0$*'$/(1$:2ţ1,$. .LHOFH8QLYHUVLW\RI7HFKQRORJ\ DO7\VLłFOHFLD3DŐVWZD3ROVNLHJR .LHOFH3RODQG 1 HPDLO ]\JDGOR#WXNLHOFHSO 2 HPDLO DVHZHU\Q#DQUU]SO 3 HPDLO PDND#WXNLHOFHSO
EVALUATION OF THE USE OF COAL FLY ASH FROM
MUNICIPAL HEAT POWER PLANT WITH REGARD
TO FOREIGN EXPERIENCES
A b s t r a c t
7KHUHVLGXHVIURPFRDOFRPEXVWLRQDUHFODVVL¿HGDVDE\SURGXFWKDUPIXOWRWKHHQYLURQPHQWGLI¿FXOWIRUWUDQVSRUWDWLRQ DQGXVH7KHVHDUHPDLQO\À\DQGERWWRPDVKHVDQGVODJ$OWKRXJKVRPHRIWKHP¿QGSUDFWLFDODSSOLFDWLRQPDLQO\LQWKH construction industry, the majority is still stored. This is particularly true for ashes from power plants. Understandably, the disposal of ashes is of great ecological and economic importance. Recycling and recovery are the best available options KHUH)RUHLJQH[SHULHQFHVKDYHVKRZQWKDWÀ\DVKHVFDQEHDYDOXDEOHUHVRXUFHIRUSURGXFWLRQRIV\QWKHWLF]HROLWHV
Natural zeolites are used in numerous economic and industrial sectors. Their limited resources raise the need to look for and DSSO\V\QWKHWLFSURGXFWV6LQFHÀ\DVKHVREWDLQHGIURPFRDODUHVLPLODUWRQDWXUDO]HROLWHVLQWHUPVRIVWUXFWXUHDQGFKHPLFDO composition, it is possible to use them as a raw material for the synthesis of zeolites. The aim of the research was to assess WKHSRVVLELOLW\RI]HROLWHV\QWKHVLVIURPÀ\DVKREWDLQHGIURPWKHPXQLFLSDOSRZHUSODQW±E\PHDQVRIFKHPLFDOFRQYHUVLRQ method. In the experiment, the coal ash collected from under electrostatic precipitators in Kielce Power Plant was used. The effect of chemical activation on the sorption properties of coal ash was examined. The chemical conversion consisted LQÀ\DVK±1D2+VROXWLRQLQWHUDFWLRQXQGHUVSHFL¿HGWHPSHUDWXUHDQGSUHVVXUH7KHLQÀXHQFHRIFKDQJHVLQWKHVWUXFWXUH RILQGLYLGXDOJUDLQVRIÀ\DVK 6(0VWXGLHV RQWKHLUVRUSWLRQSURSHUWLHVZDVHVWLPDWHG7KHOHYHORIDGVRUSWLRQRQWKH PRGHOVWDQGZDVWHVWHGE\PHDQVRIVSHFWURSKRWRPHWULFPHWKRGXVLQJPHWK\OHQHEOXH7KHPRGL¿FDWLRQUHVXOWVDQGVRUSWLRQ SURSHUWLHVRIDVKHVIRUWKHVHWSDUDPHWHUV 1D2+FRQFHQWUDWLRQWHPSHUDWXUHUHDFWLRQWLPH ZHUHDVVHVVHG7KHPLFURVFRSLF DQG;UD\REVHUYDWLRQVDVZHOODVVSHFL¿FVXUIDFHFKDQJHVLQGLFDWHWKDWDIWHUPRGL¿FDWLRQQHZFU\VWDOVWUXFWXUHVLPSURYLQJ sorption capacity were obtained.
The aim of the paper is to assess the possibility of utilizing the furnace waste from Kielce Power Plant. A necessary condition for the recovery and utilization of the waste is to identify their characteristics and properties.
Keywords:FRDOÀ\DVKÀ\DVKUHF\FOLQJ]HROLWHV
1. Introduction
$FFRUGLQJ WR WKH 3ROLVK VWDQGDUG 3((1 WKH criteria limiting the use of ash in concrete production is a high content of chlorides, sulfates and loss on ignition. The high ignition loss is usually typical of ashes from power plants and makes them unsuitable for use in construction engineering. Therefore, they DUH GHSRVLWHG LQ ODQG¿OOV 7KLV KRZHYHU JHQHUDWHV costs connected with securing and monitoring the ODQG¿OOVDQGSRVHVDWKUHDWWRWKHHQYLURQPHQW7KXV WKHQHHGDULVHVIRU¿QGLQJZD\VDQGPHDQVIRUVHFXUH DSSOLFDWLRQRIWKHÀ\DVKHV
A relatively new direction discussed in the literature is the use of sorption capacity of ash (Woolard et al., 2002). Ashes collected directly from under the electrostatic precipitators have high sorption capacity for pollutants in wastewater so they are applied in the production of sorbents used in the treatment of wastewater and waste gases (Cheerarot and -DWXUDSLWDNNXO ,\HU
&KHPLFDOO\ PRGL¿HG DVKHV VKRZ HYHQ KLJKHU sorption capacity. Fly ashes, especially those with VLJQL¿FDQWFRQWHQWRIDOXPLQXPDQGVLOLFRQFDQEH used to manufacture zeolites by means of chemical
conversion. The impact of alkalis (NaOH, KOH) on WKHFRDODVKHVDWVSHFL¿HGWHPSHUDWXUHDQGSUHVVXUH conditions leads to the creation of zeolite-structure ERGLHV>=RQHVDQG'DYLV :RRODUGHWDO Hollman et al., 1999].
