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World Review of Science, Technology and Sust. Development, Vol. 8, Nos. 2/3/4, 2011

Investigation of benefit of using coal wastes in cement production A. Sarrafi*

Department of Chemical Engineering, Shahid Bahonar University of Kerman, Kerman 76175-133, Iran E-mail: sarafi@mail.uk.ac.ir *Corresponding author

M.R. Izadpanah
Department of Materials Science and Engineering, Shahid Bahonar University of Kerman, Kerman 76175-133, Iran E-mail: izad@mail.uk.ac.ir

A. Ebrahimi
Department of Chemical Engineering, Shahid Bahonar University of Kerman, Kerman 76175-133, Iran E-mail: refigha@gmail.com

A.I. Mansouri
International Center of Science, High Technology and Environmental Science, Kerman, Iran E-mail: mansori@icst.ac.ir
Abstract: Waste disposal in coal preparation plants leads to serious environmental problems. These wastes usually contain about 20% carbon, and the composition of the remaining ash is similar to clay. Addition of these wastes to cement clinker raw material utilises carbon as a source of energy. In this investigation, the effect of addition of these waste materials to the raw materials used in cement manufacture is studied. Ordinary type II cement and sulphoaluminate cement may be produced from the wastes. Mechanical strength, chemical and phase analysis, setting time and particle size distribution of the cement were studied. The results of the experiments show that an addition of about 3% of the coal wastes to the raw materials used in cement manufacture produces cements with good quality. Further, energy consumption may be reduced by up to 15%. Keywords: coal; waste processing.

Copyright 2011 Inderscience Enterprises Ltd.

Investigation of benefit of using coal wastes in cement production

Reference to this paper should be made as follows: Sarrafi, A., Izadpanah, M.R., Ebrahimi, A. and Mansouri, A.I. (2011) Investigation of benefit of using coal wastes in cement production, World Review of Science, Technology and Sustainable Development, Vol. 8, Nos. 2/3/4, pp.268275. Biographical notes: Amir Sarrafi received his PhD in Hydrodynamics of Bubble Column Reactors from the Department of Chemical Engineering at Surrey University. He has been a member of academic staff at Departments of Chemical Engineering and Material Science at Shahid Bahonar University of Kerman. He has also been a Consultant for Kerman Gas Company and Sarcheshmeh Copper Complex. He has published over 70 papers in conferences as well as international journals. At the moment, he is supervising research works as well as teaching. M.R. Izadpanah received his PhD in Fluid Flow and Heat Transfer from the Department of Chemical Engineering at Surrey University. He has been a member of academic staff at Departments of Mechanical Engineering and Material Science at the University of Kerman. He has also held administrative positions in governmental and private sectors. He has published over 70 papers in conferences as well as international journals. He has also published one book in Heat Transfer and Fluid Flow in Material Science and Engineering as well as one in Furnace Technology. At the moment, he is supervising research works as well as teaching. Abdolhadi Ebrahimi received his BSc and MSc from Shahid Bahonar University of Kerman Iran. His main field of interest is in mining materials in chemical industries. Abdolreza Iraj Mansouri graduated with Bachelors and Masters Degrees in Chemistry from Shahid Bahonar University, Kerman, Iran. After graduation, he worked for three years (from 1989 to 1991) in the Institute of Standard and Industrial Researches, Kerman, Iran, as a Technician of chemistry lab. Following this, he employed as a Staff of Iranian Research Organization for Science and Technology for 10 years (19912001). Subsequently, from 2001 to present, he was the Staff of International Center for Science, High Technology and Environmental Sciences. During his work career in research centres, he did 12 industrial projects in the field of cement and coal wastes and published up to 20 ISI articles and conference abstracts.

