PORTLAND CEMENT PRODUCTION WITH DREGS AND GRITS FROM KRAFT PULP MILLS INCORPORATION TO THE CLINKER

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Universidade Federal de Viçosa PORTLAND CEMENT PRODUCTION WITH DREGS AND GRITS FROM KRAFT PULP MILLS INCORPORATION TO THE CLINKER Authors: Caio Torres Cláudio Silva Leonardo Pedroti Wellington Fernandes Fabiane Ballotin

INTRODUCTION It is estimated that in 2016 in Brazil were generated : 282,000 tons of Dregs 94,000 tons of Grits 2

INTRODUCTION Dregs, originated from green liquor clarification are impurities originating mainly from carbon, hydroxides and metal sulfides with ph approximately 11 and generated of up to 15 kg.adt -1 of pulp produced 3

INTRODUCTION Grits, originated in the slakers are composed of unreacted lime with ph approximately 11 and generation of up to 5 kg.adt -1 of pulp produced 4

Green Liquor INTRODUCTION lime Filtration Clarification of Green Liquor Dregs Grits Slaker limestome Causticizers Lime kiln Lime mud filter Lime mud tank White liquor storage tank Weak white liquor 5

INTRODUCTION Source: PUC-RIO 6

INTRODUCTION The Brazilian market has 8 cement options The factors that differentiate the types of cement are the addition in the process of grinding different proportions of Clinker, calcium sulphates, carbonatic material and additions (slag, pozzolans and calcareous) Cimento Comum (CP I) Cimento Composto (CP II) Cimento de Alto-Forno (CP III) Cimento Pozolânico (CP IV) Cimento de Alta Resistência Inicial (CP V-ARI) Cimento Resistente a Sulfatos (RS) Cimento de Baixo Calor de Hidratação (BC) Cimento Portland Branco (CPB) 7

OBJECTIVES This paper proposes the incorporation, in different proportions (2.5; 5; 7.5; 10 and 15%), of alkaline solid wastes from pulp mills, namely dregs and grits, to clinker in the cement industry 8

MATERIAL AND METHODS Dregs and grits were obtained from a Brazilian bleached kraft pulp mill Clinker was obtained from a Brazilian cement These materials were characterized in the laboratories of the Federal University of Vicosa UFV and the Federal University of Minas Gerais UFMG 9

MATERIAL AND METHODS The dregs and grits were submitted to an experimental path described by the flowchart Dregs / Grits / Clinker Drying Milling Sieving Characterization Mixture Percente of Dregs + Clinker Grits + Clinker Physical Specific Mass Specific Area Fineness SEM Chemical EDX EDS XRD Pozzolanic TG/DTG 0% 2.5% 5% 7.5% 10% 15% Soundness by the Le Chatelier Determination of the paste with normal consistency Compressive Strength Elasticity Modulus Setting Times Cold Hot 3 days 7 days 28 days 10

Dregs / Grits / Clinker Drying Milling Sieving Characterization Mixture Percente of Dregs + Clinker Grits + Clinker Physical Specific Mass Specific Area Fineness SEM Chemical EDX EDS XRD Pozzolanic TG/DTG 0% 2.5% 5% 7.5% 10% 15% Soundness by the Le Chatelier Determination of the paste with normal consistency Compressive Strength Elasticity Modulus Setting Times Cold Hot 3 days 7 days 28 days11

In the present research for each incorporation of dregs and grits (2.5; 5; 7.5; 10 e 15%) to the clinker Samples Dregs Grits Series Dosage materials for experimental clinker Cliker Trace (%) Dose Compressive strength Amount of specimens Elasticity modulus CPo - 0 100 0 12 9 CPd - 2.5 97.5 2.5 12 9 CPd - 5.0 95.0 5.0 12 9 CPd - 7.5 92.5 7.5 12 9 CPd - 10.0 90.0 10.0 12 9 CPd - 15.0 85.0 15.0 12 9 CPg - 2.5 97.5 2.5 12 9 CPg - 5.0 95.0 5.0 12 9 CPg - 7.5 92.5 7.5 12 9 CPg - 10.0 90.0 10.0 12 9 CPg - 15.0 85.0 15.0 12 9 Total 132 99 12

MATERIAL AND METHODS For each dose, four specimens were tested in each age (3, 7 and 28 days). The elasticity modulus test was carried out only in the last three specimens. The used universal testing machine was a EMIC, model DL600KN compressive strength and elasticity modulus 13

