Challenges in the cement industry solved by XRF and XRD D. Bonvin and C. Wiedmann Thermo Scientific XRF and XRD Products Portfolio for Cement Industry precision 9900 Perform X Optim X Quant X 2 throughput 3 Thesis to be proven today 1. XRD can make your final cement resistance better by analyzing the Quartz content 2. Measuring with XRD gives a much better picture of the clinker phases than the Bogue formula 3. Even simple XRF instruments can do a great job in analyzing your alternative fuels. 3 3 Thesis to be proven today 1. XRD can make your final cement resistance better by analyzing the Quartz content 2. Measuring with XRD gives a much better picture of the clinker phases than the Bogue formula 3. Even simple XRF instruments can do a great job in analyzing your alternative fuels. 4 Quartz in raw materials • Quartz veins in quarry • Particle size: > 45 microns • Quality issues when quartz content too high 5 Effect of quartz content on 28-day resistance 20 45 MPa 28-day resistance 1 6 2 3 (%) quartz content in raw meal PHASE ANALYSIS APPLICATIONS IN CEMENT INDUSTRY 1. Quartz in raw meal 7 ARL 9900 with integrated XRD 8 Quartz in raw meal X-ray Workstation • X-ray Workstation diffractograms on three raw meal samples 9 Quartz in raw meal X-ray Workstation 10 Calibration curve for quartz – ARL 9900 Total Cement Analyzer XRF-XRD Multi Variable Regression curve for the quartz Correlation of XRD intensity at quartz position with concentration in sample 11 Repeatability test on quartz determination Raw meal 1 Quartz % 12 Run 01 6.8 Run 02 6.7 Run 03 6.9 Run 04 6.8 Run 05 6.6 Run 06 6.7 Run 07 6.8 Run 08 6.9 Run 09 6.8 Run 10 6.7 Run 11 6.6 Avg 6.8 Std Dev 0.1 • Repeatability test for quartz determination • 11 runs on the same raw meal pressed sample • Good repeatability using 40s counting time (ARL 9900 Total Cement Analyzer) Conclusion to case study 1 Thermo Scientific ARL 9900 • Determination of Quartz done by XRD helps avoid quality problems in cement industry • X-Ray Diffraction can be used for a fast determination • integrated XRF-XRD system to make it simpler 13 3 Thesis to be proven today 1. XRD can make your final cement resistance better by analyzing the Quartz content 2. Measuring with XRD gives a much better picture of the clinker phases than the Bogue formula 3. Even simple XRF instruments can do a great job in analyzing your alternative fuels. 14 Applications for Phase Analysis in Cement Industry 3 Free lime in clinker Clinker phases 15 Problem statement Cement Producers would like to know about the clinker phases: • • • • • C 3S C 2S C 3A C4AF CaO Alite Belite Aluminate Ferrite Free Lime This helps to understand: • Final resistance and strength of cement • Efficiency of burning process and energy savings ! define right energy balance 16 3 ways to get to the cement phases: Microscopy counting Bogue Formula Elemental Analysis %C3S = (%CaO - %CaO free) x 4.07 - (%SiO2 x 7.6 + %Fe2O3 x 1.43 + %Al2O3 x 6.72) %C2S = %SiO2 x 2.87 - C3S x 0.75 %C4AF = %Fe2O3 x 3.04 %C3A = %Al2O3 x 2.65 - %Fe2O3 x 1.69 17 XRD spectroscopy 3 ways to get to the cement phases: Microscopy counting Bogue Formula Elemental Analysis %C3S = (%CaO - %CaO free) x 4.07 - (%SiO2 x 7.6 + %Fe2O3 x 1.43 + %Al2O3 x 6.72) %C2S = %SiO2 x 2.87 - C3S x 0.75 %C4AF = %Fe2O3 x 3.04 %C3A = %Al2O3 x 2.65 - %Fe2O3 x 1.69 18 XRD spectroscopy 3 ways to get to the cement phases: Microscopy counting Bogue Formula Elemental Reference Analysis XRD spectroscopy Method! but: %C3S = (%CaO - %CaO free) Requires time and specialist x 4.07 - (%SiO2 x 7.6 + %Fe2O3 x 1.43 + %Al2O3 x 6.72) %C2S = %SiO2 x 2.87 - C3S x 0.75 %C4AF = %Fe2O3 x 3.04 %C3A = %Al2O3 x 2.65 - %Fe2O3 x 1.69 19 3 ways to get to the cement phases: Microscopy counting Bogue Formula Elemental Analysis %C3S = (%CaO - %CaO free) x 4.07 - (%SiO2 x 7.6 + %Fe2O3 x 1.43 + %Al2O3 x 6.72) %C2S = %SiO2 x 2.87 - C3S x 0.75 %C4AF = %Fe2O3 x 3.04 %C3A = %Al2O3 x 2.65 - %Fe2O3 x 1.69 20 XRD spectroscopy Numerical Results – Quantification of Clinker Phases 21 C3S: Microscopy vs Bogue Comparison for 13 clinker samples: there is no correlation! ! Basing the kiln control decisions on the Bogue values can cause serious mistakes!!! 