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Introduction

Industrial waste disposal is one of the key challenges in the industrial community. In particular, the disposal of wastes produced by coal concentration plants, which amount millions of tons every year, is an important environmental issue. Cement industries are potentially capable of consuming this kind of waste. Disposal of solid or liquid wastes by cement industries is very common in industrial countries, but the utilisation of energy from the carbon content of coal wastes assumes several environmental benefits. Much literature is available concerning utilising wastes as raw material in clinker production (Beretka et al., 1996; Popescu et al., 2003; Krammart and Tangtermsirikul, 2004; Aubert et al., 2006; Guerrero et al., 2004). However, only some investigations have considered the energy content of the wastes. Trezza and Scian (2000), Mokrzycki et al. (2003), Garg

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et al. (2009), Karstensen et al. (2010), Al-Otoom (2006) and Trezza and Scian (2005) studied the use of industrial wastes in production of cement with the intention of taking advantage of their energy content. The production of special cements such as Sulpho-Aluminate Cement (SAC) and the utilisation of coal fly ash in producing this type of cement are the topics of several investigations. Sahu and Majling (1994), Ali et al. (1994), Majling et al. (1993), Singh et al. (1996) and Quillin (2001) studied the properties of this kind of cement and the methods for its preparation from different raw materials. SAC raw materials are mainly lime, bauxite and gypsum. The main crystalline phases of the produced cement are C2S, C 4 A 3 S and C4AF [cement nomenclature are used: C : CaO, S : SiO2, A : Al2O3, F : Fe2O3, S : SO3 and so on.]. Coal fly ash rich in Al2O3 may be a good substitute for bauxite. The yeelimite phase (C 4 A 3 S) which is present in this kind of cement is fast setting, while compressive strength and sulphate resistance properties are also improved. The following are the main reactions defining these important properties (Sahu and Majling, 1994; Quillin, 2001).
C4 A 3 S + 2CSH 2 + 34H C6 AS3 H 32 + 2AH 3 C4 A 3 S + 8CSH 2 + 6CH + 74H 3C6 AS3 H 32

(1)

The firing temperature for producing SAC is lower due to the absence of liquid and C3S phases. Also, the need for lime in its production is lower than for OPC (Ordinary Portland Cement). These are the main factors which result in lowering of CO2 emission by 16% in the production of SAC (Quillin, 2001). The aim of this work is to produce sulphoaluminate cement and ordinary type II cement with the incorporation of coal waste.

Methods and materials

Samples of coal wastes were collected from the Zarand coal concentration plant in the Kerman province of Iran and lime, gypsum, clay and iron ore were obtained from relevant mines in the same province. These materials were analysed for their chemical composition using X-ray Fluorescence (XRF) technique (ARL8680S), the results of which are given in Table 1.
Table 1 Weight percent composition of raw materials used in the experiments CaO Lime Clay Gypsum Iron ore Coal waste 1* Coal waste 2* 51.61 13.58 31 1.36 1.91 2.13 SiO2 3.77 42.61 1.3 3.1 65.39 52.23 Al2O3 0.68 12.03 1.4 0.12 24.89 31.73 Fe2O3 0.43 4.83 0.4 88.9 4.6 4.58 SO3 0.04 0.25 42.6 1.3 0.15 0.71 Na2O 0.27 1.85 0.15 0.19 1.81 2.1 K2O 0.19 2.03 0.07 0.1 3.9 4.15 LOI 41.2 15.09 21 3.29 29.31 34.78

*Weight percents of oxides are based on ash analysis.

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Loss on Ignition (LOI) in coal wastes is mainly due to unburned carbon. Application of the so-called wastes not only reduces environmental pollution, but also reduces the energy consumption from other sources in the kiln due to its carbon content. For example, addition of 3% of these wastes, which contains about 10000 kj/kg of energy, to the raw material in a cement production kiln will introduce 15% of excess energy, which will consequently increase the production rate or decrease fuel consumption. According to the specifications of ASTM C150 (1997) mixtures of the raw materials were prepared. Suitable mixtures compositions are shown in Table (2). After mixing the raw materials, they were ground in a disk mill and pelletised into coin-like shapes, for closer contact of materials, with a diameter of about 35 mm by compressing in a mould. Raw mixtures of SAC cement had been made according to Popescu et al. (2003) and Sahu and Majling (1994). Type II cements samples were fired in an electric furnace at a temperature of 1400C for 30 min, and then cooled in the air. The SAC sample was sintered at 1300C for 20 min and then cooled in the air. To determine the phases formed in the produced clinker, XRD patterns were obtained using a Philips XRD machine. The complex nature of the samples made the quantitative evaluation of different phases by XRD quite difficult. The modified Bouge method (Taylor, 1997) was used to predict the quantity of the phases present in the samples of type II cements. The amount of phases present in SAC was predicted from the mass balance and equilibrium of phases and Al2O3 and Fe2O3 contents in the produced clinker. Hence, weight percent of C 4 A 3 S phase can be predicted by the following equation:
%C4A3S = 1.993 (%Al2O3 0.6389 %Fe2O3).

