A SYSTEMATIC QUALITY

ASSESSMENT OF ALTERNATIVE

FUELS – AN IMPORTANT STEP

TOWARDS ENHANCING TSR

Anjan K Chatterjee

Conmat Technologies Private Ltd

Kolkata ,India

3rd international Conference on AFR in Cement

Industry

New Delhi

23-24 March 2017

Need for an Assessment Plan

To achieve the 2025 target of 25% TSR by AF

To handle multiplicity of waste streams

To differentiate the hazardous wastes from the non-

hazardous ones

To obtain reliable test results with both the attributes of

precision and accuracy

To know the ground state of contaminants and their

environmental reaction potentials including emissions

due to pyroprocessing

To make contaminants exposure and risk calculations, if

necessary.

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The AF Streams for the 2025 TSR Target

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Prime Chemical Criteria for Differentiating the

Hazardous WastesNature of hazard Nature of reaction Illustrations

Corrosivity A substance with an ability

to destroy tissue by

chemical reaction.

Rust removers, waste acid,

alkaline cleaning fluids and

waste battery fluids. pH

<2.0 or >12.5.

Ignitability A substance that readily

oxidizes by burning;

spontaneously combusts at

54.3ºC in air or at any

temperature in water or any

strong oxidizer.

Paint and coating wastes,

some degreasers, and other

solvents.

Reactivity A substance that can react,

detonate, or decompose

explosively at environmental

temperature and pressures.

Wastes from cyanide-based

plating operations,

bleaches, waste oxidizers

and waste explosives.

Toxicity A substance that causes

harm to organisms either

Pesticide, heavy metals,

mobile or volatile

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Biologically-Based Classification Criteria

for Hazardous WastesCriterion Significance

Bioconcentration The process by hich living organisms

concentrate a chemical to levels

exceeding the surrounding

environmental media.

Lethal dose (LD) A dose of chemical calculated to

expect a certain percentage of

mortality in a population of an

organism exposed through a route

other than respiration.

Lethal concentration (LC) A calculated concentration of a

chemical in air, a 4-hour exposure to

which through respiration by a

population of an organism will kill a

certain percentage.

Phytotoxicity The chemical’s ability to elicit

biochemical reactions that harm flora.

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The Plan for Essentially Non-Hazardous

AFR Assessment

Bulk sampling

Sample preparation

Proximate Analysis

Chlorides & Sulfate Contents

Ultimate Analysis

Ash Composition

Calorific Value

Grindability for solid fuels

Ignitability

Safety & Precautionary Measures

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Objective of the Assessment Scheme –

Precision & Accuracy

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Bulk Sampling for Pet Coke

Recommended to follow IS 436 (Pt 2):1965

Preferable to do sampling in motion

If not possible, to do stationary sampling with nine equal increments about 30 cm below the surface of loaded shipments

A separate gross sample for each 250 tonnes

For determining Total Moisture, a special sample of 25 kg to be drawn.

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Bulk Sampling for Other Secondary Fuels

Recommended to follow CEN/TS 15442

May cover Agricultural wastes, Municipal Solid Wastes,

Industrial Wastes, Tyre chips, Rubber wastes, etc.

To be drawn from trucks – a minimum of 24 samples

For a typical supply of 60 trucks, preferable to plan

sampling in two groups of 30 trucks each; from each

group one sample to be drawn from every two trucks, the

selection of trucks being random

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Sample Preparation for Analysis - I

A. Pet Coke : 7 kg of 6.3 mm size first reduced to 3.2 mm

size to draw 2 kg sample, which is then reduced to 212

µm for retaining 0.5 kg sample. The analytical sample is

to be air-dried for 24 h, mixed thoroughly and stored.

B. MSW & Agricultural Wastes: Record the weight,

spread the sample in a non-corroding tray, remove non-

millable contaminants, record the weight. Sieve and

separate the fines and record the weight. Treat the

sample in liquid nitrogen, transfer to Fritsch mill, pass

the sample through 500µm sieve. The analysis sample

is preserved in sealed containers.

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Sample Preparation for Analysis - II

A. Paint sludge – if wet, to be dried at 107ºC, treated with liquid nitrogen and milled.

B. Spent carbon – a powder checked to be passed through 212µm before analysis.

C. Organic sludge – when received in a mix of powder and lumps, the sample is ground in an agate mortar to pass 212µm sieve.

