Proximate Analysis

Proximate analysis is a way to determine the distribution of products when the

samples are heated under specified conditions.

From: Fuel Flexible Energy Generation, 2016

Related terms:

Lignite, Biomass, Hydrogen, Nitrogen, Fixed Carbon, Flue Gas, Ultimate Analysis,
Volatile Matter

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Learn more about Proximate Analysis

Introduction
Leonel Jorge Ribeiro Nunes, ... João Paulo Da Silva Catalão, in Torrefaction of
Biomass for Energy Applications, 2018

1.2.1 Proximate Composition (Ash, Fixed Carbon, and Volatiles)

Proximate analysis of a fuel provides the percentage of the material that burns in a
gaseous state (volatile matter), in the solid state (fixed carbon), and the percentage
of inorganic waste material (ash), and is therefore of fundamental importance for
biomass energy use [37].

There is a positive relationship between fixed carbon from biomass and charcoal yield
while the volatile content and ash relate negatively with charcoal yield [38]. Thus, it
is expected that with greater biomass volatile content lead to greater gas production
instead of the solid phase.

> Read full chapter

Analytical Techniques
Prabir Basu, in Biomass Gasification, Pyrolysis and Torrefaction (Third Edition), 2018

14.1.2 Proximate Analysis

Proximate analysis gives the gross composition of the biomass and hence it is
relatively easy to measure. One can do this without any elaborate set up or expensive
analytical equipment. For wood fuels, we can use standard E-870-06. Separate ASTM
standards are applicable for determination of the individual components of biomass
as listed in Table 14.2.

Table 14.2. Standard Methods for Proximate Analysis of Biomass

Fuel constituents Standard methods

Volatile matter E 872 for wood fuels
Ash D 1102 for wood fuels
Moisture E 871 for wood fuels
Fixed Carbon By difference

The moisture and ash determined in proximate analysis refer to the same moisture
and ash determined in ultimate analysis. However, the fixed carbon in proximate
analysis is different from the carbon in ultimate analysis. In proximate analysis, it
does not include the carbon in the volatile matter and is often referred to as the char
yield after devolatilization.

14.1.2.1 Volatile Matter

For the determination of volatile matter, the fuel is heated to a standard temperature
and at a standard rate in a controlled environment. The applicable ASTM standard
for determination of volatile matter is E-872 for wood fuels and D-3175-07 for coal
and coke.

Standard E-872 specifies that 50 g of test sample be taken out of no less than a
10 kg representative sample of biomass using the ASTM D-2013 sample reduction
protocol. This sample is ground to less than 1 mm in size through cutting or
shearing, and 1 g is taken from it. The sample is put in a covered crucible, so as
to avoid contact with air, during devolatilization. The covered crucible is placed in a
furnace maintained at 950 ± 20°C. The volatiles released are detected by luminous
flame observed from the outside. The crucible is heated for 7 min. After 7 min, the
crucible is taken out, cooled in a desiccator, and weighed as soon as possible to
determine the weight loss due to devolatilization.

For nonsparking coal or coke, Standard D-3175-07 is used which, follows a similar
process except that it requires a 1.0 g sample ground to 250 micron size (as per
D-346 protocol). The rest of the procedure is the same as above. For sparking
samples, it should be slowly heated to 600°C in 6 min and then heated at 950°C
exactly for 6 min.

14.1.2.2 Ash
The ash content of fuel is determined by ASTM test protocol D-1102 for wood,
E-1755-01 for other biomass, and D-3174 for coal.

The standard D-1102 specifies a 2.0 g sample of wood (sized below 475 μm) dried
in a standard condition and placed in a muffle furnace with the lid of the crucible
removed. The temperature of the furnace is raised slowly to 580–600°C to avoid
flaming. When all the carbon is burnt, the sample is cooled and weighed. Standard
E-1755-01 specifies 0.5–1.0 g of dried biomass to be heated for 3 h at 575 ± 25°C.
After that the sample is cooled and weighed.

For coal or coke, standard D-3174-04 may be used. Here a 1.0 g sample (pulverized
below 250 μm) is dried under standard conditions and heated to 450–500°C for the
first 1 h and then to 700–750°C (950°C for coke) for the second 1 h. The sample is
heated for 2 h or longer at that temperature to ensure that the carbon is completely
burnt. It is then removed from the furnace, cooled, and weighed.

14.1.2.3 Moisture
Moisture content (M) is determined by the test protocol given in ASTM standards
D-871-82 for wood, D-1348-94 for cellulose, D-1762-84 for wood charcoal, and
E-949-88 for RDF (total moisture). For equilibrium moisture in coal one could use
D-1412-07. In these protocols, a weighed sample of the fuel is heated in an air oven
at 103°C and weighed after cooling. To ensure complete drying of the sample, the
process is repeated until its weight remains unchanged. The difference in weight
between a dry and a fresh sample gives the moisture content in the fuel.