Fly ash is collected by electrostatic or mechanical SUHFLSLWDWLRQ àąF]Q\ ,W LV D ¿QHJUDLQHG SRZGHU D KHWHURJHQHRXV PL[WXUH RI SDUWLFOHV RI different shapes and sizes, composed of spherical glass particles, a large number of irregular aggregates and balls of colorless slag glaze with an empty interior. Fly ash contains also a small amount of elongated slivers of unburned carbon.
Grain size of furnace waste is closely related to WKHVSHFL¿FVXUIDFHDUHDRIDVKDVPHDVXUHGE\ERWK %ODLQH DQG %(7 PHWKRG %ODQFR HW DO The VSHFL¿F VXUIDFH DUHD RI DVK GHWHUPLQHG E\ %ODLQH¶V PHWKRG IRU VLOLFDWH DVK LV DERYH P2/kg, for
DOXPLQXPDVKDERYHP2/kg, and for calcium ash
UDQJHVIURPWRP2NJ àąF]Q\
The density of the furnace waste depends on the W\SHRIFRDOEXUQHG7KHGHQVLW\RIÀ\DVKLVDIIHFWHG by: the composition of mineral matter, the amount of unburned carbon and the shape and structure of individual grains of ash (Bastian, 1980). The density RI IXUQDFH ZDVWH LV · JFP, and is smaller
than the density of sandy and silty soil, which is ·JFP (Kucowski, 1997).
7KHGHJUHHRIGHYHORSPHQWRIÀ\DVKJUDLQVXUIDFH DQG WKH VL]H RI WKH VSHFL¿F VXUIDFH DUHD WR D ODUJH H[WHQWGHWHUPLQHWKHLUXVHIXOQHVV àąF]Q\ ,Q WKHEDVLFSKDVHFRPSRVLWLRQRIÀ\DVKWKHIROORZLQJ SKDVHVDUHGLVWLQJXLVKHG àąF]Q\DQG$GDPVNL ,OLFHWDO
glassy phase (with a large number of irregular aggregates) and considerable number of spherical grains,
crystalline phase which consists of mullite, TXDUW] KHPDWLWH PDJQHVLXP R[LGH J\SVXP PDJQHWLWHFDOFLWHFDOFLXPR[LGH
clay phase (amorphous).
The following mineral composition of furnace ash ZDV IRXQG 6NDOPRZVNL 6FKHHW] DQG (DUOH 1998):
± R[LGHPLQHUDOV±$O2O, Fe2O0J2&D2
metallic grains mainly Fe (having a spherical IRUP
silicates and aluminosilicates of the the insular, ring, chain, layered and spatial structure. The morphological diversity of ash particles is shown in Figure 1.
Fig. 1. A porous char residue (unburnt carbon) VKRZLQJFDSWXUH WUDSSLQJ RI¿QHSDUWLFOHVRIÀ\DVK (microspheres). SEM carbon natural surface on the ESP
À\DVKVDPSOH *RRGDU]LL6DQHL
The chemical composition of the furnace waste varies in broad ranges which is one of the reasons KLQGHULQJWKHLUIXOOXWLOL]DWLRQ7KHSURSHUWLHVRIÀ\ ash are determined by a number of factors, of which the most important are: the type of coal burned and the type of installation in which the coal is burned (a type of boiler and technological conditions of coal EXUQLQJ *LHUJLF]Q\
Figure 2 illustrates the areas of coal ash utilization limited by the following criteria: pozzolanic properties, particle size and chemical composition. Pozzolanic properties of coal ash enable obtaining materials of low mechanical strength that can be used to stabilize the waste and as an ingredient in cement production.
'XHWRKLJKVSOLWWLQJDVKFDQEHXVHGDV¿OOHUIRU asphalt, plastics, paper and its coarser fractions for grinding and polishing powders. In addition, ash is used for the production of ceramic products such as brick, glass and refractory materials.
:LWK WKH ULJKW FKHPLFDO FRPSRVLWLRQ À\ DVK FDQ be a valuable source for the recovery of magnetite PLFURVSKHUHV D YHU\ JRRG ¿OOHU IRU UXEEHU DQG plastics), coal, silica, alumina, iron. It is also used as a raw material in cement production if the quality FRQGLWLRQLVIXO¿OOHG,QDGGLWLRQLWFDQEHDEHQH¿FLDO additative to agricultural soils.
The construction and road industries are the areas ZKHUH À\ DVK LV PRVW ZLGHO\ DSSOLHG ,W LV XWLOL]HG LQ ODQGUHFODPDWLRQ¿OOLQJVLQXQGHUJURXQGPLQLQJ ODQG¿OOLQJVIRUWL¿FDWLRQVRIHPEDQNPHQWVKLJKZD\ engineering and construction of dams.
