Powder Technology 123 2002. 5358 www.elsevier.

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Porous structure of waste fly ashes and their chemical modifications

Z. Sarbak ) , M. Kramer-Wachowiak
Faculty of Chemistry, Adam Mickiewicz Uniersity, Grunwaldzka 6, 60-780 Poznan, Poland Received 1 December 2000; received in revised form 1 March 2001; accepted 6 July 2001

Abstract Changes in the porous structure of fly ashes ZS-13 subjected to chemical treatment with solutions of NaOH, NaOHrNH 4 HCO 3 , EDTA, and HCl are examined. The initial material with 3 m2rg surface area and 0.01 cm3rg pore volume after modification revealed an increased surface area and pore volume. The greatest increase in the surface area equal to 105 m2rg was noted for the sample treated with HCl, while the greatest increase in pore volume equal to 0.18 cm3rg was obtained for the sample treated with EDTA. In the modified products, meso- and macropores prevail, although in the sample treated with HCl, the presence of a small contribution of micropores was detected. All the modifications, except that treated with HCl, were found to contain slit-shaped macropores. In the sample treated with HCl, the pores were in the shape of nonparallel plates. A study by scanning electron microscopy SEM. allowed a detailed determination of the shape of the isles and agglomerates. Chemical treatment of the initial fly ashes resulted in a transformation of the ball-shaped agglomerations into different products characterised by specific size and shape of particles. q 2002 Elsevier Science B.V. All rights reserved.
Keywords: Fly ashes; Chemical treatment; BET; Pore size; Pore volume; SEM

1. Introduction Fly ashes are waste products of coal combustion in electric and thermal power plants. The ashes are captured electrostatically in electrofilters or mechanically by cyclones and then they are deposited directly into ponds or landfills, where they can become hazardous to the environment w1x. Fly ashes are oxides whose composition depends on the type of coal subjected to combustion and the combustion conditions. The main components of ashes are minerals such as kaolinite, mullite, quartz, calcite, and pyrite w2x. High contents of silicates and aluminasilicates suggest their susceptibility to transformation into zeolite-like crystalline materials as a result of chemical treatment w36x. It is also expected that the obtained materials may be efficient adsorbents of environmental pollutants w7x. The aim of the present study is to determine changes in the surface area and porous structure of fly ashes from Konin Power Plants Poland. firing brown coal and their chemical modifications with different chemical agents.

2. Experimental The study was performed on fly ash denoted by the symbol ZS-13 from the Konin Power Plant combusting brown coal. 2.1. Modification of fly ashes Twenty grams of fly ash from the Konin Power Plant was mixed with 160 cm3 3.5 M solution of NaOH and heated in a water bath under reflux at 90100 8C for 24 h, and then filtered off and washed with distilled water until pH s 7. The obtained material was dried at 120 8C for 12 h. The same procedure was applied to obtain other modifications of ashes using 160 cm3 3.5 M solution of NaOH and 0.015 molar equivalent of NH 4 HCO 3 , 200 cm3 2.5 M solution of HCl, and 0.05 molar equivalent of EDTA in 100 cm3 of water. 2.2. Chemical analysis Chemical analysis was performed on a solution obtained after melting the sample in a Philips type PW 2400 fluorescence X-ray spectrometer.

Corresponding author. E-mail address: sarbak@main.amu.edu.pl Z. Sarbak..

0032-5910r02r$ - see front matter q 2002 Elsevier Science B.V. All rights reserved. PII: S 0 0 3 2 - 5 9 1 0 0 1 . 0 0 4 3 1 - 4

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Z. Sarbak, M. Kramer-Wachowiak r Powder Technology 123 (2002) 5358

Table 1 Chemical composition of ZS-13 fly ashes Component SiO 2 Al 2 O 3 Fe 2 O 3 TiO 2 MgO CaO Na 2 O K 2O Content wt.%. 27.37 6.63 3.75 0.96 8.23 34.48 1.08 0.41

2.3. X-ray diffraction studies Diffractograms of the starting material and the obtained modifications were made on a TUR M-62 diffractometer .. using CuK a radiation and Ni filter l s 1.5418 A 2.4. Infrared spectroscopy studies The studies were performed on a Perkin-Elmer Model 180 spectrometer within the range of 1800400 cmy1 , using a 1.5-mg sample mixed with 200 mg of KBr and pressed into a thin transparent tablet. 2.5. Scanning electron microscopy (SEM) Microscopic observations were made using a Philips type SEM 515 scanning electron microscope at the accelerating voltage 15 kV. At the first stage, a suspension of the samples was made and the smear was covered with a thin film of gold in the atmosphere of argon, in Balzers type SCD 050 evaporator. 2.6. Surface area and pore characterisation To determine the surface area, specific volume, and mean pore radius, the samples were first degassed at 350 8C and then subject to N2 adsorption using BET method. The study was performed using a Sorptometer ASAP 2010 made by Micromeritics. 3. Results and discussion Results of the chemical analyses of the initial fly ash ZS-13 are shown in Table 1.
Table 2 The effect of chemical modifications of ZS-13 fly ashes on the pore properties and surface area Chemical treatment None NaOH NaOHr NH 4 HCO 3 EDTA HCl BET surface area m2 rg. 3 59 60 60 105 Mean pore . radius A 34 48 43 50 17 Pore volume cm3 rg. 0.01 0.14 0.13 0.18 0.10 Fig. 1. Pore volume distribution as a function of the pore radius for fly ash ZS-13.

