COMPARATIVE ANALYSIS OF DEMINERALIZATION OF DIFFERENT INDIAN COALS DURING CHEMICAL BENEFICIATION AT ELEVATED TEMPERATURE UNDER ATMOSPHERIC PRESSURE

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ABSTRACT Coking industries, and especially, blast furnaces, are more sensitive to high ash contents in coals. As a result, enormous efforts are being extended to make coal a better source of energy. Accordingly, physical as well as chemical coal cleaning processes have been explored. In contrast to physical coal cleaning, chemical coal cleaning techniques are in an early stage of development. In the present work, an effort has been made to study the effect of aqueous alkali leaching alone and in combination with acid leaching and washing on the removal of mineral matter from different Indian coals containing high ash under elevated temperature at atmospheric pressure. Chemical leaching experiments were conducted for five different coals of Indian origin at various process conditions using the laboratory and bench scale experimental set up. The research study revealed that it is possible to reduce the ash content in all the coals by this method. The degree of demineralization however varies from coal to coal. The degree of demineralization was improved by increasing the reaction time and alkali concentrations. The effect of this treatment on the alkali, silica, alumina and phosphorous content of the coals were also evaluated. The mechanism of demineralization was evaluated by analyzing the coal samples before and after the alkali and acid treatment using XRD technique. KEY WORDS: coal, leaching, mineral processing 1. INTRODUCTION Most of the coals are associated with mineral matter, which makes it unsuitable for efficient utilisation, such as carbonisation, gasification, combustion, or liquefaction. Coking industries, and especially, blast furnaces, are more sensitive to high-ash contents in coals. As a result, enormous efforts are being extended to make coal a better source of energy. Accordingly, physical as well as chemical coal cleaning (beneficiation) processes have been explored. In general, physical coal cleaning processes involve pulverizing the coal to release the impurities, wherein the fineness of the coal generally governs the degree to which the impurities are released. Based on the physical properties that effect the separation of the coal from the impurities, physical coal cleaning methods are generally divided into four categories: gravity, flotation, magnetic and electrical. In contrast to physical coal cleaning, chemical coal cleaning techniques are in an early stage of development. A review of the literature of the chemical cleaning of coals shows that the methods used include acid leaching, alkali leaching under high pressure and at elevated temperatures and leaching by molten

Corresponding Author: E-mail: pratikswarupdash@tatasteel.com Ph: +91 657 6642596/6647421, Fax: +91 657 2271570

caustic baths. Choudhary and Bhaktavatsalam [1] worked in the area of chemical treatment of coal where ammonia treated coal was reacted with a mixture of concentrated sulphuric acid and calcium fluoride in a two stage process at a reaction temperature of 350 deg. C. Demineralization/desulphurization of coal by aqueous or fused sodium hydroxide alone or followed by mineral acids have been reported by many investigator [2-6]. They achieved different levels of success in removing mineral matter and sulphur from coal from different sources by treatment with sodium hydroxide alone or in combination with other substances. Sharma and Gihar [4] applied the method of chemical cleaning of low grade coals through alkali-acid leaching employing mild conditions under ambient pressure resulting in substantial demineralization. The removal of sulphur and ash from coal treated with aqueous hydrogen peroxide/sulphuric acid solutions has been studied at ambient temperature, under a variety of experimental conditions. Almost complete elimination of the sulphate and the pyritic sulphur was observed. Waugh and Bowling [6] reported 90% reduction of the mineral matter content of coal from Australia by caustic wash. In the present work, an effort has been made to study the effect of aqueous alkali leaching alone and in combination with acid leaching and washing on the removal of mineral matter from five different Indian coals containing high ash under elevated temperature at atmospheric pressure. The results obtained in the laboratory scale studies are reported here. The research was carried out keeping in mind the high ash content and finely disseminated mineral matter content typical of Indian coals. 2. METHODOLOGY/EXPERIMENTATION Five different coal samples were selected for the chemical leaching experiments using alkali and acid. The coals used for this study are West Bokaro (WB) clean coal, Jamadoba, WB ROM, WB Middling and WB Sink-Float coals. Various properties of these five coals are listed in Table 1. WB clean coal is a physically beneficiated medium coking coal from West Bokaro coal field and Jamadoba coal is a prime coking coal from the Jharia mines located in the eastern part of India. WB ROM coal is a runof-mine coal sample collected from the WB collieries. WB Middling and WB Sink-Float coal samples are artificially generated from the froth flotation feed using sink-float method. Coals at low ash level are separated out from the original materials to generate these samples at moderate to high ash levels. All these coal samples are ground to desired size (-0.5 mm), preserved in desiccators, and used for all subsequent analyses under this study. The ash content of these coals varies in between 15% for WB coal to 26.4% incase of WB ROM coal. Aqueous solution of sodium hydroxide (NaOH) in combination with and HCl of various concentrations were prepared and used for carrying out the experiments. Table 1: Properties of Various Coals
Properties WB Clean Coal Jamadoba Clean Coal WB ROM Coal WB Middling WB Sink-Float