)LJXUH LOOXVWUDWHV XWLOL]DWLRQ RI FRDO DVK LQ WKH construction industry.
)LJ8WLOL]DWLRQRI)O\$VK,QWKH&RQVWUXFWLRQ,QGXVWU\ DQG8QGHUJURXQG0LQLQJ,Q(XURSH (8 LQ total utilization: 17.7 million tonnes. (European Coal Combustion Product Association, http://www.ecoba.org)
7KHXVHRIÁ\DVKLQWKHHQYLURQPHQWDO protection
Several studies have shown that adsorptive capacity of À\DVKLVXVHGIRUZDVWHJDVWUHDWPHQWQDPHO\ UHPRYDO RIVXOIXUFRPSRXQGVWKHDGVRUSWLRQRI12[ 6KDRELQ and Hongwei, 2006), removing heavy metals from wastewater (Wang et al., 2006, Wang et al., 2007, Hui HWDO UHPRYDORIPHUFXU\DQGWKHDGVRUSWLRQRI RUJDQLFJDVHV 0DMFKU]DN.XFĊEDDQG1RZDN
A separate research direction developed recently LVWKHPRGL¿FDWLRQRIÀ\DVKVWUXFWXUHWR]HROLWHE\ chemical conversion. A considerable diversity of PHWKRGVIRUREWDLQLQJ]HROLWHVZLWKÀ\DVKXVHGDV a raw material is observed. Different ranges of heat treatment, proportions of components (ash: NaOH) and procedures are applied. It should be stressed that numerous zeolite structures can be synthetized LQGLIIHUHQWSURFHVVFRQGLWLRQV 4XHUROHWDO 7DQDND7DQDND 7DQDND +ROOPDQ et al., 1999).
=HROLWHVDUHFU\VWDOOLQHDOXPLQRVLOLFDWHPHWDOVRI,$ and IIA groups, such as Na, K, Mg, Ca. The general IRUPXOD LV DV IROORZV =LROHN DQG 6PLWK Paderewski, 1999): M2/nO · Al2O · ySiO2 · wH2O where: \ n cation valence, w water content, 0±H[WUDODWWLFHFDWLRQ
The basic unit of three-dimensional crystal structure of zeolite are tetraedrits (Si,Al)O, characterized by varying ratio of silicon to aluminum and creating different multi-ZDOOHGFRQ¿JXUDWLRQV±RFWDKHGUDOXQLWV
Free spaces in the zeolite structure are so well developed that the cations and water molecules are
able not only stay in them but also roam freely under WKHLQÀXHQFHRISK\VLFDODQGFKHPLFDOIDFWRUV )LJ
)LJ7KH;]HROLWHVWUXFWXUH±WKHPDLQFDWLRQLFVLWHV in the unit cell (Resonant Contrast Diffraction for Direct
/RFDOLVDWLRQRI$WRPVLQ0L[HG2FFXSDQF\3RZGHUV http://www.esrf.eu/UsersAndScience/Publications/
+LJKOLJKWV0DWHULDOV0$7
7KH H[WUD ODWWLFH FDWLRQV XQGHUJR LRQ H[FKDQJH HDVLO\ DV WKH\ DUH PRELOH =HROLWHV LQ WKH GU\ VWDWH show the sorption, catalytic and molecular-sieve properties.
Sieve effect means that only the particles below a certain critical size (window size) pass to the interior channels while larger ones remain outside the sieve. The sorption properties of zeolites are determined by their internal structure. Thanks to it they are used for drying, cleaning and separating of gases. The zeolites VKRZ VHOHFWLYLW\ DQG VLJQL¿FDQW VRUSWLRQ FDSDFLW\ in relation to water (due to its dipole properties) which makes them useful in drying inert gases and atmospheric air.
A characteristic feature of zeolites is the surface area RI WKH RUGHU RI ± P2 · g-1. (Payra i Dutta,
=LyáHNL1RZDN
The process of zeolite synthesis from the coal ash can be single or multistage. Four methods of obtaining ]HROLWHVIURPÀ\DVKFDQEHGLVWLQJXLVKHG 6XFKHFNL
FODVVLFDONDOLQHFRQYHUVLRQRIÀ\DVK
DONDOLQH IXVLRQ FODVVLF DONDOLQH FRQYHUVLRQ RI À\DVK
FRQYHUVLRQRIGU\RUPROWHQVDOW WZRVWDJHV\QWKHVLV
The concept of chemical conversion of ash into the zeolite consists in treating the grains rich in alumina DQGVLOLFD DPRUSKRXVIRUPV ZLWKDONDOL,QWKH¿UVW stage the aluminosilicate gel is formed which then FU\VWDOOL]HV WR ]HROLWH (OOLRW DQG 'RQJNH =KDQJ 0XUD\DPDHWDO
The zeolitization mechanism according to Murayama LVVKRZQLQ)LJXUH
)LJ3URSRVHGUHDFWLRQPHFKDQLVPIRU]HROLWHV\QWKHVLV IURPFRDOÀ\DVK 0XUD\DPDLLQ
7KHPHFKDQLVPIRU]HROLWHV\QWKHVLVIURPÀ\DVKLQ a batch hydrothermal synthesis process includes three stages:
1) the dissolution of aluminium and silicon from À\DVK
2) the deposition of aluminosilicate gel on ash surface,
the crystallization of zeolite from aluminosilicate gel (Murayama i in., 2002).