Standard E-871-82, for example, specifies that a 50 g wood sample be dried at 103°C
for 30 min. It is left in the oven at that temperature for 16 h before it is removed and
weighed. The weight loss gives the moisture (M) of the proximate analysis.

Standard E-1358-97 provides an alternative means of measurement of moisture

using microwave. However, this alternative represents only the physically bound
moisture; moisture released through chemical reactions during pyrolysis constitutes
volatile matter.

Klass (1998) proposed an alternative means of measuring the proximate composition

of a fuel using thermogravimetry (TG). In these techniques, a small sample of the fuel
is heated in a specified atmosphere at the desired rate in an electronic microbalance.
This gives a continuous record of the weight change of the fuel sample in a TG
apparatus. The differential TG apparatus gives the rate of change in the weight of the
fuel sample continuously. Thus, from the measured weight loss-versus-time graphs,
we can determine the fuel’s moisture, volatile matter, and ash content. The fixed
carbon can be found from Eq. (3.23). This method, though not an industry standard,
can quickly provide information regarding the thermochemical conversion of a fuel.

TG analysis provides additional information on reaction mechanisms, kinetic pa-

rameters, thermal stability, and heat of reaction. A detailed database of thermal
analysis is given in Gaur and Reed (1995).

> Read full chapter

Biomass fuels for small and micro com-

bined heat and power (CHP) systems:
resources, conversion and applications
H. Liu, in Small and Micro Combined Heat and Power (CHP) Systems, 2011

5.2 Characterisation of solid biomass fuels

Proximate analysis, ultimate analysis and calorific value are commonly used to
characterise solid biomass fuels. The proximate analysis serves as a simple means for
determining the behaviour of a solid biomass fuel when it is heated. It determines
the contents of moisture, volatile matter, ash and fixed carbon of the fuel. On the
other hand, the main purpose of an ultimate analysis is to determine the elemental
composition of the solid fuel substance. The calorific value of a fuel is a direct
measure of the chemical energy stored in the fuel.

Due to the inhomogeneous nature of solid biomass fuels, it is notoriously difficult

to prepare small quantities (in the order of grams) of representative samples for bio-
mass characterisation tests. Therefore, strict sampling and preparation procedures
specified by the British/European standard BS EN 14778-1:2005 have to be followed
by any proximate, ultimate and calorific value tests of solid biomass fuels described
below.

5.2.1 Proximate analysis

Since an appreciable amount of water vapour is released when a solid biomass fuel is
heated to above the boiling temperature of water, the first parameter of a proximate
analysis is the moisture content of the fuel. The moisture content is determined by
drying solid biomass samples at 105 °C in air atmosphere until constant mass is
achieved and percentage moisture calculated from the loss in mass of the sample.
Standard procedures for the determination of moisture content of solid biomass
fuels are specified by three British/European standards BS EN 14774-1:2009, BS EN
14774-2:2009 and BS EN 14774-3:2009.

Another major loss occurs when a solid biomass fuel is heated in a covered crucible
or in other apparatus which prevents the oxidation of the carbon residue. This loss
is referred to as the volatile matter and constitutes the second parameter of the
proximate analysis. Volatile matter is determined with the sample being heated
out of contact with ambient air at 900 °C for 7 minutes. Standard procedures for
the determination of volatile matter of solid biomass fuels are specified by the
British/European standard BS EN 15148:2009.

If the remaining residue is further combusted, the residue left after the combustion
is called ash, and the weight loss on combustion is referred to as ‘fixed carbon’. Fixed
carbon and ash contents constitute the third and fourth parameters of the proximate
analysis. This part of proximate analysis, i.e. the combustion of the residue, is
carried out in a furnace at 550 °C and the standard procedures are specified by the
British/European standard BS EN 14775:2009.

It is not always practical to conduct the above various determinations stepwise.

Therefore, one set of samples could be used for the moisture content determination,
and another set of samples for the combined moisture and volatile matter loss, and
still another set of samples for ash determination.

5.2.2 Ultimate analysis

The main purpose of ultimate analysis is to determine the elemental composition of
a solid biomass fuel. The main elements of solid biomass fuels include carbon (C),
hydrogen (H), nitrogen (N), sulphur (S) and oxygen (O) but for some solid biomass
fuels chlorine (Cl) and other elements may also be of interest. Nowadays, the
ultimate analyses of sold biomass fuels are usually carried out with fully automated
instruments. The instrumental method for the determination of total carbon, hy-
drogen and nitrogen contents in solid biomass fuels is described by the British/Eu-
ropean standard CEN/TS 15104:2005, whereas the methods for the determination
of the total sulphur and total chlorine content in solid biomass fuels are specified by
the British/European standard CEN/TS 15289:2006. Sometimes, the determinations
of the major elements (Al, Ca, Fe, Mg, P, K, Si, Na and Ti) and the minor elements
(As, Cd, Co, Cr, Cu etc.) of solid biomass fuels are also necessary and required. The
British/European standards CEN/TS 15290:2006 and CEN/TS15297:2006 describe
and specify the corresponding methods and procedures.