22 3 ways to get to the cement phases: Microscopy counting Bogue Formula Elemental Analysis %C3S = (%CaO - %CaO free) x 4.07 - (%SiO2 x 7.6 + %Fe2O3 x 1.43 + %Al2O3 x 6.72) %C2S = %SiO2 x 2.87 - C3S x 0.75 %C4AF = %Fe2O3 x 3.04 %C3A = %Al2O3 x 2.65 - %Fe2O3 x 1.69 23 XRD spectroscopy Total Cement Analyzer • XRD scans on three clinker samples showing the finger prints of alite, belite, aluminate and ferrite in addition to the free lime 24 Numerical Results – Quantification of Clinker Phases • XRD data from ARL 9900 Total Cement Analyzer 25 C3S: Microscopy vs Bogue vs Compact XRD system • Good correlation between XRD results and microscopy XRD data by ARL 9900 Total Cement Analyzer 26 • No correlation between Bogue values and microscopy C3S: Microscopy vs Bogue vs Compact XRD system • Good correlation between XRD results and microscopy XRD data by ARL 9900 Total Cement Analyzer 27 • No correlation between Bogue values and microscopy Conclusion to case study 2 Thermo Scientific ARL 9900 • Bogue calculation can be seriously in error • Phase determination is done fast and with better accuracy with X-ray diffraction • integrated XRF-XRD system, with analysis at same time 28 3 Thesis to be proven today 1. XRD can make your final cement resistance better by analyzing the Quartz content 2. Measuring with XRD gives a much better picture of the clinker phases than the Bogue formula 3. Even simple XRF instruments can do a great job in analyzing your alternative fuels. 29 Examples of Alternative Fuels: All Kinds of… 30 Challenge: Liquid Hazardous Waste Fuels Toxic? 31 Elements and Typical ranges of concentrations (ppm) Element Typical concentration (ppm) Element Typical concentration (ppm) Cl 100 Mn 100 S 100 Ni 100 Sb 50 Pb 50 As 50 Ti 10 Co 50 V 100 Cd 10 Sn 100 Cr 20 Te 100 Cu 100 Se 100 Hg 3 Zn 100 32 Analytical Requirements for Alternative Fuels Analysis Ministry of Environment, Indonesia: No. 1 2 3 4 5 6 7 8 9 10 11 Element As Cd Cr Pb Hg Tl Sb Co Ni Cu V Conc. (ppm) 15 10 1500 500 1.5 2 120 12 100 1000 25 Required LOD (ppm) 3 2 300 100 0.3 0.4 24 2.4 20 200 5 Defines the minimum required Limit of Detection (LOD) 33 Option A for alternative fuel analysis Alternative Fuels Lab Quant’X • Benchtop high performance EDXRF • Transportable to the main lab • Can be used as backup system 34 Main Cement Plant Lab ARL 9900 Total Cement Analyzer • Integrated WDXRF-XRD • main 10 to 14 elements/oxides • Analysis of free lime and clinker phases ARL QUANT X – Analytical Performance ARL QUANT'X LODs for 300s measurement time (Live Time) in AIR No. 1 2 3 4 5 6 7 8 9 10 11 Element Required LOD (ppm) Quant'X LOD (ppm) Remarks As 3 1 Cd 2 <1 Cr 300 3 Pb 100 <1 Hg 0.3 <1 Varies greatly with sample matrix Tl 0.4 <1 Varies greatly with sample matrix Sb 24 <1 Co 2.4 2 Varies greatly with sample matrix Ni 20 1 Cu 200 1 V 5 3 Can the ARL QUANT X meet the required LODs? 35 YES, it can! Alternative fuels • Lignite • Pips from grapes • Contaminated saw dust • Wheat husk 36 Option B for alternative fuel analysis Main Cement Lab ARL 9900 Total Cement Analyzer • Integrated WDXRF-XRD • main 10 to 14 elements/oxides • Analysis of free lime and clinker phases 37 Optim’X • WDXRF support instrument • Non routine samples, additives and quarry samples • Alternative fuels analyzer Analysis of alternative fuels – contaminated saw dust 38 Elément UniQuant 5 UniQuant 5 Cellulose (estimée) 97.9 97.9 Ca 0.67 0.67 Si 0.72 0.72 Al 0.19 0.19 K 0.11 0.11 S 0.12 0.12 Fe 580 ppm 580 ppm Ti 350 ppm 350 ppm Mg 710 ppm 710 ppm Cl 650 ppm 650 ppm P 380 ppm 380 ppm Zn 130 ppm 130 ppm Ba 140 ppm 140 ppm Pb 60 ppm 60 ppm Mn 70 ppm Sn 60 ppm Ni <10 ppm Cr <10 ppm Sr <10 ppm <10 ppm V <10 ppm <10 ppm 70 ppm Analysis covering more than 70 elements 60 ppm • <10 25ppm min analysis with OptiQuant (ARL Optim’X) • <10 Much ppm more longer by ICP or other techniques Conclusion to case study 3 Thermo Scientific on alternative fuels • X-ray Fluorescence is the technique of choice • XRF standard-less programs permit quick analysis of most elements of the Mendeleev table • Necessary Precision can be achieved even with low cost XRF products 39 3 Thesis to be proven today 1. XRD can make your final cement resistance better by analyzing the Quartz content 2. Measuring with XRD gives a much better picture of the clinker phases than the Bogue formula 3. Even simple XRF instruments can do a great job in analyzing your alternative fuels. 40 Thank you for your attention !! For any additional questions please visit us at our Stand in Exhibition area Or Visit us at our HQ and factory in Switzerland (close to Geneva) !! 41 Thank You! 42 43

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