Development of eco-efficient binders to encapsulation of heavy metals

Transcription

1 Development of eco-efficient binders to encapsulation of heavy metals Eliz Paula Manfroi,a, Malik Cheriaf,b*, Janaíde Cavalcante Rocha,c,, University Federal of Santa Catarina, Department of Civil Engineering a elizmanfroi@yahoo.com.br, b malik.cheriaf@gmail.com, c janaide.rocha@ufsc.br Keywords: binder, encapsulation, ettringite, red mud, FGD gypsum. Abstract. The use of eco-efficient binders, ie binders produced with reduced environmental impacts, such as: reduction of the extraction of raw materials, calcination energy and CO emissions; use of wastes as raw material and heavy metal encapsulation provides an alternative for the sustainable development. In this work were produced binders with partial replacement of the calcium aluminate cement by FGD gypsum and red mud. The partial replacement of calcium aluminate cement for FGD gypsum was carried out with the aim of form ettringite, which was used to encapsulate heavy metals from wastes FGD gypsum and red mud. For this, pastes and mortars were produced with different proportions of aluminate cement, FGD gypsum and red mud. Hydrated compounds and phases in pastes and mortars were investigated using X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM). The results showed that closer is the ratio CA/FGD (calcium aluminate cement/fgd gypsum) to the theoretical ratio (stoichiometric ratio CA/FGD for optimized ettringite formation), greater is the amount of the ettringite formed. Compressive tests, water absorption by capillarity and evaluation of the encapsulation of heavy metals in mortars showed that the ratio CA/FGD most appropriate is,. The result of this research showed that calcium aluminate cement can be replaced partially by FGD gypsum and red mud to produce eco-efficient binders. Introduction The FGD gypsum is a waste generated in the coal-fired power plants. This residue is produced during the desulphurization process of flue gases. In this process, the reaction between sulfur dioxide (SO ) from flue gas, calcium carbonate, limestone and oxygen form the FGD gypsum (CaSO.H O) as a by-product. The FGD gypsum is composed mainly of calcium oxide and sulfur trioxide [, ]. In the alumina industry, the red mud (RM) is the residue that causes major environmental impacts. This residue is from the refining of bauxite during the Bayer process for the production of alumina and the posterior production of aluminum. The red mud from the Bayer process is composed mainly of alumina, iron oxide and silica. Besides, the red mud is classified as a hazardous residue (class I), because the red mud has chromium and selenium concentrations higher than the limits values defined in annex F of the Brazilian standard NBR []. Studies have been developed to valorization of the red mud for the production of cement composites [,,, ]. One of the effective ways to increase the use of FGD gypsum is used it as partial replacement of calcium aluminate cement (CAC) for production of eco-efficient binders, because calcium sulfate, main component of natural gypsum, it is also the main component of the FGD gypsum. When calcium sulfate reacts with calcium aluminate from alumina cement and water, the ettringite is formed [, ]. Researchers found that ettringite is able to partially encapsulate the chromium from galvanic sludge []. This researchers detected the presence of chromium in the particles of bottom ash and the ettringite needles by scanning electron microscopy analysis in the pastes. The potential of ettringite in the encapsulation of heavy metals present in solid waste, was also investigated by other researchers [,, ]. Given this context, eco-efficient binders were developed for FGD gypsum and calcium aluminate cement for encapsulating heavy metals of the red mud and FGD gypsum in the ettringite structure.