5.2.3 Calorific value

The calorific value of a fuel is the number of heat units evolved when unit mass (or
unit volume in the case of a gas) of a fuel is completely burned and the combustion
products are cooled to 298 K. This definition of calorific value includes the provision
that the products of combustion are cooled to 298 K which means the sensible heat
and the latent heat of condensation of the water produced during combustion are
included in the heat liberated. Therefore, the calorific value of the fuel is designated
as ‘ gross calorific value (GCV)’ or ‘high heating values (HHV)’. However, with many
industrial applications, the latent heat of condensation is not given up and the total
heat liberated per unit mass (or volume) of the fuel is less. The calorific value in the
case where the water remains as vapour is designated as ‘net calorific value (NCV)’
or ‘low heating value (LHV)’.

The gross calorific value of a solid biomass fuel is usually determined experimentally
by a bomb calorimeter, whereas the net calorific value of the fuel is usually calculated
from the gross calorific value and the ultimate analysis of the fuel. Specific exper-
imental procedures and calculation formulae are detailed by the British/European
standard BS EN 14918:2009. Many solid biomass fuels contain high moisture
content which greatly affects the net calorific value as illustrated by Fig. 5.2 and
Table 5.1 (Larkin et al. 2004).

5.2. Effect of moisture content on the net calorific value of a biomass fuel.

Table 5.1. Average net calorific value of solid biomass fuels (Larkin et al. 2004)

Fuel Net calorific value

(GJ/tonne) (GJ/m3)
Wood (green, 60% moisture) 6 7
Wood (air-dried, 20% moisture) 15 9
Wood (oven-dried, 0% mois- 18 9
ture)
Grass (fresh-cut) 4 3
Straw (as harvested, baled) 15 1.5
Domestic refuse (as collected) 9 1.5
Coal (UK average) 28 50
5.2.4 Calculation of analyses to different bases
The analytical data of solid biomass fuels may be reported on different bases
including as analysed (air-dried, ad), as-received (ar), dry basis (db) and dry and
ash-free (daf ). Most analytical values on a particular basis may be converted to any
other basis by multiplying it by the appropriate formula given in Table 5.2, after
insertion of the numerical values for the symbols. However, for some parameters
(H, O and net calorific value) there is a direct involvement of the moisture content.
Further details on the calculation of analyses to different bases are described by the
British/International standard CEN/TS 15296:2006.

Table 5.2. Formulae for calculation of results to different bases*

Given Wanted
As analysed (air As received (ar) Dry (d) Dry, ash, free (daf )
dried, ad)
As analysed (air 1
dried, ad)
As received (ar) 1
Dry (d) 1
Dry, ash, free 1
(daf )

* M - moisture content (%), A - ash content (%)

Table 5.3 shows the proximate, ultimate analyses and gross calorific values of select-
ed solid biomass fuels (Gaur and Reed 1995). The proximate and ultimate analyses
of more solid biomass fuels can be found in many references such as Gaur and Reed
(1995), Annalmalai and Puri (2007), and biomass databases such as Phyllis (2010).

Table 5.3. Proximate, ultimate analyses and gross calorific values of selected solid
biomass fuels (dry basis) (Gaur and Reed 1995)

Name Fixed Volatiles(%)

Ash(%) C(%) H(%) O(%) N(%) S(%) GCV-
carbon (MJ/kg)
(%)
Wood- 17.17 82.54 0.29 49.25 5.99 44.38 0.06 0.03 20.02
Pon-
derosa
pine
Energy 16.35 82.32 1.33 48.45 5.85 43.89 0.47 0.01 19.38
crop
poplar
Processed biomass
15.77 Plywood
82.14 2.09 48.13 5.87 42.46 1.45 0.00 18.96
Agricul- 19.80 71.30 8.90 43.20 5.00 42.18 0.61 0.11 17.51
tural
Wheat
straw
55.80 33.90 10.30 75.50 5.00 4.90 1.20 3.10 31.75
CoalPitts-
burgh
seam

> Read full chapter

Analytical Techniques
Prabir Basu, in Biomass Gasification, Pyrolysis and Torrefaction (Second Edition),
2013

13.1.2 Proximate Analysis

Proximate analysis gives the gross composition of the biomass and hence it is
relatively easy to measure. One can do this without any elaborate set up or expensive
analytical equipment. For wood fuels, we can use standard E-870-06. Separate ASTM
standards are applicable for determination of the individual components of biomass:

• Volatile matter: E-872 for wood fuels

• Ash: D-1102 for wood fuels

• Moisture: E-871 for wood fuels

• Fixed carbon: determined by difference.