7KUHHSKDVHVLQÀ\DVKIURPZKLFKWKHDOXPLQLXP and silicon come are observed:
1) amorphous aluminosilicate glass, 2) quartz, and
mullite.
The aluminosilicate glass phase is the largest and most unstable of the phases in the hydrothermal environment, and therefore has the highest rate of dissolution, and is the largest contributor to the zeolites produced. Quartz is less stable than mullite, athough quartz and PXOOLWH SKDVHV DUH VLJQL¿FDQWO\ PRUH VWDEOH WKDQ WKH JODVV SKDVH WR WKH H[WHQW WKDW some authors report little to no reactivity for quartz DQG IRU PXOOLWH (OOLRW L 'RQJNH =KDQJ Murayama i in., 2002).
Different pore sizes and the presence of H[FKDQJHDEOHFDWLRQVLQWKHVWUXFWXUHRI]HROLWHVPDNH them applicable in the selective adsorption of gaseous PL[WXUHFRPSRQHQWV7KHUHVHDUFKRQDSSOLFDWLRQRI zeolites in removal of CO2, SO2 or NO[ from gaseous PL[WXUHV UHVXOWHG LQ D SRVLWLYH RXWFRPH DOVR IRU ]HROLWHV V\QWKHVL]HG IURP À\ DVK $KPDUX]]DPDQ &KHHUDURWDQG-DWXUDSLWDNNXO ,\HU
The development of methods for the synthesis of ]HROLWHVIURPFRDOÀ\DVKFDXVHGFRQVLGHUDEOHLQWHUHVW in the possibility of their utilization in industry and environmental protection.
3. Materials and research methods
&KDUDFWHULVWLFVRIÁ\DVKXVHGLQWKHUHVHDUFK
The ash used in the research was collected in the years 2007, 2008, and 2009 from the heat recovery installation of Kielce Power Plant. The criterion of ash selection was its chemical composition making it usuitable for use in the construction engineering OLPLWLQJ FULWHULD 3((1 7KH DVK ZDV collected directly from under the electrical precipitator in accordance with the standard POBOR PROB BS (1 7KH VHOHFWHG DVK VKRZV D KLJK FRQWHQW of unburned carbon and high content of silicon and DOXPLQXPR[LGHV 7DEOH
Table 1.3K\VLFDODQGFKHPLFDOFKDUDFWHULVWLFVRIÀ\DVK used in the research
Chemical properties Oxide composition Percentage[%] Mineral composition Percentage [%] Si O2 45.67 Quarto 12.4
SiO2 reactive 33.17 0XOOLWH 13.3
Fe2O3 8.01 CaO 0.7 Al2O3 23.47 periclase 2.4 CaO 5.09 hematite 1.8 0J2 3.69 maghemite 1.1 SO3 0.61 anhydrite 2.4 wCaO 0.064 amorphous f. 66.0 Na2O 0.83 K2O 1.40 Physical properties Loss on ignition 7.52 Fineness 6SHFL¿F density JFP 3 6SHFL¿F surface area 6170 cm 2J
To estimate the repeatability of burned coal quality and hence ash quality the basic parameters of the coal burned in Kielce Power Plant are presented in Table 2.
Table 2. Parameters of coal burned in Heat and Power Station in Kielce 2007 2008 2009 &DORULÀFYDOXH>N-NJ@ 22614 23010 23565 Ash content [%] 17.3 16.8 14.5 Sulphur content [%] 0.57 0.49 0.39 6L]HGLVWULEXWLRQRIÀ\DVKZHUHPHDVXUHGZLWK laser diffractometer Malvern Mastersizer Microplus which DOORZVPHDVXUHPHQWLQWKHUDQJHIURPWRPP 7KH PHDVXUHPHQWV ZHUH FRQGXFWHG LQ VRGLXP pyrophosphate solution in recirculation conditions. During the measurement process ultrasounds were used to break up agglomerates the time of ultrasound application was dependent upon the moment of re-agglomeration. The results are presented on a graph showing sample grain-size distribution.
)LJ6L]HGLVWULEXWLRQRIÀ\DVKVDPSOHWDNHQIURP electrical precipitator at power plant in Kielce
The analysis of qualitative and quantitative phase composition was performed by X-ray diffraction using D8 Discover X-ray diffractometer produced by Bruker AXS. Data recording was carried out in the DQJXODUUDQJH± Ĭ&X.ĮIRUDVWHSRI DQGFRXQWLQJWLPH VHFRQGVSHUVWHS7KHFRQWHQW of crystalline phases was determined quantitatively with internal parameters computed on the basis of the standard NIST SRM 660a LaB6. In order to quantify crystalline phases and determine the total content of amorphous phase the X-ray method with the inserted internal formula was used. Due to chemical stability
DQGLQFRPSDWLELOLW\ZLWKLPSRUWDQWUHÀHFWLRQVRIWKH SKDVHV]LQFR[LGH =Q2 ZDVVHOHFWHG ĝ52'21HW al., 2001).