2 This paper presents the results of the physical evaluation, chemical and mechanical properties of mortars produced with these binders, and the evaluation of the eco-efficiency point of view of the encapsulation of heavy metals. Materials and Methods Materials. The sample of FGD gypsum was collected in a coal-fired power plants in the state of Rio Grande do Sul. The FGD gypsum was calcined at C (hemihydrate). According to the measurements % of FGD gypsum particles are smaller than. mm (laser diffraction, Microtrac S). The sample of red mud was collected in an alumina industry in the northern Brazil. Pastes and mortars were produced with red mud calcined at C, based on previous studies []. Before calcination, the red mud was dried in an oven at ± C (for h). The maximum particles size of red mut at C were smaller than. mm (Malvern laser diffraction Mastersizer dispersant water). The pastes and mortars were produced with Fondu calcium aluminate cement. The mortars were produced with standard sand. The chemical characteristics of the raw materials were carried out using energy dispersive X-ray fluorescence spectrometry (EDX, Model HS, Shimadzu). The chemical composition of raw materials are shown in Table. Table : Chemical composition (wt.%) of the aluminous cement, FGD gypsum and red mud Oxides (%) Sample Al O CaO TiO Fe O K SO SiO Cement FGD gypsum Red mud The presence of the elements arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni) and zinc (Zn) from red mud and FGD gypsum were identified by inductively coupled plasma mass spectrometry analysis (PerkinElmer, model NexIon D). Table shows the amount (mg/kg) of these elements from red mud and FGD gypsum. Table : Elements arsenic, cadmium, chromium, copper, nickel and zinc present in the FGD gypsum and red mud Elements (mg/kg) Sample Cr As Cd Cu Ni Zn Red mud.±..±..±..±..±.. ±. FGD gypsum.±. <. <..±..±. <. Methods. Production of Pastes and Mortars. The investigation of the hydrated compounds and assessment of the proportion of the phases were carried out in pastes composed by to % of FGD gypsum, in a mass substitution of the calcium aluminate cement. The pastes were produced with a water/binder ratio of. and.% of superplasticizer additive (polycarboxylate ether based). In order to evaluate the potential encapsulation of heavy metals from the red mud and FGD gypsum in the ettringite structure, mortars with % of calcium aluminate cement and to % FGD gypsum in replacement of calcium aluminate cement were produced (A to A). Afterwards, mortars were produced with to % of FGD gypsum (amount calculated on the mass CACFGD % to % CACFGD) and % (B to B), % (C to C) or % (D to D) of red mud in substitution of the total mass of the cement plus FGD gypsum. Table shows the mix proportions of the different mortars.

3 Mortars were produced according the binder to sand ratio of : (in mass). The water/binder ratio kept constant at. and.% of superplasticizer additive (polycarboxylate ether based) was used. Table : Composition of the mortars Mortar Composition CAC+FGD (%) CAC (%) FGD (%) CAC/FGD RM (%) A..... A..... A..... A..... A..... B..... B..... B..... B..... B..... C..... C..... C..... C..... C..... D..... D..... D..... D..... D..... Investigation of Hydrated Compounds and Proportion of the Mineralogical Phases. After the hydration periods ( days), pastes and mortars were ground (particle size <. mm) and analysed by X-ray diffraction (Model X-Pert, Philips) and diferencial scanning calorimetry (Model SDT Q- TA). The microstructures of the pastes were investigated by scanning electron microscopy analysis (Model JSM-LV, JEOL). The diffraction X-ray analysis and integrated intensity methodology were used to estimate the proportions of the mineralogical phases of pastes produced with calcium aluminate cement and FGD gypsum. The integrated intensities of the peaks in a diffractogram of a phase were related to the amount of this phase in the sample. This relationship has been used for many years in the quantitative analysis of mineralogical phases []. Researchers used the method of the integrated intensity to estimate the amount of mineralogical phases present in zeolites and estimate the crystallinity of the bottom ash [, ]. The proportion of each phase was determined based on integration of the most intense peak of each phase []. Evaluation of Compressive Strength, Water Absorption by Capillarity and Encapsulation of Heavy Metals in Mortars. The compressive strength was carried out in mortar in accordance with the procedures described in Brazilian standard NBR []. In order to evaluate the water absorption by capillarity of the mortars was used a procedure that consists in the measure of the height variation of a water column contained in a graduated Mariotte tube in function of time []. The height variation of the water column is directly related with the amount of water absorbed by the sample. The volume of water absorbed by section of the sample was called absorption index (I = cm /cm ). The inclination of the straight (absorption index versus square root of time) corresponds to sorptivity. In Brazil there are no standards on environmental assessment of monolithic materials produced with waste. Thus, to evaluate the release of heavy metals from mortars the leaching test was performed in accordance with the procedure established by Dutch standard NEN []. After days, the leachate extract obtained was filtered and analyzed using energy dispersive X-ray fluorescence spectrometry (Modelo HS, Shimadzu).