The moisture and ash determined in proximate analysis refer to the same moisture
and ash determined in ultimate analysis. However, the fixed carbon in proximate
analysis is different from the carbon in ultimate analysis. In proximate analysis, it
does not include the carbon in the volatile matter and is often referred to as the char
yield after devolatilization.

13.1.2.1 Volatile Matter

For the determination of volatile matter, the fuel is heated to a standard temperature
and at a standard rate in a controlled environment. The applicable ASTM standard
for determination of volatile matter is E-872 for wood fuels and D-3175-07 for coal
and coke.

Standard E-872 specifies that 50 g of test sample be taken out of no less than a
10 kg representative sample of biomass using the ASTM D-2013 sample reduction
protocol. This sample is ground to less than 1 mm in size through cutting or
shearing, and 1 g is taken from it. The sample is put in a covered crucible, so as
to avoid contact with air, during devolatilization. The covered crucible is placed in
a furnace maintained at 950±20°C. The volatiles released are detected by luminous
flame observed from the outside. The crucible is heated for 7 min. After 7 min, the
crucible is taken out, cooled in a desiccator, and weighed as soon as possible to
determine the weight loss due to devolatilization.

For nonsparking coal or coke, Standard D-3175-07 is used which, follows a similar
process except that it requires a 1.0 g sample ground to 250 micron size (as per D-346
protocol). The rest of the procedure is the same as above. For sparking samples, it
should be slowly heated to 600°C in 6 min and then heated at 950°C exactly for
6 min.

13.1.2.2 Ash
The ash content of fuel is determined by ASTM test protocol D-1102 for wood,
E-1755-01 for other biomass, and D-3174 for coal.

Standard D-1102 specifies a 2.0 g sample of wood (sized below 475 µm) dried in
a standard condition and placed in a muffle furnace with the lid of the crucible
removed. The temperature of the furnace is raised slowly to 580–600°C to avoid
flaming. When all the carbon is burnt, the sample is cooled and weighed. Standard
E-1755-01 specifies 0.5–1.0 g of dried biomass to be heated for 3 h at 575±25°C.
After that the sample is cooled and weighed.

For coal or coke, standard D-3174-04 may be used. Here a 1.0 g sample (pulverized
below 250 µm) is dried under standard conditions and heated to 450–500°C for the
first 1 h and then to 700–750°C (950°C for coke) for the second 1 h. The sample is
heated for 2 h or longer at that temperature to ensure that the carbon is completely
burnt. It is then removed from the furnace, cooled, and weighed.

13.1.2.3 Moisture
Moisture content (M) is determined by the test protocol given in ASTM standards
D-871-82 for wood, D-1348-94 for cellulose, D-1762-84 for wood charcoal, and
E-949-88 for RDF (total moisture). For equilibrium moisture in coal one could use
D-1412-07. In these protocols, a weighed sample of the fuel is heated in an air oven
at 103°C and weighed after cooling. To ensure complete drying of the sample, the
process is repeated until its weight remains unchanged. The difference in weight
between a dry and a fresh sample gives the moisture content in the fuel.

Standard E-871-82, for example, specifies that a 50 g wood sample be dried at 103°C
for 30 min. It is left in the oven at that temperature for 16 h before it is removed and
weighed. The weight loss gives the moisture (M) of the proximate analysis.

Standard E-1358-97 provides an alternative means of measurement of moisture

using microwave. However, this alternative represents only the physically bound
moisture; moisture released through chemical reactions during pyrolysis constitutes
volatile matter.

Klass (1998) proposed an alternative means of measuring the proximate composition

of a fuel using thermogravimetry (TG). In these techniques, a small sample of the fuel
is heated in a specified atmosphere at the desired rate in an electronic microbalance.
This gives a continuous record of the weight change of the fuel sample in a TG
apparatus. The differential thermogravimetry apparatus gives the rate of change
in the weight of the fuel sample continuously. Thus, from the measured weight
loss-versus-time graphs, we can determine the fuel’s moisture, volatile matter,
and ash content. The fixed carbon can be found from Eq. (3.23). This method,
though not an industry standard, can quickly provide information regarding the
thermochemical conversion of a fuel.

TG analysis provides additional information on reaction mechanisms, kinetic pa-

rameters, thermal stability, and heat of reaction. A detailed database of thermal
analysis is given in Gaur and Reed (1995).