3URFHGXUHRIFKHPLFDOPRGLÀFDWLRQIRUDVK
In order to assess the usefulness of ashes as VRUEHQWV FKHPLFDO PRGL¿FDWLRQ ZDV FDUULHG RXW LQ NaOH. The effectiveness of chemical conversion of ash into a hypothetical form of zeolite was evaluated by comparing ash sorption for methylene blue after conversion with ash sorption before chemical conversion. In addition, sorption isotherms, FKHPLVRUSWLRQDQG%(7ZHUHH[DPLQHG
Chemical treatment consisted in treating ash with NaOH solution at room temperature 180oC ±10oC
and at atmospheric pressure. For this purpose, 1g of ash was placed in a solution of 7M NaOH. The contact time of ash with NaOH was 21 hours. Then the precipitate was drained, washed with hot distilled ZDWHU DQG HWKDQRO ¿OWHUHG DQG GULHG DW oC. In
order to determine the differences in sorption capacity RI À\ DVK EHIRUH DQG DIWHU FKHPLFDO PRGL¿FDWLRQ the sorption intensity of organic compounds using methylene blue as a model organic compound was H[DPLQHG&RQVHTXHQWO\WKHORVVRIFRORUVXEVWDQFH in the solution was analyzed by spectrophotometry.
6RUSWLRQWHVWVFRQVLVWHGLQPL[LQJJRIDVKZLWK 0.1 dmof a suitably prepared dye solution (methylene blue). The concentration of dye was determined H[SHULPHQWDOO\ DW WKH RSWLPXP OHYHO LQ RUGHU WR measure the color intensity by spectrophotometry. 7KH VXVSHQVLRQ ZDV VKDNHQ IRU KRXUV DQG WKHQ ¿OWHUHG7KHFRQFHQWUDWLRQRIWKHG\HZDVGHWHUPLQHG LQ D ¿OWHUHG VROXWLRQ XVLQJ WKH VSHFWURSKRWRPHWHU 7KHUPR6FLHQWL¿F$48$0$7
7KH VRUSWLRQ FDSDFLW\ RI WKH PRGL¿HG DVK ZDV calculated from the difference of dye concentrations
before and after the sorption process. This result was compared to the one obtained for sorption of ash not undergoing chemical conversion. Grain morphology EHIRUHDQGDIWHUPRGL¿FDWLRQZDVH[DPLQHGE\6(0 Neophot 2.
4. Results and discussion
It should be noted that ash collected directly from under the electrical precipitator shows high sorption capacity towards dye and can serve as a good sorbent EHIRUHFKHPLFDOPRGL¿FDWLRQ$VDUHVXOWRIFKHPLFDO UHDFWLRQ WKH PDWHULDO RI VLJQL¿FDQWO\ LQFUHDVHG sorption capacity towards methylene blue was obtained, as shown in Figure 8.
)LJ6RUSWLRQFDSDFLW\RIUDZDQGPRGL¿HGÀ\DVKFROOHFWHG from power plant in Kielce in the period 2007-2009
The process is caused by changes of ash surface character as shown in Figure 9. and Figure 10. 8QPRGL¿HGDVKJUDLQVKDYHDOPRVWVPRRWKVXUIDFHV (Fig. 9A). However, as a result of chemical treatment new structures are formed on the surface of ash particles highly increasing their porosity (Fig. 9B DQG 7KHREVHUYDWLRQLVFRQ¿UPHGE\WKHUHVXOWV REWDLQHGIRUWKHVSHFL¿FVXUIDFHDUHD 7DEOH 7KH change of ash surface character determins the increase of their sorption properties towards methylene blue.
A
B
Fig. 9. SEM. Microscopic structure of individual grains RIÀ\DVKEHIRUHPRGL¿FDWLRQ $ DQGDIWHUFKHPLFDO
PRGL¿FDWLRQ± % 3RZHU3ODQWLQ.LHOFH [PDJQL¿FDWLRQ
Fig. 10. SEM. Microscopic structure of individual grain RIÀ\DVKDIWHUPRGL¿FDWLRQ +HDWDQG3RZHU6WDWLRQLQ
.LHOFH [PDJQL¿FDWLRQ
The amorphous phase with the aluminium and silicon compounds is particularly susceptible to chemical conversion (Table 1). During chemical treatment Si / Al glass on the grain surface turns into gel and then crystallization of a zeolite structure takes SODFH (OOLRWDQG'RQJNH=KDQJ 0XUD\DPD et al., 2002). The more of amorphous phase in the ash sample the more effective the process.As shown by
;UD\ H[DPLQDWLRQ WKH DVKHV FRQWDLQ DERXW RI amorphous phase, which facilitates the formation of zeolite structures.
