analysis strategies for alternative fuels in the cement … strategies for alternative fuels in the...

Analysis strategies for alternative fuels in the cement industry

D. Bonvin, R. Yellepeddi and S. Terrazzoni

Thermo Fisher ScientificCH-1024 Ecublens, Switzerland

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Thermo Fisher Scientific: Two Premier Brands

New capabilities acquired from Fisher

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All from Thermo Fisher Scientific

• High performance analytical instruments, software and services to enable integrated laboratory workflow solutions from sample preparation to distribution of results.

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equipment, consumables, reagents and supplies used in scientific research, safety, healthcare and science education

Thermo’s world-class analytical technologies

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XRF is used for the elemental analysis of a variety of materials

Oils

Metals, Slags

Ores and raw materials

Chemicals

Food productsGlass

Polymers

Ceramics

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WDXRF offers detection limits from sub-ppm and a wide dynamic range up to 100%

ICP-MS

ICP-AES

GFAAS

AAS

1 ppq 1 ppt 1 ppb 1 ppm 1,000 ppm 100%

X-ray Fluorescence

Arc-Spark OES

TRACE BULK

Liquids

Solids

Combustion : TOC; TN; TS, TOX

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What is so great about X-ray Fluorescence ?

• Precise, non-destructive multi-element analysis of conducting and non-conducting samples:

• Solids• Liquids• Loose powders

• Multi-element analysis: Be - F to U• Inorganic and Organic materials• High precision and highly reliable • Wide dynamic range: sub-ppm to 100%• Powerful “standard-less” elemental analysis for totally unknown samples

http://www-tech.mit.edu/cgi-bin/imagemap/Projects/Chemicool/pertable.map�

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WD-XRF Data Processing

Now and for the future

INTERPRET

DISPLAY

Scan

QUALITATIVE

QuantAS % +GRAPHICS

S/W INTERPRETS

Scan from F to U0.1s per step3 to 12 mn total

Scan based

UniQuant %DATA

up to 79 Elements

Peak Hopping4 to 10s per peak

8 to 14 mn total

Peak based

DATA %

CHOOSE LINES

CalibrationSpecific standardsSpecific % range

QUANTITATIVE

XRF Analysis

---> Increasing Accuracy of Analysis -->

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UniQuant®: Peak Hopping versus Scanning

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Standard-less Analysis of totally unknown samplesin X-ray Fluorescence

UniQuant: peak hopping• Peak based standard-less program for 79 elements 131 line positions, alternative lines and background positions 4s to 12s counting time depending on element Counting time is programmable for each element to get better limit of

detection or optimize the overal analysis time Total time 8 to 14 minutes

• Samples : solids, liquids, loose powders, filter papers, etc.• Shape : flat or odd, small quantities or small pieces, etc.• Spinning of sample in analysis position:

• important when analysing small or odd shaped samples• Allows to average out any inhomogeneities of the sample

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Comparison of methods without/with UniQuant®

1. Sample& Preparation

2. Search & buy matching Standards

3. Measure Standards +Calibrate

4. Analyze unknown sample prepared

5. Quantitative results

1. Sample & prepared or not 2. Search & buy

matching Standards

3. Measure Standards +Calibrate

2. Analyze unknown sample prepared or not

3. Quantitative results

UniQuant® METHOD

CONVENTIONAL METHOD

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Examples of Alternative Fuels: All Kinds of…

• Typical Alternative Fuels• Waste oils, paints, thinners, etc.• Wood chips, paper, textile• Sewage sludge• Rubber, e.g. tires• Packing waste, Household waste• Etc.