> Read full chapter

Blending Coal with Biomass

David A. Tillman, ... N. Stanley Harding, in Solid Fuel Blending, 2012

4.6.4 Proximate and Ultimate Analysis and Higher Heating

Value
The proximate and ultimate analysis and higher heating value of a fuel provide a
broad understanding of its combustion characteristics. General parameters such
as fixed carbon, volatile matter, ash concentration, moisture, and others provide a
crude estimate of how the fuel will behave when it is burned and can provide certain
traditional measures such as ash loading and estimates for emission constituents
such as sulfur. Proximate and ultimate analysis along with higher heating values for
several of the biomass fuels was given in the preceding tables. These parameters are
necessary but are not sufficient to define and detail the behavior of a particular
fuel and/or fuel blend. Other measures such as reactivity for both the organic and
inorganic fractions will be discussed later.

> Read full chapter

Utilization of coal in IGCC systems
Sarma V. Pisupati, Vijayaragavan Krishnamoorthy, in Integrated Gasification Com-
bined Cycle (IGCC) Technologies, 2017

2.3.1 Chemical composition

Proximate analysis is one of the first analyses performed on coal after mining. The
test involves heating the coal under various conditions for variable amounts of time
to determine moisture, volatile matter, fixed carbon, and ash yield. Moisture in coal
is determined by heating the coal to a temperature slightly above the boiling point of
water (377–383K) and holding it at that temperature until there is no further weight
loss. Volatiles are measured based on additional weight loss by heating the coal to
950°C 1223K in a N2 atmosphere. The leftover residue, known as char, is burnt in
O2 to measure the incombustible residue called ash. Fixed carbon is the organic
matter in the char, determined by the difference between 100 and the sum of the
percentages of volatile matter, ash, and moisture.

One of the most important parameters obtained from proximate analysis is the
moisture content. A higher moisture content in the coals tends to reduce the gasifier
temperature and consequently the rate of conversion of carbon during gasification
(Schobert, 1995). Moreover, moisture can also affect the way the coal is fed into
the gasifier. When the inherent moisture increases, the pulverized particles in the
dry feed system tend to agglomerate, resulting in unsteady feeding of the coal.
Based on a study conducted with a KBR transport gasifier, inherent moisture of
greater than 28% for a particle size distribution between 200–800 µm can result in
an unsteady operation of lock hopper feeders (Dorminey et al., 2009). For finer feed
particles fed into entrained-flow gasifiers, a guideline of less than 2 wt% moisture is
recommended. The limit on moisture is to ensure acceptable pneumatic conveying
characteristics of coal (Yun et al., 2007). Besides affecting the dry feeding system,
high-moisture coals can also affect the overall efficiency of slurry-feed gasifiers.
High-moisture coals are typically low-rank coals, which are of low calorific value.
Feeding such coals as slurry with added water can affect the overall energy density
of the slurry, leading to lower efficiency of the gasifier.

Another parameter in the proximate analysis is ash. It is important to recognize

that coal has mineral matter and not ash. Ash is the product of combustion or
gasification (high temperature oxidation or reduction of mineral matter). Coals with
high ash yield are not preferred, as a large feed rate is needed to generate the same
amount of energy (Mastalerz et al., 2008). Additionally, the sensible heat available
for gasification reactions is reduced in the presence of a substantial amount of ash
in the gasifier, resulting in reduced efficiency. Besides the loss of sensible heat,
melt phase derived from ash can cover char structure, leading to a higher amount of
unconverted carbon in the slag. Mastalerz et al. (2008) reported that the maximum
ash yield from coal that fixed-bed, fluidized-bed, and entrained-flow gasifiers can
handle are 15%, 40%, and 25%, respectively.

The other parameter that is determined is the volatile matter. Higher volatile matter
in coals is advantageous because it is evolved as gas instantaneously, leaving behind
a small amount of char with higher porosity (Mastalerz et al., 2008). The rate of
conversion of char to gas phase is much slower, and therefore a lesser amount of
char in the gasifier results in higher gasification efficiency. The amount of volatile
matter in coal decreases with increasing rank.

Ultimate analysis is the elemental composition of coal: C, H, N, and S. This analysis

is very important for gasification processes for three reasons: 1. It enables one
to determine the amount of oxidant/steam required; 2. The H/C ratio of a coal
determines the H2/CO ratio in the product gas; and 3. The amount of sulfur in coal
must be known to design syngas cooler systems and acid gas removal systems. This
final reason is because most of the sulfur in coal is released as H2S (Krishnamoorthy
and Pisupati, 2016). H2S can damage syngas coolers significantly, and the extent
of corrosion of the syngas cooler is dependent on PS2/PO2 and on the presence of
chlorine (Collot, 2006). Besides, the concentration of H2S in syngas is necessary to
design the size of the acid-recovery unit.

Heating value is another important parameter without which gasification efficiency-

, heat balances, and process simulations cannot be performed. Moreover, the
heating value of the feed determines the gasifier capacity and dimensions (Mastalerz
et al., 2008). Heating value varies with the rank of coal. Anthracites have twice the
calorific value compared to lignites because lignites contain higher amounts of
moisture and oxygen. Subbituminous and bituminous coals have heating values that
are higher than lignites, while the heating values of some low-volatile bituminous
coals sometimes may exceed those of anthracite coals.