Proximate Analysis (db), % Ash Volatile Matter Fixed Carbon Ash Composition, % Total Alkali (Na2O + K2O) SiO2 Al2O3 Phosphorous (P) Sulphur (S) Calorific Value (CV), kcal/kg Crucible Swelling Number (CSN)

15.0 27.2 57.8

17.9 21.1 61.0

26.4 25.3 48.3

19.0 26.1 57.8

25.0 27.2 57.8

0.282 8.120 3.670 0.133 0.850 6992 6.5

0.309 9.710 4.000 0.134 0.670 6344 6.5

0.560 12.170 6.160 0.196 1.100 5408 2.5

The experiments were carried using the laboratory scale setup as shown in Figure 1. The equipment assembly consisted of a Reactor which is three-necked 1000 ml round bottom flask. The main centre neck was utilized for assembling the motor and stirrer. The speed of the motor for stirring was controlled through a variac. A condenser was connected to one of the other two necks which, in turn, was connected to a conical flask with water for trapping the volatile gases generated during the reaction. The third neck is used to facilitate addition of reagents using a dropping funnel and also to monitor the temperature of the reaction bath using a thermometer. Rotamantle was the source of heat input for the reactor to raise the temperature to the reaction temperature of 80-85 C. This rotamantle does a two-fold job of controlling the temperature as well as speed of the stirring (when the magnetic stirrer is used). Both these parameters can be controlled through the variacs. The experiments were also repeated in a bench scale reactor. The feed coals were treated 10-40% aqueous NaOH solution for 5.0 hr at 80-85 deg. C with stirring. The alkali treated coal is first filtered and washed with only water or water followed by 10% HCl solution and then dried. The dried product coal samples after chemical treatment were analyzed for their properties.

D C

LEGEND A Rotamantle B Three necked round bottomed flask C Water condenser D Motor & stirrer E Reagent addition and temperature measurement F Conical flask containing water

Fig. 1: Laboratory Scale Experimental Setup

3. RESULTS AND DISCUSSION 3.1 Effect of Alkali Concentration followed by Acid Treatment on the Demineralization To study the effect of chemical leaching process involving alkali treatment followed by acid washing on demineralization of different coals, the coal samples were treated with NaOH of 10-40% concentrations at 85 C under atmospheric pressure maintaining a coal to reagent ratio of 1:10. All the experiments were conducted for 2.5 h. After the alkali treatment the coals samples were washed first with water and then using 100 ml 10% HCl solution. The product coal samples, after filtration, were analyzed for their ash contents. The test results are shown in Fig. 2. From Fig. 2, it can be seen that alkali treatment, depending on the concentration of alkali, decreases the ash content of different coals to various degrees. The percentage ash removal increases with the increase of NaOH concentration up to a critical value. At higher NaOH concentration, the extent of demineralization becomes invariant of the NaOH concentration. The reduction in ash content on acid treatment of the alkali treated coal was found to increase with increase in concentration of alkali. Increase in alkali concentration exhibits positive influence on the ash removal up to 30% NaOH concentration incase of WB, Jamadoba and WB ROM coals. Further ash reduction is insignificant above 30% NaOH concentration incase of these coals. The rates of reduction in ash percentage incase of WB Middling and WB Sink and Float coal samples are less than that of the rest of the three coals. Even if the rate of removal of ash decreases at higher concentrations of alkali for these coals, the ash removal continues even after 30% NaOH concentration. It shows that the mineral matter are firmly bound and finely distributed inside the coal matrix for these coals. Hence the ash reduction rate is low as compared to other three coals. Prolonging the treatment time or increasing the alkali concentration may even lead to continuous gain in ash of some coals as stated in literature. The gain in ash content or decrease in degree of demineralization of the coal samples with increase in alkali concentration is attributed to sodium aluminosilicate formation. Alkali also reacts with silica and alumina in clay and other silica and alumina-bearing materials present in the coal forming soluble silicates and aluminates as per the following simplified reactions. SiO2 + 2 NaOH Na2SiO3 + H2O Al2O3 + 2 NaOH 2NaAlO2 + H2O The concentrations of silicate and aluminate ions in the solution gradually increase with alkali concentration and treatment time till the same exceed the solubility product of sparingly soluble sodium aluminosilicates. The later is precipitated as per the following simplified reaction: Na2SiO3 (aq) + NaAl(OH)4 (aq) + NaOH (aq) + H2O [Naa(AlO2)b(SiO2)c . NaOH . H2O]
Sodium-aluminosilicate gel