• Analysis of alternative fuels required to prevent:• Illegal emissions• Changes in the process parameters

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Elements and Typical ranges of concentrations (ppm)

• Cl 100• S 100• Sb 50• As 50• Co 50• Cd 10• Cr 20• Cu 100• Hg 3• Mn 100• Ni 100• Pb 50• Tl 10• V 100• Sn 100• Te 100• Se 100• Zn 100

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Alternative Fuels Lab

Option A for alternative fuel analysis

• Benchtop high performance EDX instrument

• In the Alternative fuels lab away from the main lab

• Transportable to the main lab• If needed as backup

− In case of maintenance to the main WDXRF instrument that ensures the cement plant quality control

Main Cement Plant Lab

• Total Cement Analyzer• Integrated WDXRF-XRD

instrument• Analysis of main 10 to 14

element/oxides• Analysis of free lime in

each clinker• Analysis of clinker phases

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ARL QUANT’X Spectrometer

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• Up to 8 primary filters• Collimators

• 1.0 mm• 3.5 mm• 6.8 mm

• Chamber Environment• Air• Vacuum• Helium

• End-window X-ray tube

ARL QUANT’X: Analysis chamber

ARL QUANT’X chamber

Detector

Filters wheel

X-ray tube

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Elemental Analysis with XRF

Si

Al

Rh

K

Mg

Ba

Ba

Ce

La

Inelastic

Elastic

Zr

Nb

Zr

Rb

Sr

Y

Pb

Zn

Sn

Fe

Mn

Ca

Ti

Filter 0 Filter 1 Filter 2 Filter 5 Filter 6

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• Measuring time : 12 minutes to 20 minutes (4 to 5 excitation conditions) up to 30 minutes to have Na, Mg, Al, Si, P to their Limit of detection

• Sample preparation : liquid cell (grinded at least)

• Pressed pellets

• Universal Calibration : UniQuant

Option A for alternative fuel analysis

ARL Quant’X

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Best limits of detection / Quantification UNDER AIR

LOD (200 sec)

Limit of Quantification(200 sec)

S, Cl 15ppm 50ppm

Ti, V, Cr, Mn, Co, Ni,Fe, Cu, Zn, As, Se,

Ga, Ge, Br

<1ppm 3ppm

Hg, Bi, Pb, U <1ppm 3ppm

Cd, Sn, Ba <1ppm 3ppm

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ExampleAnalysis of Liquid Hazardous Waste Fuels

Example: Analysis of Liquid Hazardous Waste Fuels (LHWF)

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Analysis of Liquid Hazardous Waste Fuels (LHWF)

• Liquid hazardous waste (fuel) is industrial waste:• Mixtures of solvents• Oils• Paints and pigments

• Such waste may be a single phase or multi-phase liquid and often contains suspended solids (sedimentation or suspension)

• Before incineration, it is usually required by governmental regulations to screen the LHWF for the presence of toxic and/or volatile elements above certain concentration levels

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• ASTM D5839 describes a method for the determination of trace element concentrations by EDXRF in typical LHWF used by industrial furnaces.

• A total of 11 elements; Ag, As, Ba, Cd, Cr, Hg, Ni, Pb, Sb, Se, and Tl can be monitored in a wide concentration range ranging from ppm to %.

• This application describes the analysis of 6 elements (Ag, Cd, Cr, Ni, Pb and Sb) in LHWF with concentration ranges of 0 to 500 ppm.

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• Sample Preparation:• 5g of the LHWF sample is thoroughly mixed with 5g of graphite powder for

five minutes using a ball mixer mill giving a paste.• Four grams paste in a sample cup with a 4 µm thick Propylene film.

• Calibration:• Calibration is done using a total of 24 samples.• Six elements at concentration ranges of 0 to 500 ppm.

• Results:Conc. Range

SEE

(ppm) (ppm)Cr 0 – 500 0.999896 3Ni 0 – 500 0.999961 2Ag 0 – 500 0.999761 4Cd 0 – 500 0.999857 3Sb 0 – 500 0.999623 5Pb 0 – 500 0.999824 3

Element R²

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Calibration Results: Nickel

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Calibration Results: Cadmium

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• The ARL QUANT’X EDXRF spectrometer with Si(Li) detector can be used to successfully analyze trace elements in liquid hazardous waste fuels.

• Sample preparation using graphite as described in ASTM D5839 offers a fast and straightforward method to deal with the variety in LHWF samples.

• A four minutes analysis time per condition under air yields detection limits of 2 ppm or less.