> Read full chapter

Coal
Balasubramanian Viswanathan, in Energy Sources, 2017

Proximate Analysis
A proximate analysis is not approximate analysis! It is unfortunate that the name
“proximate” sounds much like the word “approximate.” The procedures for prox-
imate analysis are rigorously established by the American Society for Testing and
Materials along with the standards for acceptable levels of error within a laboratory
and among different laboratories.

In this described method of analysis of percent moisture, percent volatile matter,

percent ash, and therefore percent fixed carbon, the actual components of the
volatile matter, ash, or fixed carbon are never determined. That is, the carbon
dioxide evolved in the volatile matter is never collected, determined, and reported as
some percentage of carbon dioxide. In analytical chemistry the practice of lumping
together a variety of components and reporting them as a single entity is called
proximate analysis. The proximate analysis of coal is therefore the determination of
moisture of volatile matter, fixed carbon, and ash.

Ash Content
Strictly speaking, there is no ash in coal. The incombustible residue, ash, remaining
after the combustion of coal is actually the product of high-temperature reactions of
inorganic components, termed “mineral matter,” originally present in the coal. The
amount of ash is not necessarily equal to the amount of original mineral matter.

Fuel Ratio of Coal

The fuel ratio of coal is defined as the ratio of fixed carbon to volatile matter. Coal
with a high-volatile matter is usually easy to ignite, burn with a large, often smoky
flame, and burn quickly. Coal with high-fixed carbon is hard to ignite but it burns
slowly with a short, clean flame [7].

> Read full chapter

Biomass Characteristics
Prabir Basu, in Biomass Gasification and Pyrolysis, 2010

2.6.2 Proximate Analysis

Proximate analysis gives the composition of the biomass in terms of gross com-
ponents such as moisture (M), volatile matter (VM), ash (ASH), and fixed carbon
(FC). It is a relatively simple and inexpensive process. For wood fuels, we can use
standard E-870-06. Separate ASTM standards are applicable for determination of
the individual components of biomass:

• Volatile matter: E-872 for wood fuels

• Ash: D-1102 for wood fuels

• Moisture: E-871 for wood fuels

• Fixed carbon: determined by difference

The moisture and ash determined in proximate analysis refer to the same moisture
and ash determined in ultimate analysis. However, the fixed carbon in proximate
analysis is different from the carbon in ultimate analysis: In proximate analysis it
does not include the carbon in the volatile matter and is often referred to as the char
yield after devolatilization.

Volatile Matter
The volatile matter of a fuel is the condensable and noncondensable vapor released
when the fuel is heated. Its amount depends on the rate of heating and the tempera-
ture to which it is heated. For the determination of volatile matter, the fuel is heated
to a standard temperature and at a standard rate in a controlled environment. The
applicable ASTM standard for determination of volatile matter is E-872 for wood
fuels and D-3175-07 for coal and coke.

Standard E-872 specifies that 50 g of test sample be taken out of no less than a 10-kg
representative sample of biomass using the ASTM D-346 protocol. This sample is
ground to less than 1 mm in size, and 1 g is taken from it, dried, and put in a covered
crucible so as to avoid contact with air during devolatilization. The covered crucible
is placed in a furnace at 950 °C and heated for seven minutes. The volatiles released
are detected by luminous flame observed from the outside. After seven minutes, the
crucible is taken out, cooled in a desiccator, and weighed to determine the weight
loss due to devolatilization.

Standard D-3175-07, when used for nonsparking coal or coke, follows a similar
process except that it requires a 1-g sample ground to 250 µm. The sample is heated
in a furnace at 950 °C for seven minutes. For sparking coal or coke, the heating
process deviates slightly from that specified in E-872: D-3175-07 specifies that the
sample be gradually heated to 600 °C within six minutes and then put in a 950 °C
furnace for six minutes. After this, the crucible containing the sample is removed
and cooled for 15 minutes before it is weighed. Heating rates faster than this may
yield higher volatile matter content, but that is not considered the volatile matter of
the fuel's proximate analysis.

Ash
Ash is the inorganic solid residue left after the fuel is completely burned. Its primary
ingredients are silica, aluminum, iron, and calcium; small amounts of magnesium,
titanium, sodium, and potassium may also be present. Ash content is determined
by ASTM test protocol D-1102 for wood, E-1755-01 for other biomass, and D-3174
for coal.

Standard D-1102 specifies a 2-g sample of wood (sized below 475 micron) dried
in a standard condition and placed in a muffle furnace with the lid of the crucible
removed. Temperature of the furnace is raised slowly to 580 to 600 °C to avoid
flaming. When all the carbon is burnt, the sample is cooled and weighed. Standard
E-1755-01 specifies 1 g of biomass dried, initially heated to 250 °C at 10 °C/min,
and held there for 30 minutes. Following this, the temperature is increased to 575
°C and kept there until all the carbon is burnt. After that the sample is cooled and
weighed.