4 Intensidade Intensity (cps) (cps) Results and Discussion Mineralogy and Microstructures of the Pastes. Fig. shows the diffractograms of the pastes at days. The phases detected in the pastes with % calcium aluminate cement were monocalcium aluminate - CA (), calcium dialuminate- CA (), gelenite- C AS (), C AH (), C AH () and gibbsite AH (). %FGD %FGD %FGD - CA - CA - C AS - C AH - C AH -AH - Ettringite - Gypsite -CaSO.,H O %FGD %FGD %FGD %FGD %CA θ CAC FGD+CAC FGD+CAC FGD+CAC FGD+CAC FGD+CAC FGD+CAC FGD+CAC Figure Diffractograms of the pastes produced with calcium aluminate cement and FGD gypsum at days Differently from the pastes with % of calcium aluminate cement, pastes with % FGD gypsum showed the phases gypsite () and CaSO.,H O (). The hydration of the calcium sulfate hemihydrate (CaSO.,H O) resulted in the formation of gypsite (CaSO.H O). However, the presence of CaSO.,H O phase shows that part of calcium sulfate hemihydrate (FGD C) added into the mixture did not react with the compounds of calcium aluminate cement and/or water to form hydrated products. Furthermore, in the pastes with % of FGD gypsum was not detected the presence of ettringite. The lack of the peak corresponding to ettringite in these pastes is related to the low amount of calcium sulfate present in the mixture to react with the compounds calcium aluminate cement and water to form ettringite. As well as pastes produced with %CA+%FGD, the pastes with to % of FGD gypsum in replacement of calcium aluminate cement showed the mineralogical phases: CA (), CA (), C AS (), C AH (), AH (), gypsite () e CaSO.,H O (). However, in the pastes with to % of FGD gypsum was identified the presence of ettringite () and the absence of the C AH (). Moreover, the higher the content of FGD gypsum, the higher the intensity of the peak of ettringite. The lack of the C AH phase is related to least amount of calcium aluminates available for hydration due to reduction of calcium aluminate cement. Also due to the reactions between the calcium sulfate from FGD gypsum and calcium aluminate from cement for formation of ettringite Fig. shows the percentage of the areas of the more intense peaks of the phases C AH, C AH e ettringite, which are related to the amount of formed phases [,, ]. In the pastes with to % of gypsum, the higher the FGD gypsum content, the higher the peak area and consequently the higher the amount of ettringite formed. The paste with % of FGD gypsum showed the highest ettringite content (.%), in accordance with the calculations of the proportion of gypsum needed

