Eltra GmbH

Retsch-Allee 1-5 QUALITY CONTROL OF

COAL WITH ELEMENTAL
42781 Haan
Germany

Phone 02104/2333-400
E-Mail info@eltra.com ANALYZERS
www.eltra.com
AN OVERVIEW OF RELEVANT STANDARDS AND
SUITABLE ANALYTICAL EQUIPMENT

Introduction
Coal is one of the most important fossil fuels. In 2018, the global stone coal output was
about 7 billion metric tons1. A huge amount of the worldwide traded stone coal is
mined in China, USA, Russia and India. Compared to the very large amount of mined
coal the required sample volume for the characterization of coal, varying from a few
mg up to 1 gram, seems unbelievably small. Correct sampling and sample preparation
is a must for any subsequent measurement.

The correct characterization of coal is important for its quality assessment and further use.
Depending on the product quality, coal is suitable for coking, steel production or electrical
power generation. This article describes the chemical background of proximate and
ultimate coal analysis and their correct determination with ELTRA’s combustion and
thermogravimetric analyzers.

The most common types of coal are lignite, bituminous and anthracite coal which can be
distinguished by their chemical and physical properties. General (physical) parameters of
coal are gross calorific value as well as moisture, volatile and ash content. Chemical analysis
for coal samples usually means the determination of the elements carbon (C ), hydrogen
(H), nitrogen (N), sulfur (S) and oxygen (O).
Apart from coal analysis, the characterization of coal combustion products, like ash, is also
considered in this article. Ashes can be analyzed for their sulfur content, ash fusion
temperature and loss on ignition value. Due to the large number of international standards

1 www.kohlenstatistik.de

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 for the analysis of coal and their ashes, this article summarizes all relevant standards and
gives recommendations regarding the suitable analytical equipment.

Gross calorific value

Given the variety of parameters which influence the quality of coal, it seems rather
ambitious to name one parameter which best describes the coal quality. Due to the fact
that coal is mostly used as fuel, the calorific value is suitable to give a first impression of the
product quality.

Table Nr. 1 shows the main types of coal with their calorific value and the content of volatiles.

Calorific value
Type Volatile content
kj/kg

Lignite 6,700- 25,000 45 – 60 %

Bituminous coal 25,000 – 35,000 14- 45 %
Anthracite coal ≥35,000 < 14 %

The gross calorific value can be determined with standard bomb calorimeters and is
described in the ISO 1928 and ASTM D5865 standard. Calorimeters for coal analysis can be
divided into isoperibolic and adiabatic. In both types a previously dried coal sample is
introduced in a calorimetric bomb, oxygen is added and the coal is combusted. The
combustion heat is measured and gives the gross calorific value.

Proximate coal analysis

Beside the calorific value of a coal sample, its moisture, ash and volatile content is of
relevance. According to ISO 17246 and ASTM D 3172 these coal parameters are named
proximate coal analysis. Both standards (ASTM and ISO) define proximate coal and coke
analysis, but they refer to different standards like ISO 562, ASTM D 3175 or ASTM D 7582
which describes the determination of one analysis parameter (e. g. volatiles) in more detail.
Standard-compliant proximate coal analysis can be performed by utilizing furnaces and
balances (ISO 562) or, according to ASTM D 7582, by using automated thermogravimetric
analyzers like ELTRA’s TGA Thermostep (Fig 1) or TGA Thermostep ML (Fig2).
The reliable and standard-compliant determination of moisture, ash and volatiles requires
the application of different temperatures, atmospheres and measuring conditions like
measuring time or stability of weight. Adjusting the different settings is time-consuming
when single furnaces and balances are used because the sample always has to cool down
in a desiccator before the final weight can be measured.

Fig. 1: TGA Thermostep Fig. 2: TGA Thermostep ML

Automated thermogravimetric analyzers like the ELTRA TGA Thermostep series consist of a
programmable furnace with integrated balance, a carousel with 19 sample positions and
can measure all requested proximate coal parameters in a single run. Users just need to
activate the application in the software, fill a suitable sample weight of approx. one gram
into the ceramic crucibles and start the measurement. During analysis the carousel rotates
and subsequently places every single crucible on a weighing pedestal to measure the
current weight.

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 During the whole measuring process different temperatures and atmospheres are applied
depending on the analysis step. For reliable determination of the thermogravimetric
parameters an additional empty crucible at position 20 of the carousel is measured to
compensate the thermal buoyancy. This procedure reduces the analysis time for proximate
coal analysis significantly because the samples don’t need to cool down in a desiccator to
ensure correct measurement. The settings for an automated measurement of moisture,
volatile and ash are defined in the ASTM D 7582 standard (table 2).