For coal or coke, standard D-3174-04 may be used. Here a 1-g sample (pulverized
below 250 micron) is dried under standard conditions and heated to 450 to 500 °C
for the first one hour and then to 700 to 750 °C (950 °C for coke) for the second
hour. The sample is heated for two hours or longer at that temperature to ensure
that the carbon is completely burnt. It is then removed from the furnace, cooled,
and weighed.

Strictly speaking, this ash does not represent the original inorganic mineral matter in
the fuel, as some of the ash constituents can undergo oxidation during burning. For
exact analysis, correction may be needed. The ash content of biomass is generally
very small, but may play a significant role in biomass utilization especially if it
contains alkali metals such as potassium or halides such as chlorine. Straw, grasses,
and demolition wood are particularly susceptible to this problem. These components
can lead to serious agglomeration, fouling, and corrosion in boilers or gasifiers
(Mettanant et al., 2009).

The ash obtained from biomass conversion does not necessarily come entirely from
the biomass itself. During collection, biomass is often scraped off the forest floor
and then undergoes multiple handlings, during which it can pick up a considerable
amount of dirt, rock, and other impurities. In many plants, these impurities consti-
tute the major inorganic component of the biomass feedstock.

Moisture
High moisture is a major characteristic of biomass. The root of a plant biomass
absorbs moisture from the ground and pushes it into the sapwood. The moisture
travels to the leaves through the capillary passages. Photosynthesis reactions in
the leaves use some of it, and the rest is released to the atmosphere through
transpiration. For this reason there is more moisture in the leaves than in the tree
trunk.
The total moisture content of some biomass can be as high as 90% (dry basis), as
seen in Table 2.9. Moisture drains much of the deliverable energy from a gasification
plant, as the energy used in evaporation is not recovered. This important input
design parameter must be known for assessment of the cost of or energy penalty in
drying the biomass. The moisture in biomass can remain in two forms: (1) free, or
external; and (2) inherent, or equilibrium.

TABLE 2.9. Moisture Content of Some Biomass

Bio- Corn Wheat Rice Rice Dairy Wood Saw- Food RDF Water
mass Stalks Straw Straw Husk Cattle Bark dust Waste Pellets Hy-
Ma- acinth
nure
Mois- 40–60 8–20 50–80 7–10 88 30–60 25–55 70 25–35 95.3
ture
(wet
basis)

Source: Compiled from Kitani and Hall, 1989, p. 863.

Free moisture is that above the equilibrium moisture content. It generally resides
outside the cell walls. Inherent moisture, on the other hand, is absorbed within
the cell walls. When the walls are completely saturated the biomass is said to have
reached the fiber saturation point, or equilibrium moisture. Equilibrium moisture
is a strong function of the relative humidity and weak function of air temperature.
For example, the equilibrium moisture of wood increases from 3 to 27% when the
relative humidity increases from 10 to 80% (Jenkins, 1996, p. 864).

Moisture content (M) is determined by the test protocol given in ASTM standards
D-871-82 for wood, D-1348-94 for cellulose, D-1762-84 for wood charcoal, and
E-949-88 for RDF (total moisture). For equilibrium moisture in coal one could used
D-1412-07. In these protocols, a weighed sample of the fuel is heated in an air oven
at 103 °C and weighed after cooling. To ensure complete drying of the sample, the
process is repeated until its weight remains unchanged. The difference in weight
between a dry and a fresh sample gives the moisture content in the fuel.

Standard E-871-82, for example, specifies that a 50-g wood sample be dried at 103
°C for 30 minutes. It is left in the oven at that temperature for 16 hours before it
is removed and weighed. The weight loss gives the moisture (M) of the proximate
analysis.

Standard E-1358-06 provides an alternative means of measurement using mi-

crowave. However, this alternative represents only the physically bound moisture;
moisture released through chemical reactions during pyrolysis constitutes volatile
matter. The moisture content of some biomass fuels is given in Table 2.10.

TABLE 2.10. Comparison of Proximate Analysis of Biomass Measured by Two Meth-

ods
Fuel FC (% dry) VM (% dry) ASH (% dry) Technique
Corn cob 18.5 80.1 1.4 ASTM
16.2 80.2 30.6 TG
Rice husk 16.7 65.5 17.9 ASTM
19.9 60.6 19.5 TG

Source: From Klass, 1998, p. 239.

Moisture Basis

Biomass moisture is often expressed on a dry basis. For example, if Wwet kg of wet
biomass becomes Wdry after drying, its dry basis (Mdry) is expressed as

(2.20)

This can give a moisture percentage greater than 100% for very wet biomass,
which might be confusing. For that reason, the basis of moisture should always be
specified.