Table 3. &RPSDULVRQ RI FKDQJHV LQ WKH VSHFL¿F VXUIDFH DUHDRIÀ\DVKEHIRUHDQGDIWHUPRGL¿FDWLRQ
Test method 5DZÁ\DVK
[m2J@
Fly ash after PRGLÀFDWLRQ1D2+ [m2J@ 6SHFL¿FVXUIDFHDUHD measured by BET method 3.8719 104.8395 6SHFL¿FVXUIDFH area measured by Langmuir method 4.9153 132.1400
In order to estimate the impact of time when the samples were collected (the ashes collected in three different years were tested) upon repeatability of results the statistical test was conducted on the basis of monoagent analysis of variance of sorption results. At the beginning the assumption was made that sampling time affects the adsorption capacity RIÀ\DVK,QWKHFDVHRIUDZÀ\DVKFROOHFWHGLQWKH \HDUV WKHERUGHUOHYHORIVLJQL¿FDQFHZDV ZKLFKSURYHVWKDWWKHWHVWVDPSOHVRIÀ\DVKDUH relatively homogeneous and the sampling time has no VLJQL¿FDQWHIIHFWRQWKHVRUSWLRQFDSDFLW\
5. Summary
$OWKRXJKÀ\DVKLVZHOOUHFRJQL]HGDQGZLGHO\XVHG it seems reasonable to look for its new applications, especially as far as ash from power plants is concerned.
2XUUHVHDUFKFRQ¿UPVWKDWDVKHVZKLFKGXHWRWKHLU chemical properties are not utilized in construction engineering can be used in raw state as sorbents. Sorption capacity of ash was improved by chemical conversion in NaOH solution. The chemical FRQYHUVLRQZDVFRQ¿UPHGE\WKHH[DPLQDWLRQRIDVK VSHFL¿FVXUIDFHDUHDDQGPRUSKRORJ\SLFWXUHRIDVK grains. The results of obtained by electron microscopy FRQ¿UPHG ERWK WKH IRUPDWLRQ RI QHZ FU\VWDOOLQH structures on the surface of ash particles and the increase of roughness. The BET results showed that VSHFL¿F VXUIDFH DUHD RI VDPSOHV LQFUHDVHV UDGLFDOO\ DIWHU FKHPLFDO PRGL¿FDWLRQ 7KH REVHUYDWLRQ LV consistent with the results obtained for the sorption of PHWK\OHQHEOXHLQZKLFKWKHFKHPLFDODFWLYDWLRQRIÀ\ DVKFDXVHGWKHLQFUHDVHRIWKHVSHFL¿FVXUIDFHDUHD
%DVLQJRQRXUUHVHDUFKLWVHHPVMXVWL¿HGWRIXUWKHU H[SORUH WKH VRUSWLRQ FDSDFLW\ RI WKH DVKHV WRZDUGV
SROOXWDQWV LQ PXQLFLSDO RU ODQG¿OO ZDVWHZDWHU 7KH DSSOLFDWLRQ RI À\ DVK WR SURGXFH VRUEHQWV DOORZV WR make use of furnace waste which has not been used but VWRUHGVRIDU&XUUHQWO\GHSRVLWLQJZDVWHRQODQG¿OOV in power plants requires both large areas and constant PRQLWRULQJWKHUHE\JHQHUDWLQJVLJQL¿FDQWFRVWV References
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[2] Bastian S., 1980, &RQVWUXFWLRQFRQFUHWHZLWKÀ\DVK Arkady, Warsaw (in Polish).
>@%ODQFR)*DUFLD03$WDOD-9DULDWLRQLQÀ\ ash properties with milling and acid leaching, Fuel, YROSS
>@&KHHUDURW 5 -DWXUDSLWDNNXO &K A study of GLVSRVHG À\ DVK IURP ODQG¿OO WR UHSODFH 3RUWODQG cement, in: Waste ManagementSS >@(OOLRW$''RQJNH=KDQJControlled Release
Zeolite Fertilisers: A Value Added Product Produced from Fly Ash, International Ash Utilization Symposium ,$86 DQG:RUOGRI&RDO$VK :2&$ .
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>@*LHUJLF]Q\=Fly ash with high lime content: Cement Wapno BetonQULQ3ROLVK [8] Goodarzi F., Sanei H., 2009, Plerosphere and its role in
UHGXFWLRQRIHPLWWHG¿QHÀ\DVKSDUWLFOHVIURPSXOYHUL]HG FRDO¿UHGSRZHUSODQWV, in: FuelSS > @+ROOPDQ**6WHHQEUXJJHQ*-DQVVHV-XUNRYLþRYi
M., 1999, $ WZRVWHS SURFHVV IRU WKH V\QWKHVLV RI ]HROLWHVIURPFRDOÀ\DVK, in: )XHOSS >@+XL.6&KDR&<+.RW6&Removal of
mixed heavy metal ions in wastewater by zeolite 4A DQGUHVLGXDOSURGXFWVIURPUHF\FOHGFRDOÀ\DVK, in: Journal of Hazardous materials, B127, pp.89-101. >@,OLF0&KHHVHPDQ&K6ROODUV&K.QLJKW-
Mineralogy and microstructure of sintered lignite coal À\DVK, in: FuelSS
[12] Iyer R., 2002, The surface chemistry of leaching coal À\DVK, in: Journal of Hazardous Materials,% SS
>@àąF]Q\ - $GDPVNL 0 The Mathematical Model RI WKH ,PSDFW RI /DQG¿OOV 6WRULQJ :DVWH (QHUJ\ Products upon Environment, =DNáDG 1DURGRZ\ LP 2VVROLĔVNLFK:\GDZQLFWZR3ROVNLHM$NDGHPLL1DXN :URFáDZ:DUV]DZD.UDNyZ LQ3ROLVK >@àąF]Q\ 0- Unvonventional Methods of Fly
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>@.XFRZVNL - /DXG\Q ' 3U]HNZDV 0 Power Engineering and Environmental Protection, Wydawnictwo Naukowo-Techniczne, Warszawa 1997 (in Polish).