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Analytical Requirements for Alternative Fuels Analysis

• List of max. permissible concentration per element according to the Ministry of Environment, Indonesia

• Reliable results require analyses at the Limit of Quantification (LOQ)• Defines the minimum required Limit of Detection (LOD)• LOQ = 5 x LOD

No. Element Conc. (ppm) Required LOD (ppm)1 As 15 32 Cd 10 23 Cr 1500 3004 Pb 500 1005 Hg 1.5 0.36 Tl 2 0.47 Sb 120 248 Co 12 2.49 Ni 100 2010 Cu 1000 20011 V 25 5

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ARL QUANT’X EDXRF Analyzer → A Perfect Match

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ARL QUANT’X – Analytical Performance

• Elements posing difficulties to any ED-XRF system• Co → Peak overlap with Fe, often present at high conc.• Hg, Tl → Peak overlap with Pb, Zn and As, often present at high conc.

• In practice, LODs are in the range of 1 to 2 ppm

• Can the ARL QUANT’X meet the required LODs?

ARL QUANT'X LODs for 300s measurement time (Live Time) in AIR

No. Element Required LOD (ppm) Quant'X LOD (ppm) Remarks1 As 3 12 Cd 2 < 13 Cr 300 34 Pb 100 < 15 Hg 0.3 < 1 Varies greatly with sample matrix6 Tl 0.4 < 1 Varies greatly with sample matrix7 Sb 24 < 18 Co 2.4 2 Varies greatly with sample matrix9 Ni 20 110 Cu 200 111 V 5 3

YES, it can!

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ARL QUANT’X – Analytical Performance (II)

• Next to the list of hazardous elements to be monitored other elements and compounds are also of importance to cement production process

• S & Cl• Na2O, MgO, K2O, CaO, Al2O3, SiO2, Fe2O3, etc.

• All these compounds can be determined during the same analysis

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Strengths of the ARL QUANT’X

• Electrically (Peltier) cooled Si(Li) detector• No liquid nitrogen required to cool down the detector• Si(Li) detector is 3.5 mm thick & a surface area of 15 mm²• Robust with long life time

• Direct excitation with 8 primary beam filters• Direct excitation produces highest element characteristic X-rays yield • Optimized peak to background ratios for all elements (Na – U)

• Choice of excitation voltages: 4kV to 50kV• Can be changed by steps of 1kV• 4kV = lowest excitation voltage in the market → Eliminates Ca excitation• 50kV allows for K line excitation of heavy elements (Pb, Cd, Sn, Sb, Ba…)

• Software• Standard WinTrace software is intuitive and powerful

• Empirical calibration (Alpha coefficients) for best results• Fundamental Parameters calibration

• UniQuant standardless FP software makes using an ED-XRF easy

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Strengths of the QUANT’X– UniQuant Standardless FP

• Advanced standard-less fundamental parameters software• Pre-calibrated at the factory – no standards required!!!• Allows for a lot of sample flexibility by correcting for

• Sample height, density, unknown matrix, morphology, XRF film, environment…• Complete sample composition down to the ppm range• Ideal to screen & analyze a variety of sample types with minimal user input

• As typically encountered in alternative fuels analysis

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Typical users

NUA-Niederoesterreich Umwelt Analytik Austria Water, oil, air and related materials for incineration

Fernwaerme Austria Alternative fuels and incineration center)

Saubermacher Austria Waste disposal and management

Antwerp University Belgium Oils

STREAM POWER INTL China Oils

CETIM-CERMAT France Contract lab

AREVA NC France Nuclear waste

CSA Italy Soils, air filters, environmental lab

Indam Italy Environmental, oils, air filters

Carpatcement (Heidelberger group) Romania Alternative Fuels

GE WATER PROCESS TECHNOLOGY Singapore Heavy elements in waste waters

CRIDEC Switzerland Alternative Fuels Lab for Holcim Cement

Société Industrielle de Genève - SIG Switzerland Waste materials analysis, recycling

Thommen Furler Switzerland Alternative fuels

VEOLIA ENVIRONMENTAL SERVICES U.K. Waste materials and recycling

PYROS ENVIROMENTAL LIMTED U.K. Waste materials and incineration

ABERDEEN PROVING GROUNDS USA Heavy Metals

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Option B for alternative fuel analysis