RESULTS AND DISCUSSION EDX of clinker, dregs and grits CaO SiO 2 Al 2 O 3 Fe 2 O 3 SO 3 MgO K 2 O Na 2 O TiO 2 Cl Others Clinker (%) 64.55 20.65 3.02 3.23 1.00 0.33 1.47 1.71 0.27 0.07 3.72 Dregs (%) 68.85 6.67 0.74 3.27 6.44 3.14 0.91 3.64 0.18 0.39 5.78 Grits (%) 83.36 5.21 0.29 1.16 0.97 0.66 0.50 2.77 0.08 0.27 4.73 14

SEM Dregs EDS Dregs SEM Grits EDS Grits

Tests Results of material characterization tests Normal Consistency (A(%)) Soundness by the Setting Times (h:min) Le Chatelier (mm) Stard End Hot Cold Clinker 30.88 1:45 2:40 0 0.27 2.5% 5.0% 7.5% 10.0% 15.0% Dregs --- 1:55 2:47 0 0 Grits --- 1:15 2:15 0 0 Dregs --- 1:20 2:25 0 0 Grits --- 1:30 2:45 0 0 Dregs --- 1:11 2:43 0 0 Grits --- 1:40 3:26 0 0 Dregs --- 1:16 2:37 0 0 Grits --- 1:24 2:56 0 0 Dregs --- 0:32 3:10 0 0 Grits --- 0:55 2:42 0 0 Limits --- 1h 10hs 5 5 16

Tests Specific mass (g/cm³) Specific Area (m²/kg) Fineness (%) Pozzolanic (ms/cm) Clinker 3.00 246 0.26 0.98 Dregs 2.44 1031 0.78 0.87 Grits 2.67 972 95.20 0.31 2.5% 5.0% 7.5% 10.0% Dregs 2.94 282 0.22 --- Grits 3.05 325 1.28 --- Dregs 2.99 315 0.28 --- Grits 3.01 306 2.46 --- Dregs 2.93 307 1.00 --- Grits 2.99 301 5.36 --- Dregs 2.87 335 0.54 --- Grits 3.00 361 2.72 --- Dregs 2.98 404 0.44 --- 15.0% Grits 2.95 352 3.96 --- Limits --- 245 12 --- 17

The results of the COMPRESSIVE STRENGTH TESTS on four of the percentages Dregs and Grits 3, 7 and 28 days of age

The results of the ELASTICITY MODULUS TESTS on four of the percentages Dregs and Grits 3, 7 and 28 days of age

CONCLUSIONS The physical-chemical characterization of dregs and grits showed a great potential to use these materials for incorporation into the clinker Portland cement production The different incorporation of dregs and grits (2.5; 5.0; 7.5 and 10%) to the clinker proved viable for ordinary Portland cement production with addition (CP I-S) and Portland composite cement (CP II-F) 20

CONCLUSIONS The incorporation of both materials to clinker fulfilled the minimum limits for the compressive strength test and modulus of elasticity established by the Brazilian standard Grits showed, in general, better results than Dregs 21

REFERENCES BRAZILIAN ASSOCIATION OF TECHNICAL NORMS. NBR NM 23: Determination of density. 1 ed. Rio de Janeiro. 2001. 5p. (available only in Portuguese). NBR 11,578: Portland composite cement Specification. 1 ed. Rio de Janeiro. 1991 Erratum 1997. 5p. (available only in Portuguese). NBR 8,522: Determination of elasticity modulus by compression. 2 ed. Rio de Janeiro. 2008. 16p. (available only in Portuguese) KINNARINEN, Teemu et al. Separation, treatment and utilization of inorganic residues of chemical pulp mills. Journal of Cleaner Production, v. 133, p. 953-964, 2016 BURUBERRI, Leire H.; SEABRA, M. P.; LABRINCHA, J. A. Preparation of clinker from paper pulp industry wastes. Journal of Hazardous Materials, v. 286, p. 252-260, 2015 222

ACKNOWLEDGEMENTS The authors thank the dedication of all servers and students DEF (LCP), DEC (LMC) UFV and the UFMG microscopy center for the images We also acknowledge the CNPq, CAPES, FAPEMIG and Bioforest for the support provided to this investigation 23

Universidade Federal de Viçosa Questions? Thank you! Caio Torres caiomiquelino@yahoo.com.br Cláudio Mudadu Silva mudado@ufv.br Tel: +55 31 3899-2081