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[22] A Statistical Yearbook, Environmental Protection, 2008 (in Polish).
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[29] Tanaka H., Furusawa S., Hino R.: Synthesis, 2002, &KDUDFWHUL]DWLRQ DQG IRUPDWLRQ 3URFHVV RI 1D; Zeolite from Coal Fly Ash, in: Journal of Materials Synthesis and Processing, SS
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: FHOX RNUHĞOHQLD UyĪQLF Z ]GROQRĞFL VRUSF\MQHM SRSLRáyZSU]HGLSRPRG\¿NDFMLFKHPLF]QHMEDGDQR LQWHQV\ZQRĞü VRUERZDQLD ]ZLą]NyZ RUJDQLF]Q\FK
Z\NRU]\VWXMąF MDNR PRGHO ]ZLą]NX RUJDQLF]QHJR EáĊNLWPHW\OHQRZ\7\PVDP\PPRĪOLZDE\áDDQD-OL]DXE\WNXVXEVWDQFMLEDUZQHMZUR]WZRU]HPHWRGą VSHNWURIRWRPHWU\F]Qą
Badania sorpcji SROHJDá\QDZ\PLHV]DQLXQDZDĪNL SRSLRáX J ]RGSRZLHGQLRSU]\JRWRZDQ\PUR]WZR-UHPEDUZQLND EáĊNLWPHW\OHQRZ\ ZLORĞFLGP.
'REyUVWĊĪHQLDEDUZQLNDXVWDORQRHNVSHU\PHQWDOQLH QDSR]LRPLHRSWLPXP]HZ]JOĊGXQDPRĪOLZRĞFLSR-PLDUX LQWHQV\ZQRĞFL EDUZ\ PHWRGą VSHNWURIRWRPH-WU\F]Qą=DZLHVLQĊZ\WU]ąVDQRSU]H]F]WHU\JRG]LQ\ DQDVWĊSQLHSU]HVąF]DQR:SU]H¿OWURZDQ\PUR]WZR- U]HRNUHĞORQRVWĊĪHQLHEDUZQLND2]QDF]HQLDSURZD-dzono na spektrofotometrze AQUAMATE Thermo 6FLHQWL¿F
=GROQRĞü VRUSF\MQą ]PRG\¿NRZDQHJR SRSLRáX REOLF]RQR ] UyĪQLF\ VWĊĪHĔ EDUZQLND Z UR]WZRU]H przed i po procesie sorpcji. Wynik ten porównano GR Z\QLNX VRUSFML SRSLRáX QLHSRGGDQHJR NRQZHUVML chemicznej. Badania SEM, morfologii ziaren przed L SR PRG\¿NDFML SU]HSURZDG]RQR QD PLNURVNRSLH skaningowym typ Neophot 2.
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=ZUDFDXZDJĊĪHSRSLyáORWQ\SREUDQ\EH]SRĞUHGQLR VSRG HOHNWUR¿OWUD Z\ND]XMH GXĪą ]GROQRĞü VRUSF\MQą Z]JOĊGHPEDUZQLNDDZLĊFMHV]F]HSU]HGPRG\¿NDFMą FKHPLF]QąPRĪHSHáQLüUROĊGREUHJRVRUEHQWX:Z\QL-ku przeprowadzonej reakcji chemicznej uzyskano ma-WHULDáR]QDF]QLHSRGZ\ĪV]RQHM]GROQRĞFLVRUSFMLZREHF EáĊNLWXPHW\OHQRZHJRFR]LOXVWURZDQRQDU\VXQNX Jest to spowodowane zmianami charakteru powierzchni ]LDUHQSRSLRáyZ co zilustrowano na rysunkach 9 i 10 =LDUQD SRSLRáX QLHPRG\¿NRZDQHJR SRVLDGDMą SUDZLH JáDGNLH SRZLHU]FKQLH U\V $ 1DWRPLDVW Z Z\QL-NX REUyENL FKHPLF]QHM QDVWĊSXMH XWZRU]HQLH QRZ\FK VWUXNWXU QD SRZLHU]FKQL ]LDUHQ SRSLRáyZ Z Z\QLNX F]HJRFHFKXMąVLĊRQHZ\VRNąSRURZDWRĞFLą U\V %L =QDMGXMHWRSRWZLHUG]HQLHZZ\QLNDFKEDGDĔSR- ZLHU]FKQLZáDĞFLZHM WDEHOD =PLDQDFKDUDNWHUXSR-ZLHU]FKQLEDGDQ\FKSRSLRáyZGHF\GXMHRZ]URĞFLHLFK ZáDĞFLZRĞFLVRUSF\MQ\FKZREHFEáĊNLWXPHW\OHQRZHJR 6]F]HJyOQLH SRGDWQD QD NRQZHUVMĊ FKHPLF]Qą MHVW ID]D DPRU¿F]QD ] REHFQRĞFLą W\FK ]ZLą]NyZ JOLQX LNU]HPX WDEHOD 3RGF]DVREUyENLFKHPLF]QHMQDVWĊ- SXMHUHDNFMDV]NáD6L$OQDSRZLHU]FKQL]LDUHQGRIRU- P\ĪHOXDQDVWĊSQLHNU\VWDOL]DFMDVWUXNWXURFKDUDNWH-U]H]HROLWyZ (OOLRWL'RQJNH=KDQJ 0XUD\DPD i in., 2002). Proces ten jest tym bardziej efektywny im ZLĊFHMID]\DPRU¿F]QHMZ\VWĊSXMHZSUyELHSRSLRáX
-DN Z\ND]Dá\ EDGDQLD UHQWJHQRZVNLH EDGDQH SR-SLRá\ ]DZLHUDMą RNRáR ID]\ DPRU¿F]QHM FR sprzyja tworzeniu tych struktur.