5 % the peak area of the mineralogical phase to form the ideal ettringite (theoretical) []. As the peaks of C AS, CaSO.H O, CA, CaSO.,H O phases were overlapped was not possible to determine exactly the areas these peaks and to estimate the amount of these phases in the samples. Content of FGD gypsum (%) CAH CAH Ettringite Figure - Percentages of the areas of the main peaks of the diffractograms of C AH, C AH phases and ettringite in pastes with calcium aluminate cement and FGD gypsum The analysis of differential scanning calorimetry (DSC) carried out in the FGD gypsum (dry C), reference paste (% CAC) and the pastes with to % FGD gypsum in replacement of calcium aluminate cement at days are shown in Fig.. The DSC curve of the paste with % of calcium aluminate cement show the presence of an endothermic peak at ºC, which is associated to the loss of moisture. The endothermic peak at ºC of the DSC curve of the paste with % de CAC indicates the presence of the C AH compound. The double endothermic peak approximately at C is related to the presence of the gibbsite and C AH. The peaks correspondent to the presence of gibbsite and C AH are more evident in the curve of the derivative thermogravimetry []. The C AH, gibbsita e C AH hydrated compounds in the pastes with % of CAC were also detected by means of the analysis of X-ray diffraction. Although endothermic peak correspondente to gypsum does not appear in the DSC curves of the pastes with up to % of FGD gypsum (overlapping peaks), the results of the analysis of X-ray diffraction confirmed that all pastes produced with the FGD gypsum have gypsite in their mineralogical composition (Fig. ). The endothermic peaks at C of the DSC curves of pastes with FGD gypsum containing more than % of FGD gypsum are most evident. The DSC curves of pastes with % CAC + % FGD, DSC curves of pastes with to % FGD gypsum in replacement to calcium aluminate cement showed endothermic peaks at C, C, C, and ºC that are attributed to the loss of moisture, presence of gypsite, CaSO.,H O, gibbsite and C AH, respectively. However, differently from DSC curves of the pastes with % FGD gypsum in replacement to calcium aluminate cement, the DSC curves of the pastes with to % FGD gypsum showed an endothermic peak at C associated to presence of ettringite and have not showed endothermic peak at C associated to C AH. The presence of the gypsite, CaSO.,H O, gibbsite, C AH and ettringite in these pastes were also detected by means of the analysis of X-ray diffraction.

6 Heat flow /mass(mw/mg) Dihydrate C AH Gypsite Ettringite Hem. C AH Hem. C AH Gibbsite Hemihydrate Soluble anhydrite (CaSO.ƐH O) Hemihydrate Temperature (ºC) FGD_dry_ºC CAC FGD+CAC FGD+CAC FGD+CAC FGD+CAC FGD+CAC FGD+CAC FGD+CAC %FGD %FGD %FGD %FGD %FGD %FGD %CAC Figure - Analysis of differential scanning calorimetry of the FGD gypsum, of the paste with % CAC and of the pastes with at % of FGD gypsum in replacement of calcium aluminate cement The image of the microstructures of the paste with % of calcium aluminate cement and % of FGD gypsum shows the presence of ettringite crystals (Fig. ). This hydrated compounds was also detected by means of the analysis of X-ray diffraction and differential scanning calorimetry. Ettringite %FGD FGD dry ºC Figure Image of the microstructure of the paste produced with % of calcium aluminate cement and % of FGD gypsum at days Mineralogy of the mortars. The mortars with, and % of red mud in replacement of calcium aluminate cement (B, C e D) showed the same mineralogical phases than the mortar A: CAH (), C AH (), C AH (), AH - gibbsite (), SiO quartz (), C AS-gelenite () e anortite (); showing that the replacement of calcium aluminate cement and FGD gypsum by red mud has not changed the mineralogical structure of mortars. Fig. shows the diffractograms of the mortars C to C. Mortars B, C e D showed the same mineralogical structure than the mortar A, which showed the phases C AH (), C AH (), AH - gibbsite (), SiO quartz (), C AS-gelenite (), CaSO.,H O () and gypsite (). However, the sample A at A, B at B, C at C and D at D did not present the CAH and C AH phases and presented the ettringite phase. The lack of the calcium aluminate hydrates CAH and C AH to due the replacement of the FGD gypsum by calcium aluminate; reducing the amount of calcium