Continuous decrease in ash removal or gain in ash with alkali concentration and reaction period is therefore attributed to progressive precipitation and accumulation of aluminosilicates. This can happen when more and more amount of silica and alumina from the coal dissolves out. 3.2 Effect of Reaction Time with Alkali on the Demineralization of Different Coals The major factors, on which degree of demineralization depends, are alkali concentration and the treatment time. To study the effect of reaction time on the demineralization of different coals, chemical leaching experiments were conducted for 2.5 h and 5.0 h reaction time. The experimental results plotted in Fig. 3 shows that regardless of the type of coal, the maximum reduction of ash content is achieved within 2.5 h. However, smaller improvement in demineralization is obtained even at longer reaction time.

Fig. 2: Effect of Alkali Concentration on the Demineralization of Various Coals

Fig. 3: Effect of Reaction Time with Alkali on Demineralization

3.3 Effect of Chemical Leaching Process on Various Properties of Coal The effect of the chemical leaching process on various properties of West Bokaro (WB) clean coal has been depicted in Table 2. There is an overall increase of nearly 5% in the calorific value. There is no significant change in the alkali content either after alkali treatment or after the acid treatment proving there is no accumulation of Na 2O or K2O during the process. The silica and alumina content reduced by nearly 50% and 70% respectively with 40% NaOH treatment followed by acid treatment. Since percentage of alumina removal is more than that of silica, a positive change is noticed in the Alumina (Al2O3) to Silica (SiO2) ratio which plays an important role during the steel making process. A marginal reduction in sulphur content is observed. There is no significant change in the phosphorous content of the coal samples after the first step where the treatment is done only with alkali. However, a sharp decrease in phosphorous content is noticed after 10% HCl washing. Table 2: Properties of Med. Coking Coal after alkali treatment and acid washing
10% NaOH 20% NaOH 30% NaOH 40% NaOH 10 % NaOH + 10% HCl 20 % NaOH + 10% HCl 30 % NaOH 40 % NaOH + 10% HCl + 10% HCl

Ash (db), % C.V., kcal/kg Alkali, %

12.6 7012 0.344

11.4 7073 0.315 21.3 31.6 0.39 0.12 0.8

10.2 7122 0.307 29.6 41.4 0.38 0.114 0.8

9.4 7220 0.300 37.6 52.3 0.35 0.12 0.75

9.9 7044 0.326 26.8 36.8 0.39 0.04 0.8

7.5 7112 0.279 41.1 59.7 0.31 0.032 0.79

6.5 7220 0.271 48.0 65.9 0.30 0.028 0.75

6.4 7312 0.238 49.5 69.2 0.28 0.028 0.68

SiO2 Removal, % 11.8 Al2O3 Removal, % 17.7 Al2O3/SiO2 P, % S, % 0.42 0.124 0.8

3.4 Analysis of the feed and product coal samples using XRD technique Analysis of the Feed and Product Coal Samples using XRD Technique Ash samples were prepared from the coal samples generated during the experimentation. The ash samples were analyzed with X-ray Diffraction (XRD) method. X-ray Diffraction was done with the Philips diffractometer using Co radiation from 10 to 80 , 2, with a 0.05 step size. Each scan is