: FHOX RV]DFRZDQLD ZSá\ZX F]DVX SRERUX SUyE EDGDQRSRSLRá\SREUDQHZWU]HFKUyĪQ\FKODWDFK QD SRZWDU]DOQRĞüZ\QLNXZ\NRQDQREDGDQLHVWDW\VW\F]-ne oparte na jednoczynnikowej analizie wariancji X]\VNDQ\FKZ\QLNyZVRUSFML3U]\MĊWRQDZVWĊSLHKL-SRWH]ĊĪHF]DVSRERUXSUyE\PDZSá\ZQD]GROQRĞFL VRUSF\MQHSRSLRáyZORWQ\FK
: SU]\SDGNX SRSLRáyZ VXURZ\FK SREUDQ\FK w latach 2007-2009 wykazano graniczny poziom LVWRWQRĞFLQDSR]LRPLHFRSR]ZDODVWZLHUG]Lü ĪH EDGDQH SUyE\ SRSLRáyZ ORWQ\FK Vą VWRVXQNRZR jednorodne i czas poboru próby nie ma istotnego ZSá\ZXQD]GROQRĞFLVRUSF\MQH Podsumowanie 0LPRĪHSRSLRá\ORWQHVąPDWHULDáHPGREU]HUR]SR- ]QDQ\PLZ\NRU]\VW\ZDQ\PZĞZLHFLHX]DVDGQLR-QHMHVWGDOV]HSRV]XNLZDQLHLFKQRZ\FK]DVWRVRZDĔ ]ZáDV]F]DGODSRSLRáyZ]HOHNWURFLHSáRZQL
: SUH]HQWRZDQ\FK EDGDQLDFK ZáDVQ\FK SRWZLHU-G]RQR ĪH SRSLRá\ NWyU\FK ZáDĞFLZRĞFL FKHPLF]QH G\VNZDOL¿NXMą LFK Z\NRU]\VWDQLH Z EXGRZQLFWZLH PRJąE\üVWRVRZDQHZFKDUDNWHU]HVRUEHQWyZZVWD- QLHVXURZ\P=GROQRĞFLVRUSF\MQHW\FKSRSLRáyZXOH- Já\SRSUDZLHZZ\QLNXNRQZHUVMLFKHPLF]QHMZĞUR-GRZLVNX1D2+.RQZHUVMĊFKHPLF]QąSRWZLHUG]RQR ZEDGDQLDFKSRZLHU]FKQLZáDĞFLZHMLVWUXNWXU\SRSLR-áyZ:\QLNLEDGDĔSU]HSURZDG]RQ\FKZPLNURVNRSLH HOHNWURQRZ\P SRWZLHUG]Lá\ WZRU]HQLH VLĊ QRZ\FK struktur krystalicznych, na powierzchni ziaren popio- áyZLZ]URVWFKURSRZDWRĞFL:\QLNLEDGDĔ%(7Z\-ND]Dá\UDG\NDOQ\Z]URVWSRZLHU]FKQLZáDĞFLZHMSUyE SR PRG\¿NDFML FKHPLF]QHM 3R]RVWDMH WR Z ]JRG]LH ] Z\QLNDPL EDGDĔ VRUSFML EáĊNLWX PHW\OHQRZHJR ZNWyU\FKDNW\ZDFMDFKHPLF]QDSRSLRáyZSU]\F]\QL-áDVLĊGRSRSUDZ\WHM]GROQRĞFL
: ĞZLHWOH SU]HSURZDG]RQ\FK EDGDĔ Z\GDMH VLĊ X]DVDGQLRQH GDOV]H UR]SR]QDQLH ]GROQRĞFL VRUSF\M-Q\FKSRSLRáyZZ]JOĊGHP]DQLHF]\V]F]HĔREHFQ\FK QSZĞFLHNDFKNRPXQDOQ\FKOXERGFLHNDFKVNáDGR-wiskowych.
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