• WDXRF support instrument• Support analyzer

• Non routine samples, additives and quarry samples

• Alternative fuels analyzer• UniQuant

Main Cement Plant Lab

• Total Cement Analyzer• Integrated WDXRF-XRD

instrument• Analysis of main 10 to 14

element/oxides• Analysis of free lime in

each clinker• Analysis of clinker phases

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With:• 50W system – no water cooling required• Wavelength Dispersive system high resolution

ARL OPTIM’X: Unique WDXRF Spectrometer

UCCO™Technology

SmartGonio™UniQuant

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UCCO: Ultra Close Coupling Optics

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Access to all elements from Fluorine to Uranium(3 crystals - 2 detectors)

Schematic Principle of the Moiré fringe SmartGonioTM

Exclusive SmartGonioTM

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Examples of Alternative Fuels for lime or cement industry

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Alternative fuels (in lime industry)

• Contaminated saw dust

• Wheat husk

• Lignite

• Pips from grapes

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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 70 ppm

Sn 60 ppm 60 ppm

Ni <10 ppm <10 ppm

Cr <10 ppm <10 ppm

Sr <10 ppm <10 ppm

V <10 ppm <10 ppm

Analysis of alternative fuels – contaminated saw dust

Analysis covering more than 70 elements• 25 min analysis with OptiQuant (ARL Optim’X)• Much more longer by ICP or other techniques

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Analysis of alternative fuels – pips from grapes



Ca 0.75 0.75

K 0.43 0.43

P 0.24 0.24

S 0.18 0.18

Mg 0.12 0.12

Si 570 ppm 570 ppm

Fe 160 ppm 160 ppm

Al 200 ppm 200 ppm

Cu <10 ppm <10 ppm

Cl 60 ppm 60 ppm

Sn 34 ppm 34 ppm

Sr <10 ppm <10 ppm

Mn <10 ppm <10 ppm

Zn <10 ppm <10 ppm

Ni <10 ppm <10 ppm


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Analysis of alternative fuels – wheat



K 1.16 1.16

P 0.54 0.54

Mg 0.18 0.18

S 0.13 0.13

Ca 950 ppm 950 ppm

Cl 500 ppm 500 ppm

Si 150 ppm 150 ppm

Mn 100 ppm 100 ppm

Fe 90 ppm 90 ppm

Zn 70 ppm 70 ppm

Ba 60 ppm 60 ppm

Al 50 ppm 50 ppm

Ni <10 ppm <10 ppm

Sn 50 ppm 50 ppm

Cs 40 ppm 40 ppm


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Analysis of alternative fuels – lignite


C (estimé) 98.7 98.7

Ca 0.35 0.35

Si 0.29 0.29

Fe 0.28 0.28

Al 0.18 0.18

Mg 0.11 0.11

S 860 ppm 860 ppm

K 110 ppm 110 ppm

Ti 70 ppm 70 ppm

Cl 80 ppm 80 ppm

Ba <10 ppm <10 ppm

Mn 30 ppm 30 ppm

Ni <10 ppm <10 ppm

Sn 30 ppm 30 ppm


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ARL OPTIM’X

ARL OPTIM’X

air cooling only - no water cooling required

Repeatability for cement analysis

Optimized counting time can be used and satisfy the requirement of the cement industry

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ARL OPTIM’X: Performance for grey cementAnalysis time: 3min16s

• Optimized counting time per element • total analysis time of 3-4 minutes depending on number of elements/oxides • including sample pumping and loading time

• 50W system • Air cooling - No water cooling required !

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ARL OPTIM’X: Excellent short term repeatability grey cement: 10 repeat analysis in 30 minutes

• Same pressed pellet of grey cement analysed 10 times• Analysis time per run for 11 elements/oxides: 3 minutes 16s

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Thank you for your attention !!

For any additional questions please visit us at our Stand in Exhibition area

OrVisit us at our HQ and factory in Switzerland (close to Lausanne) !!

analysis strategies for alternative fuels in the cement … strategies for alternative fuels in the...

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