19], and aims to achieve the
3Rs (Reduce, Recycle, Reuse) objectives Combining environmental and economic benefits, the
goals of comprehensive use of resources, recycling of reaction media, and zero emissions should
be achieved in the green process. Figure 15 illustrates the main design idea of the proposed new
green process, according to the reactions (6,7,8,9,10) [16].
Figure 15. Schematic idea of the proposed green manufacturing process for chromium
compounds.
19
1.6.1 To Reduce:
A new reaction path (reaction 6, 7, 8) was designed and no solid additives were needed in the
oxidation of chromite ore, the amount of waste residue remaining following leaching was
remarkable reduced. The reactants such as (CO2) (reaction 9) and carbon black (C) (reaction 10)
we employed to convert the semi-finished products to the final products, minimizing possible
pollution sources.[16]
1.6.2 To Recycle:
An excessive amount of potassium hydroxide (KOH), in sub-molten salt state, was employed as
the reaction medium, and most was recycled after the reaction occurred. Only a small amount
was consumed during the reaction and needed to be supplemented [16].
11. 2 KHCO3 K2CO3 + H2O + CO2
12. K2CO3 + Ca(OH)2 CaCO3 + 2 KOH
13. CaCO3 CaO + CO2
14. CaO + H2O Ca(OH)2
1.6.3 To Reuse:
The produced intermediates such as potassium carbonate (K2CO3) and potassium bicarbonate
(KHCO3) were reused to manufacture potassium hydroxide (KOH) (reaction 11, 12) the calcium
hydroxide (Ca (OH) 2) can be recovered (reaction 13, 14) [20].
In the new cleaner process, illustrated in figure 16 aluminum-bearing by products and
magnesium-bearing byproducts are manufactured, in addition to the products of potassium
dichromate (KCr2O7) and chromic oxide (Cr2O3) [21]. As the final obtained ferrite-enriched
residues were used as raw materials in the cement industry [16].
20
Figure 16.
Illustrative ow sheet of the new cleaner production process for chromic oxide
(Cr2O3).
21
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