7 Intensity (cps) aluminates available for hydration. Moreover, due to the calcium aluminates react with the calcium sulfate hemihydrate and water to form ettringite. - CAH - C AH - C AH -AH -SiO -C AS -Ettringite -CaSO.,H O - Gypsite -Anortite θ C C C C C Figure - Diffractograms of the mortars C at C at days Evaluation of Compressive Strength of the Mortars. Fig. shows the results of the average compressive strength at days of the mortars A to A, B to B, C to C and D to D. The mortars with replacement of the calcium aluminate cement by FGD gypsum and/or red mud (A- A, B-B, C-C, D-D) showed lower compressive strength values than the sample with % of calcium aluminate cement (A), because there was a reduction in the formation of the calcium aluminate hydrates due to low amount available calcium aluminates in the mixture caused by replacement calcium aluminate cement. The samples B-B, C-C e D-D produced with calcium aluminate cement, FGD gypsum and to % of red mud showed compressive strength values at days which were on average similar to the compressive strength values of the mortars A-A (CAC and FGD), showing that the compressive strength of mortars presents significant variation only when the ratio CAC/FGD changes. Moreover, of the mortars B, C and D, the average compressive strength of the samples C and D ( and % RM) remained constant, indicating that the red mud has a filler effect. In the mortars with ratio CAC/FGD varying from. to. (A-A, B-B, C-C, D-D), the lower ratio CAC/FGD, the less compressive strength. However, the compressive strength of the mortars increased when ratio CAC/FGD decreased to.. The lower compressive strength of the mortars with CAC/FGD equal to. (A, B, C and D) is related to lower formation of calcium aluminate hydrates, low ettringite content, presence of gypsite and also CaSO.,H O. As seen in the results of the analysis of X-ray diffraction, the diffractograms peaks associated to ettringite of these mortars have lower intensity than the same diffractograms peaks of the mortars produced with CAC/FGD equal to. and., respectively. The closer the ratio CAC/FGD of the theoretical ratio CAC/FGD (.) [] the larger amount of ettringite formed and consequently a higher compressive strength of the mortars.

8 S (cm /cm xmin / ) Compressive strength (MPa) ARG-A ARG-B ARG-C ARG-D Sample ARG_ ARG_ ARG_ ARG_ ARG_ Figure - Average compressive strength of the mortars A, B, C and D at days Water Absorption by Capillarity. The variations of the sorptivity of the mortars B to B, C to C and D to D are shown in Fig.. In general, the mortars B, C and D (ratio CAC/FGD =.) showed sorptivity lower than the sorptivity of the mortars B-B, C-C, D-D (ratio CAC/FGD. and., respectively), due to samples with lower ratio CAC/FGD have larger amount of ettringite formed; reducing the pore connectivity and the sorptivity of the mortars.,,,,,,,,,,,,,, ARG-B ARG-C ARG-D Sample ARG_ ARG_ ARG_ ARG_ Figure - Sorptivity of the mortars B-B, C-C and D-D In the mortars which have ettringite in its mineralogical composition, the mortars produced with ratio CAC/FGD equal to. (B, C and D) showed a lower sorptivity. Moreover, the larger the content of calcium aluminate cement replacement and FGD gypsum by red mud, the larger the sorptivity of the mortar. This is related with the larger replacement of the calcium aluminate cement and FGD gypsum by red mud, forming low amount of calcium aluminate hydrates and ettringite; increasing connectivity between the pores. Encapsulation of Heavy Metals in Mortars. The elements leached from mortars A to A and the concentrations limits defined in annex F of the Brazilian standard NBR [] are shown in Fig.. The mortars produced with % of calcium aluminate cement showed concentrations of arsenic, cadmium and chromium higher than the limits values of the Brazilian standard NBR. The elements arsenic (As), cadmium (Cd), chromium (Cr), iron (Fe), nickel (Ni), titanium (Ti) and zinc (Zn) leached from mortar are derived from the raw materials used in producing of the mortars.