According to the calculations carried out from chemical analyses, the molar ratio of SiO 2rAl 2 O 3 was equal to 7.02, whereas that of SiO 2 q Al 2 O 3 .rCa q MgO q Fe 2 O 3 . was equal to 0.62, which indicates that the ashes belong to the calciumsilica class. Modification of the ash with the solutions mentioned above brings a change in many textural parameters. Table 2 gives the pore and surface area characteristics of the chemically amended fly ash. In all instances, the surface area of the chemically amended fly ash is greater than in

Fig. 2. Pore volume distribution as a function of the pore radius for fly ash ZS-13 modified with NaOH solution.

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Fig. 3. Pore volume distribution as a function of the pore radius for fly ash ZS-13 modified with NaOHrNH 4 HCO 3 solution.

Fig. 5. Pore volume distribution as a function of the pore radius for fly ash ZS-13 modified with HCl solution.

the unmodified ash ZS-13.. The greatest increase in the surface area is observed for the ashes subjected to the modification by hydrochloric acid. This modification also resulted in the lowest mean pore radius, which is about twice as small as that of the initial ash. Chemical modification by the other solutions leads to a smaller increase in the mean pore radius. A more dramatic influence of chemical modification is a large increase, 10-fold or even greater, in the pore volume. The greatest pore volume increase was noted for the sample modified by the EDTA solution. For

this sample, the pore radius was also the largest. The sample ZS-13 HCl showing the greatest surface area was characterised by the smallest mean pore radius and the smallest pore volume of all chemically modified samples. This means that the sample has a much greater amount of micropores than the other modifications. A low surface area and small pore volume of the initial ash at a relatively large mean pore radius indicates the 10 presence of meso- pore radius between 10 and 250 A, s 1 nm. and macropores pore radius exceeding 250 A . A according to IUPAC w8x classification. This supposition is

Fig. 4. Pore volume distribution as a function of the pore radius for fly ash ZS-13 modified with EDTA solution.

Fig. 6. Nitrogen adsorption x. and desorption o. isotherms for fly ash ZS-13.

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Z. Sarbak, M. Kramer-Wachowiak r Powder Technology 123 (2002) 5358

Fig. 7. Nitrogen adsorption x. and desorption o. isotherms for fly ash ZS-13 modified with NaOH solution.

Fig. 9. Nitrogen adsorption x. and desorption o. isotherms for fly ash ZS-13 modified with EDTA solution.

confirmed by the dependence of the volume of the adsorbed nitrogen versus the pore radius Figs. 15.. In this A modification, the dominant pores have a radius of 20 A. similar conclusion has been drawn on the initial prepara occur tion ZS-13, in which mesopores of the radius 20 A in abundance. The samples obtained as a result of modification with the solutions NaOH and NaOHrNH 4 HCO 3 have the maximum contribution of pores of the radii 20 In the sample modified with EDTA, the and 100 A. maximum contribution of the mesopores of the radii 20 was established. and 35 A In our opinion, a greater surface area and volume of pores in the samples modified with NaOH solution is

mainly a consequence of conversion of fly ashes into zeolite-like structures. A similar conclusion follows from the study by Howden w9x, who reported that the treatment of kaolinite a component of fly ashes. with this solution results in the formation of zeolite structures. The increase in the parameters discussed upon the treatment with HCl and EDTA solutions is related to the process of dealumination. The course of this process in the case of synthetic silicaalumina was described by Scherzer w10x. The isotherm of nitrogen adsorption obtained for the initial ash ZS-13 Fig. 6. can be classified as type II in the IUPAC w8x classification. This kind of isotherm corre-

Fig. 8. Nitrogen adsorption x. and desorption o. isotherms for fly ash ZS-13 modified with NaOHrNH 4 HCO 3 solution.

Fig. 10. Nitrogen adsorption x. and desorption o. isotherms for fly ash ZS-13 modified with HCl solution.

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sponds to the situation when at relatively low pressures, a monolayer of nitrogen is formed, and at relatively high pressures, a nitrogen multilayer is formed. This character of the isotherm is typical of macroporous materials. The small surface area and low pore volume at a relatively large mean pore radius indicates that the fly ash tested has a macroporous structure. The fact that the hysteresis loop begins at relatively low pressures also implies a small contribution of micropores. The hysteresis loop can be classified as H3 type, which means the overwhelming presence of slit-shaped pores w11x.