Table 2: Proximate coal analysis parameter according ASTM D 7582

Step No. Parameter Temperature Atmosphere Additional lid Stop criteria

°C on crucible

1 Moisture 107 Nitrogen No Constant mass

7 minutes at
2 Volatile 950 Nitrogen Yes
950 °C

“Cooling
3 600 Nitrogen Yes Temperature
down”

4 Ash 750 Oxygen No Constant mass

One special setting in a thermogravimetric analyzer is the placing of lids on the crucibles
for a correct measurement of volatiles. The ELTRA TGA Thermostep analyzer utilizes an
additional lid carrousel which automatically applies the lids during measurement. The TGA
Thermostep ML configurations require manual application and removing of lids. A
complete proximate coal analysis cycle with the ELTRA TGA Thermostep takes approx. four
hours. Typical results of a simultaneous measurement of 19 samples are shown in Table 3
and figure 3. One special setting in a thermogravimetric analyzer is the placing of lids on
the crucibles

Table 3: Typical results of the TGA Thermostep series analyzer: Dry base means that the
given value takes the released amount of water into account. In comparison to a sample
which is measured as received, the measured ash and volatile content is respectively higher
(ISO 17247)

Sample % Moisture % Volatile dry % Ash dry base % Fixed carbon

(Coal CRM) base calculated

92570-3020
0.16 +-0.04 5.42+-0.14 0.08+-0.04 94.34+-0.13
(745418)

92550-3020
1.12+-0.02 15.79+-0.16 20.98+-0.06 62.49+-0.20
(776121)

92550-3060
1.82+-0.04 30.63+-0.11 23.42+-0.08 45.08+-0.13
(782118)

92550-3060
23.47+-0.06
(782118): 600 °C

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 Figure 3: Typical measuring graph of ELTRA TGA Thermostep series analyzer

I y-axis (left): relative weight of the sample

I y-axis (right): temperature
I red curve: temperature
I graph 1-19: weight loss of applied coal samples

The analysis of the first three samples in table 3 have been processed with a cool down
temperature of 750 °C. With this setting the TGA Thermostep can analyze the proximate
coal parameter in a fast analysis time of approx. 4 hours. Of course, the standard-compliant
lower cool down temperature of 600 °C can be applied in the software also. With application
of the lower temperature the repeatability of the ash measurement is slightly improved,
but the measuring time is prolongued by approximately one hour. Moisture and ash
measurement are not affected by these alternative settings.

The fixed carbon content of a proximate coal analysis is a calculated value and is used as an
estimate of the amount of coke that will be yielded from a coal sample. It can be calculated
by subtracting the measured amount of the volatile content from the sample mass which
was introduced into the ceramic crucible. The calculated fixed carbon is lower than the
total carbon content as some volatile hydrocarbons are removed during the analysis
process.

Ultimate coal analysis (chemical analysis)

In addition to proximate coal analysis ultimate coal analysis requires the determination of
further parameters like carbon ( C ), hydrogen (H) , nitrogen (N) , sulfur ( S) and oxygen (O)
content. The oxygen content is usually not measured directly but given by the difference
between 100 % and the sum of all other measured values. For standard compliant
determination of the elements C, H, N, S different types of elemental analyzers are available
in the market. A typical elemental (combustion) analyzer combusts the coal sample and
measures the released combustion gas with infrared cells, a thermal conductivity cell or a
combination of both. Available analyzers differ with regards to required sample weight,
combustion temperature and measured elements.

Micro elemental analyzers offer the possibility to measure C, H, N, S in one analysis cycle,
but only accept a very small sample weight of max. 10 mg. This makes the sample
preparation for these analyzers error-prone, however, the standard does not prohibit the
usage of this kind of analyzers.

The determination of the elements C, H, N is regulated in the ISO 29541 and ASTM D 5373
standards. A standard-compliant common macro elemental analyzer usually employs a
quartz or steel combustion tube and processes coal sample weights of typically 60 - 80 mg.
When using these types of combustion tubes the applied temperature is limited to
approximately 1,000-1050 °C. The requested combustion temperature of 1150 °C for coke
analysis can be provided by the application of tin foils or capsules.

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 Beside a simultaneous measurement of carbon, hydrogen and nitrogen also a standard-
compliant single carbon analysis is defined. According to ASTM D 5372 (method B), a single
carbon analysis requires combustion analyzers like ELTRA’s ELEMENTRAC CS-r or CHS-r
(Figure 4) which provide a minimum combustion temperature of 1350 °C. The resistance
heated ceramic furnace of the CS-r or CHS-r allows the application of a maximum
temperature of up to 1550 ° C which assures a complete combustion of a coal or coke
sample without adding fluxes like tin. Beside carbon also sulfur and hydrogen can be
measured simultaneously in up to two infrared cells with the ELEMENTRAC CS-r/CHS-r.
Due to the high combustion temperature, the sulfur analysis is precise, reliable and
compliant to the ISO 19579 and ASTM D 4239 standards. The application of high sample
weights of 200-350 mg in ceramic boats provides excellent repeatability (table 4, Figure 5).

