Challenges in the cement industry solved by XRF and XRD

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!
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