processed using standard JCPDS XRD search match programs for identification of mineral phases present and analyzed using Braggs Law. Qualitative analysis on various minerals present in WB clean coal was carried out and various mineral phases were identified using the XRD plots. Si and Al are by far the most abundant elements in these samples due to the high abundance of kaolinite, quartz and other clay compounds. These are usually the minerals present in coals of Indian origin. Montmorillonite was also found to be present. Fe is the next most abundant mineral element present. This is evident from the presence of pyrite, hematite and siderite minerals in these coal samples which contain Fe. Trace quantities of fluorapatite was also detected in the WB clean coal sample which shows the presence of calcium and phosphorous in coal. K, Ca, Na and Mg are the next most abundant elements. Trace amounts of potassium feldspar, gypsum, dolomite and natrojarosite may also occur in few coal samples. Al, Si, Fe, Ti, Ca, Mg, K, S and Na are often the most abundant mineral elements in coal. It was observed that intensity of the peaks belonging to the mineral matters Kaolinite, Quartz and Montmorillonite-Chlorite start decreasing after alkali treatment for 2.5 hr and new peaks appear at 28 degree, 53.8 degree and 37.4 degrees. These new peak corresponds to sodium aluminum silicate hydroxide (sodalite). The coal samples were washed with 10% HCl after treatment with alkali. Sodalite has a tendency to get dissolved in acidic solutions. The filter cake was washed with the water to remove the dissolved salts. The peaks pertaining to sodalite gets removed during the acid washing which causes further reduction in ash content during the acid treatment. 4. CONCLUSION It is possible to reduce the ash content physically beneficiated Indian coal by removing about 60% of the mineral matter by treatment with caustic solution followed by acid washing. For the present case, the coal yields are above 70% in most of the experiments. A positive change is noticed in the Alumina (Al2O3) to Silica (SiO2) ratio. A marginal reduction in sulphur content and significant reduction in phosphorous content in envisaged after the acid treatment. The degree of demineralization improved by increasing the reaction time, alkali and acid concentrations, temperature during experiment and decreasing the particle size and coal to reagent ratio. The mechanism of demineralization was evaluated by analyzing the coal samples before and after the alkali and acid treatment using XRD technique. 5. ACKNOWLEDGEMENTS The authors are grateful to Dr. Debashish Bhattacharjee, Director (R&D and Technology), Tata Steel Group for providing all the support to continue the research work. 6. REFERENCES
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Choudhury, R. and Bhaktavatsalam, A.K. (1997), Beneficiation of Indian coals by chemical techniques, Energy Convers. Mgmt., Vol. 38, No. 2, pp. 173-178. Culfaz, M., Ahmed, M. and Gurkan, S. (1996), Removal of mineral matter and sulphur from lignites by alkali treatment, Fuel Processing Technology, Vol. 47, pp. 99-109. Mukherjee, S. and Borthakur, P.C. (2003), Effect of leaching high sulphur sub-bituminous coal by potassium hydroxide and acid on removal of mineral matter and sulphur, Fuel, Vol. 82, pp. 783-788. Sharma, D.K. and Gihar, S. (1991), Chemical cleaning of low grade coals through alkali-acid leaching employing mild conditions under ambient pressure, Fuel, Vol. 70, pp. 663-665.

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Steel, K.M. and Patrick J.W. (2003), The production of ultra clean coal by sequential leaching with HF followed by HNO3, Fuel, Vol. 82, pp. 1917-1920. Waugh, A.B. and Bowling, K. McG. (1984), Removal of mineral matter from bituminous coals by aqueous chemical leaching, Fuel Processing Technology, Vol. 9, pp. 217-233.

6.

CONTACT DETAILS: Name: Dr. Pratik Swarup Dash Position: Researcher Company: Tata Steel Limited Mailing Address: Raw Materials & Coke Making Research Group, R&D, Tata Steel, At/PO: Burmamines, Jamshedpur, Jharkhand, India Post/Zip Code: 831007 E-mail: pratikswarupdash@tatasteel.com; pratik_dash@yahoo.com Telephone: +91 - 657 - 6642596/6647421 Mob: +91 9234549790

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