9 Concentration (mg/l) Concentration (mg/l) The mortar A showed concentrations of metals leached higher than the concentrations leached from of the mortars A to A. The highest concentrations of metals leached from mortar A are related to lower amount of calcium aluminate hydrates formed. Moreover, despite of the mortars A and A showed concentrations leached of chromium similar to concentration leached from mortar A; the mortars A and A have a higher amount of chromium due to the larger replacement of the calcium aluminate cement by FGD gypsum. However, in mortars with higher ettringite content was lower release of chromium. As Cd Cr Cu Fe Ni Ti Zn Elements A A A A A Lim._NBR Figure - Concentrations of elements leached from mortars A to A and limits values of the Brazilian standard The mortars C to C, B to B and D to D, produced with calcium aluminate cement, FGD gypsum and red mud showed concentrations of cadmium, arsenic and chromium higher than the limits values defined in annex F of the Brazilian standard NBR []. The accumulated concentrations at days of elements leached from mortar D to D (% RM) and the concentration limits defined in Brazilian standard are shown in Fig.. As Cd Cr Cu Fe Ni Ti Zn Elements D D D D Lim._NBR Figure - Concentrations of elements leached from mortars D to D and limits values of the Brazilian standard Fig. shows the concentrations of chromium leached from mortar B, C and D as a function of the ratio CAC/FGD. Mortars with ratio CAC/FGD equal to. and to % of red mud in replacement of the calcium aluminate cement and FGD gypsum showed concentrations of metals leached higher than concentrations of metals leached from mortars produced with ratio CA/FGD

10 Concentration (mg/l) equal to.,.,. and to % of red mud. The higher concentrations of the metals leached from mortars with ratio CAC/FGD equal to. is related to lack of ettringite in these samples and the lower amount of calcium aluminate hydrates formed. In general, the mortars with ratio CAC/FGD equal to. showed concentrations leached of arsenic, cadmium and chromium lower than the concentrations leached these metals from mortars with ratio CAC/FGD equal to., due to the mortars with ratio CAC/FGD equal to. showed lower amount of FGD gypsum in the mixture. Ratio CAC/FGD Cr_ARG_B Cr_ARG_C Cr-ARG_D Figure Concentrations accumulated leached at days of chromium from mortars B, C and D in function of the ratio CA/FGD Conclusions The mineralogical analyzes carried out in pastes and mortars showed that calcium sulfate from FGD gypsum reacted with the calcium aluminates from calcium aluminate cement and water to form ettringite. The closer the ratio CAC/FGD is of the ratio theoretical CAC/FGD, the larger the amount of ettringite formed and the lower the amount of calcium aluminate hydrates. The most appropriate ratio CAC/FGD to obtain larger amount of ettringite, higher compressive strength and lower sorptivity of the mortars would be equal to. i.e. the ratio CAC/ FGD closer to theoretical ratio CAC/FGD (.) evaluated in this study. However, due to FGD gypsum shows high concentrations of chromium leached, the ratio CAC/FGD indicated is.. The ratio CAC/FGD equal to. was also efficient for the encapsulation of metals, because despite the larger amount of FGD gypsum (higher metal content), the amount of ettringite formed in these pastes resulted in the partial encapsulation of metals. The results of the release of heavy metals from mortars produced with red mud showed that the content of replacement of the calcium aluminate cement and FGD gypsum by red mud the most appropriate is %. Lastly, the results of this research showed that is possible to use FGD gypsum residue, red mud and calcium aluminate cement to produce mortar with partial encapsulation of heavy metals in the ettringite structure. References [] D. A. Kost, J. M. Bigham, R.C.Stehouwer, J.H. Beeghly, R. Fowler, S.J.Traina, W.E. Wolfe, W.E.; W.A. Dick, Chemical and physical properties of dry flue gas desulfurization products, Journal of Environmental Quality () -. [] P. Tesárek, J. Drchalova, J. Kolísko, P.R. Kova, P. Rovnaníková, R. CERNÝ, Flue gas desulfurization gypsum: study of basic mechanical, hydric and thermal properties, Construction and Building Materials () -. [] E.P. Manfroi, M. Cheriaf, J.C Rocha, Microstructure, mineralogy and environmental evaluation of cementitious composites produced with red mud waste, Construction and Building Materials () -.

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