Properties of the produced type II clinkers were tested and evaluated according to ASTM C150 specifications. Properties of SAC were tested according to the method proposed by Glasser and Zhang (2001). Each experiment was carried out 3 times to ensure the repeatability of the results.

Results and discussion

According to Table 2 samples were prepared and the properties of the produced clinkers were compared. These samples were: ordinary portland type II cement with ordinary industrial raw materials ordinary portland type II cement with coal waste SAC with coal waste.
Raw materials of the samples used (Wt%) Lime 81.2 85.46 62.8 Clay 14.3 9.68 Gypsum 5.8 Iron ore 4.5 1.8 Coal waste 1 3.06 Coal waste 2 31.4

Table 2 Sample Type II

Type II (using coal wastes) SAC

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XRD diffractograms of produced clinkers are presented in Figures 13. Chemical compositions of the produced clinkers are shown in Table 3. As can be seen, the free lime is higher than the accepted value for cement production. It should be mentioned that this is a normal result obtained from laboratory experiments compared to the results of full scale work involving cement kilns.
Figure 1 XRD pattern of type II clinker (see online version for colours)

Figure 2

XRD pattern of type II clinker (from coal wastes) (see online version for colours)

Investigation of benefit of using coal wastes in cement production

Figure 3 XRD pattern of SAC clinker (from coal wastes) (see online version for colours)

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Table 3

Composition of the produced clinkers SAC 55.41 18.42 14.47 2.00 4.69 5.60 26.29 II 64.24 22.20 5.12 3.73 1.06 1.00 II (using coal wastes) 64.17 22.06 5.74 4.18 0.07 2.10

Clinker type %CaO %SiO2 %Al2O3 %Fe2O3 %SO3 %Free lime % C 4 A 3S %C3S

52.80 6.08

49.47 26.23 7.20 11.33

48.90 26.60 8.1 12.70

%C2S %C3A % C4AF

It is evident from the above figures that all the main phases (alite, belite, aluminate and ferrite) of type II samples are present. For the SAC sample, the unique peaks of the yeelimite (C 4 A 3 S) phase can be observed. Type II clinker samples were milled with the addition of 5% of gypsum, but the SAC sample was milled with 10% of gypsum (Glasser and Zhang, 2001; ASTM C150, 1997). The results of the specific area, compressive strength and setting time measurements of the milled clinkers are shown in Table 4. It is apparent that the cement produced from each sample satisfies the requirements suggested by ASTM specifications. The higher compressive strength of type II cement using coal waste is due to higher C3A phase present in this cement. The produced SAC exhibits lower compressive strength than type II cement due to the lower Al2O3 present in raw materials, in comparison with other researchers. The setting time for the SAC type is much lower than for type II cement; this confirms the presence of the yeelimite phase.

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Table 4

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Physical data of the produced cements
Type II Type II (using coal wastes) SAC ASTM limits

ASTM C109-Compressive strength (MPa)

3 days 7 days 28 days

21 26.1 35.4 280

21.8 27.7 37.5 284.7 200 230

18.6 21.7 28.2 290.3 60 110

10 (minimum) 17 (minimum) 28 (minimum) 280 (minimum) Not less than 45 Not more than 375

ASTM C204-Fineness, air permeability (Blaine) (m2/Kg) ASTM C191-Vicat time of set (min)

Initial Final

210 240

Conclusions

Reclamation of the coal wastes as part of raw materials in cement production not only utilises the energy of carbon content, but also reduces environmental pollution. Samples of ordinary type II cement and samples using coal wastes as raw material were prepared. Other samples were prepared for production of SAC. The produced clinkers of the samples were examined for their composition of the phases present and for their mechanical properties of the produced concrete. The first objective of this work was the examination of the suitability of this waste as part of the raw materials for cement production. The second objective is to examine the environmental impact of using this waste as a raw material in cement plants; this will be investigated in the future.

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