The adsorption isotherms and hysteresis loops obtained for the samples modified with NaOH and NaOHrNH 4 HCO 3 Figs. 7 and 8. are similar and can be classified as types II and H3, respectively. For the sample modified with EDTA Fig. 9., the shape of the isotherm is similar type II., but the hysteresis loop, although also of type H3, is much broader. A different character of the nitrogen adsorption isotherm is observed for the sample ZS-13 HCl Fig. 10.. Its adsorption significantly increases at relatively low pressure, which means that the number of micropores in this sample is much higher than in the sample ZS-13.

Fig. 11. Scanning electron micrographs of a. fly ashes ZS-13 modified with: b. NaOH solution, c and d. NaOHrNH 4 HCO 3 solution, e. HCl solution, and f. EDTA solution.

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Z. Sarbak, M. Kramer-Wachowiak r Powder Technology 123 (2002) 5358

The isotherm can be classified as type I with an admixture of type II, which corresponds to microporous adsorbents, e.g. zeolite-like crystalline solids, containing some macropores. The hysteresis loop looks like type H4 characteristic of the adsorbents with the pores formed by nonparallel plates w11x. A comparison of our results concerning the surface area and porous structure of the material studied with literature data is impossible because of the lack of the latter. SEM observations proved the presence of well-developed particles in the shape of rather smooth balls of the diameter of 24 m m and sometimes even 7 m m, in the initial fly ashes Fig. 11a.. Moreover, the occurrence of scarce agglomerates of amorphous particles, of approximately 46 m m in size, was noted. After exposure to a solution of sodium hydroxide, the smooth balls become objects of deformed ball-like shape Fig. 11b., sizes 45 or 1012 m m, with numerous plates on the surface, which testifies to the occurrence of crystallisation. Individual particles were found with well-developed smooth walls. In the background, there were numerous small particles of the size about 5 m m, as well as a number of short fibres of about 3 m m in length. Exposition of the fly ashes to solutions of sodium hydroxide and sodium bicarbonate Fig. 11c and d. causes a transformation of the ball-shaped agglomerations into large particles of the size of 1012 m m, with well-developed plates on the surface. The effect of HCl brings about a transformation of the majority of ball-shaped particles into agglomerations of undefined shape Fig. 11e.. The observations also revealed a formation of a single crystal in the form of a rod of the size 7 = 15 m m. When EDTA was used for chemical modification of the ashes, SEM Fig. 11f. shows that only scarce ball-shaped particles remained, while the majority were transformed into numerous pillars of the size 6 = 1.2 m m and individual cubic crystals with rounded edge 3 = 3 m m.. As follows from the above data, each of the procedures of chemical modification, transforms the fly ashes ZS-13 into a different product characterised by specific shape and size of particles. It should be emphasised that the fly ashes differ depending on the kind of combusted coal and combustion conditions. Therefore, a comparison of selected texture parameters seems pointless.

modification. The sample ZS-13 HCl reveals a relatively large contribution of micropores when compared to the initial fly ashes but do not occur in the other samples. The shape of the adsorption isotherms and hysteresis loop suggests that the sample ZS-13 contains mainly slit-shaped macropores. Similar pores were found in the other samples except ZS-13 HCl, in which micro- and macropores of the shape of nonparallel plates were found. The modification with solutions of NaOH, NaOHr NH 4 HCO 3 , and EDTA leads to obtaining of new materials characterised by greater surface area than that of the initial fly ashes, which is of about 60 m2rg. According to the results of the SEM study, the sample ZS-13 reveals the presence of well-developed particles in the shape of smooth balls of a diameter of 24 m m, which under the influence of NaOH treatment, undergo deformation and numerous plates and short fibres appear on their surface. The chemical treatment with NaOHrNH 4 HCO 3 solution leads to the appearance of large particles of the size of 1012 m m with well-developed plates. The modification with EDTA leads to a transformation of the ballshaped particles into numerous pillars. The treatment with HCl resulted in the appearance of agglomerations of undefined shape. In the aspect of future application of these materials as adsorbents, catalysts, or their supports, it seems that all the above-described modifications can find appropriate use. This conclusion is justified by the facts that chemical modifications of the ashes have led to a significant increase in the surface area, mean pore size, and transformation of ball-shaped structure of the initial ash ZS-13 into crystalline structures observable under a scanning electron microscope.

References
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4. Conclusions Chemical treatment of the initial fly ashes ZS-13 characterised by 3 m2rg surface and 0.01 cm3rg pore volume leads to an increase in their surface area and pore volume. The greatest pore volume of 0.18 cm3rg occurs for the sample treated with the EDTA solution, whereas the greatest surface area of 105 m2rg was observed for HCl