D. ETP sludge – when received in semi-solid form, it is dried at 107ºC and then pulverized to pass through 212µm sieve.

E. Pharmaceutical wastes – when received in fine dry powdery form, it is cross-checked to pass through 212µm

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Preferred Procedural Approaches for

Analysis and Testing • While for the Proximate Analysis of Pet Coke the procedure

stipulated in IS 1350:1984 can be followed, for the secondary

fuels the thermo-gravimetric instrumental analysis is preferred.

• For rapidity and reliability of Ultimate Analysis the instrumental

facility of CHN & S determination is suggested.

• For Calorific Value an automatic calorimeter with digital signal

processing is recommended; ii provides the gross calorific

value at constant volume.

• The Hardgrove Grindability Index is essentially developed for

coal but could be extended to other hard solid fuels with

appropriate procedural modifications.

• For ash composition the Elemental analysis is preferred.

• Calibration of instruments with SRMs is essential.

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The European Pollution Release & Transfer Register –

An Estimate of Organic Pollutants in the Mineral

IndustriesSeri

al

No.

Organic

compound

Cement

& Lime

kilns

Ceramics

production

Glass

production

Threshold

emission

values,

kg/year

1 NMVOCs + + + 100000

2 Dioxins &

Furans(PCDDs+

PCDFs) as 1-

TEQ

+ + 0.0001

3 PCBs + + 0.1

4 Anthracene + 50

5 Naphthalene + 100

6 Benzene + + + 1000

7 DEHPs + 10

8 PAHs + + + 50

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A Measurement Procedure for Organic

Pollutants : Isokinetic Sampling of Gas

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Determination of Mass Concentration of

PCDDs/PCDFs/Dioxin-like PCBs

• Sampling method – PN-EN 1948-1:2006

• The organic pollutants are captured in three stages:

• 1. Hot filtration of dust fraction on glass or quartz filter

• 2. Steam condensation by gas cooling

• 3. Gas sorption on solid phase (polyurethane foam)

• The analysis method – EN 1948-3:2006

• Gas chromatography coupled with mass spectrometry

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Determination of Mass Concentration of

Naphthalene, Anthracene, PAHs & DEHPs

• Sampling method – ISO 11338-1,2:2003

• The pollutants are captured in three stages:

• 1. Hot filtration of dust fraction on glass or quartz filter

• 2. Steam condensation by gas cooling

• 3. Gas sorption on solid phase wet with condensate

• The analytical procedures – both ISO standard and EPA

0010

• Gas chromatography coupled with mass spectrometry.

For PAHs, liquid chromatography with fluorescent detector

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Determination of Mass Concentration of

Benzene and NMVOCs

• The analytical procedures including sampling – EPA 0030

• Volatile Organic Compounds with boiling temperatures not

exceeding 100ºC

• The pollutants are captured in two stages:

• 1. Steam condensation by gas cooling

• 2. Gas sorption on solid phase (Anasorb-747)

• Gas Chromatography with flame ionization detector is

used

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Broad Observations on the emission

Measurements of Organic Pollutants

• The emission levels depend on several factors, viz.,

• composition of raw materials

• fuels used

• technology of flue gas cleaning

• The emission limits in terms of BAT-AEL are not available for the majority of pollutants

• The sampling and analytical techniques are fairly elaborate and complex

• The measured results indicated that the values for benzene NMVOCs and DEPHs are close to the limits

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Preparedness for Systematic Assessment of

Alternative Fuels in Terms of Composition & Emissions

• Environmental Science and Engineering are relatively young

professions compared to other disciplines and depend heavily

on both inorganic and organic chemistry.

• There have been rapid advances in analytical and

characterizing tools for complex hybrid materials, which are

found to be essential in Environmental Chemistry,

• If we have to move towards reliable assessment of intrinsic

quality of waste fuels and their emission impacts, one has to be

prepared with both unconventional expertise and advanced

tools for sampling, sample preparation and analysis of both

organic and inorganic substances.

• This preparedness is essential for enhancing TSR in AF firing

in the cement industry

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Summary of Important Test Facilities to be

Equipped With for PreparednessProximate Analysis

Ultimate Analysis

Elemental Determination( Cl, F, Pb, Cd, As, Hg, Cr, Co,Ni,Th,Cu, V, Sb,Mn,Se,Fe)

TOC

TCLP Test

Total Petroleum Hydrocarbon

Organo-chlorine Compounds

VOCs and Semi-VOCs

Polychloro Biphenyls (PCB) & Phenols(PCP)

Calorific Value – Gross & Net

Viscosity of Liquid Wastes

Water content in Liquid Wastes

Solid content in Liquid Wastes

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Thank you for your patience

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