Fig. 4: ELEMENTRAC CHS-r with

optional monitor holder and Table4: Typical results for coal and coke (N=10) with ELEMENTRAC CS-r & CHS-r.
touchscreen

Analyzer Sample Weight % Carbon % Sulfur % Hydrogen

ELTRA 92550-
ELEMENTRAC
3040 200 mg 67.68+-0.12 1.91+-0.02 3.97+-0.02
CHS-r
(Lot 781411)

Pet coke
ELEMENTRAC
AR 745 350 mg 96.03+-0.25 0.9+-0.002 Not possible
CS-r
(Lot 745416)

Figure 5: Measuring curve of a CHS-measurement of coal: 92550-3040(Lot 781411)

I y-axis: analysis time (sec)

I y-axis: intensity (V)
I red peak: carbon
I green peak: hydrogen
I blue peak: sulfur

Characterization of ash
Apart from the analysis of coal, the characterization of its combustion products, coal and
coke ash, can be of analytical interest. Like for coal, the analysis of ash can be divided into
physical or chemical analysis.
For steam power generation, for example, the physical ash behaviour at different
temperatures (ash fusion test) is very important (ASTM D 1857). When coal is combusted in
a furnace of an electrical power plant a powder-shaped residue or a glassy slag (clinker) are
unwanted by-products. Not every electrical power plant is able to handle clinker-forming
coal because of the cost-intensive furnace cleaning that is required.

When using an ash fusion analyzer, such as the CAF Digital from Carbolite Gero, the ash is
formed in the shape of a cone, pyramid or cube and is introduced into a furnace with a
special window. Through this window a camera can observe the sample’s behavior during

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 heating. Typically, temperatures up to 1,600 °C are applied. During the heating process
parameters such as deformation, softening, hemisphere and flow temperature are
recorded. The flow temperature is crucial for deciding on the further use of the coal.

Another physical parameter is the loss on ignition (LOI) value of solid combustion residues
(ASTM D 7348). In a standard-compliant thermogravimetric analyzer like the ELTRA
Thermostep the sample is heated from room temperature up to 950 ° C in an oxidizing
atmosphere. The LOI parameter indicates if moisture, carbon, sulfur or other species are
present in the combustion residue. The dedicated sulfur analysis in combustion residues of
coal and coke is regulated in the ASTM D 5016 standard. For correct sulfur determination, a
tube furnace analyzer like the ELEMENTRAC CS-r or CHS-r are suitable as they provide the
requested minimum combustion temperature of 1350 °C.

Conclusion and summary

Correct and reliable analysis of coal, coke and their combustion residues is challenging
because a variety of standards have to be considered and different analytical equipment
has to be used in a standard coal laboratory. ELTRA can provide economic and reliable
solutions coal, coke and ash analysis and has been accepted as a reliable partner in the coal
industry for more than 40 years.

The following table summarizes the currently valid standards for coal, coke and its ash
analysis and gives some recommendations regarding instrumentation:

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 Table 5: Relevant standards for coal, coke and ash analysis

Standard Topic ELTRA instrumentation

Overview standards with reference to other standards

ISO 17246:2010 Coal- Proximate analysis

ISO 17247:2020 Coal and coke- Ultimate analysis

ASTM D3176- 15 Ultimate analysis of coal and coke

ASTM D3172-13
Proximate analysis of coal and coke
(Reapproved 2021)

Analysis of coal and coke

Determination of C;H;N in coal ELEMENTRAC C(H)S-r (Method

ASTM D5373-16
and C in coal and coke B)

Solid mineral fuels – Determina-

ISO 29541:2010 NN
tion of C;H;N

Solid mineral fuels- Determina-

ISO 19579: 2006 ELEMENTRAC C(H)S-r
tion of sulfur by IR spectrometry

Solid mineral fuels- Determi-

ISO 20336:2017 nation of sulfur by coulomb NN
titration

Standard test method for sulfur

ASTM D4239-18 in the analysis sample of coal ELEMENTRAC C(H)S-r
and coke

Coal and coke- determination

ISO 1928:2020 NN
of the gross calorific value

Standard Test Method for Gross

ASTM D5865-13 NN
Calorific Value of Coal and Coke

Standard test methods for pro-

ximate analysis of coal and coke
ASTM D7582-15 TGA Thermostep series
by macro thermogravimetric
analysis

Analysis of ash and combustion residues

ASTM D 7348-21 Combustion residues (LOI) TGA Thermostep series

Standard test method for fusibi-

ASTM D 1857-18 CARBOLITE CAF G 5
lity of coal and coke ash

Standard test method for total

ASTM D5016-16 sulfur in coal and coke combus- ELEMENTRAC C(H)S-r
tion residues

Analysis of carbon black

ASTM D 1619-20 Carbon black – Sulfur content ELEMENTRAC C(H)S-r

ASTM D 7633-13 (Reapproved

Carbon black – Carbon content ELEMENTRAC C(H)S-r
2018)

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