The wet-basis moisture is

(2.21)

The wet basis (Mwet) and the dry basis (Mdry) are related as

(2.22)

Fixed Carbon

Fixed carbon (FC) in a fuel is determined from the following equation, where M, VM,
and ASH stand for moisture, volatile matter, and ash, respectively.

(2.23)

This represents the solid carbon in the biomass that remains in the char in the
pyrolysis process after devolatilization. With coal, FC includes elemental carbon
in the original fuel, plus any carbonaceous residue formed while heating, in the
determination of VM (standard D-3175).

Biomass carbon comes from photosynthetic fixation of CO2 and thus all of it is
organic. During the determination of VM, a part of the organic carbon is transformed
into a carbonaceous material called pyrolytic carbon. Since FC depends on the
amount of VM, it is not determined directly. VM also varies with the rate of heating. In
a real sense, then, fixed carbon is not a fixed quantity, but its value, measured under
standard conditions, gives a useful evaluation parameter of the fuel. For gasification
analysis, FC is an important parameter because in most gasifiers the conversion
of fixed carbon into gases determines the rate of gasification and its yield. This
conversion reaction, being the slowest, is used to determine the size of the gasifier.

Char

Char, though a carbon residue of pyrolysis or devolatilization, is not pure carbon;

it is not the fixed carbon of the biomass. Known as pyrolytic char, it contains some
volatiles and ash in addition to fixed carbon. Biomass char is very reactive. It is highly
porous and does not cake. This noncaking property makes it easy to handle.

> Read full chapter

Problems of Oxygen Stoichiometry in

Analyses of Coal and Related Materials
Alexis Volborth, in Analytical Methods for Coal and Coal Products, Volume III, 1979

1 Moisture
Proximate analysis of coal consists of determination, by ASTM standardized meth-
ods, of moisture, volatile matter, and ash, and calculating fixed carbon “by dif-
ference.” These techniques are described in detail in the ASTM Standards (ASTM,
1974, 1975, 1976) and in U.S. Bureau of Mines (1967) Bulletin 638. See also Volume
I, Chapter 6, Section III. An excellent critique on limitations (Rees, 1966), and an
up-to-date discussion of problems and solutions of classical coal analysis (Given
and Yarzab, 1975, see also Volume II, Chapter 20) emphasize the inadequacies, the
difficulties in interpretation, and the misleading nature of reporting of coal analysis
results in the context of what should be “modern” coal chemistry.

Volborth (1976c,d) and co-workers (Volborth et al., 1977b,c) have pointed out the
significance of adding oxygen determination to that of “moisture” before and after
drying of coal. The increasing role of instrumental analysis of coal has been reviewed
by Ignasiak et al. (1975). In this chapter only the information supplied by the oxygen
determination in coal prior to and after determination of moisture in coal ash will
be discussed.

The reason that the term “moisture” is misleading is because a chemist new to
coal science will often equate this with water (H2O), whereas, according to the
ASTM approved procedures, it is actually a weight loss determined under strictly
controlled drying conditions. Therefore, “moisture” is a quantity “by definition”
determined during coal analysis. To make the matter more complicated, several
standardized procedures are used. This is because of the nature of coal, its instability
and varying handling and the changes of ambient conditions in laboratories. Rees
(1966) distinguishes four fundamental categories of moisture in coal: (1) inherent or
equilibrium moisture that a coal can hold when in equilibrium with the atmosphere;
(2) water of hydration moisture held by the mineral matter in coal; (3) surface
moisture in excess of the inherent moisture, and (4) decomposition moisture derived
theoretically from the decomposing “coal molecule” at temperatures above 200°C.
For more information on moisture in coal, see Volume I, Chapter 7.

In practice, the coal chemist most frequently determines the weight loss at 105°C
by the so-called “oven method” of which there are two main variants, depending on
the coal grain size. This routinely reported moisture value does not correspond to
any of the previously mentioned fundamental categories. Besides, only if the water
is specifically absorbed in a U-tube filled with a dessicant is it possible to determine
the H2O by weighing. Distillation and collection in a graduated tube usually results
in two immiscible liquids, one of which is water, the other a mixture of hydrocarbons.
The lighter hydrocarbons escape as gases unless specifically trapped. This process
shows that in addition to water, the quantity called “moisture” contains varying
losses other than H2O depending on the coal, the temperature, and the time period.
Heating in air may, in addition, cause oxidation and weight gain of the residue,
depending on the type of coal, thus resulting in low data for the “weight loss.”

These considerations apply to coal conversion when working at higher tempera-

tures with coal as in coal gasification, liquefaction, solvent refining, combustion,
carbonization, and in fluidized-bed utilization processes where the relative quantities
of water (H2O) versus evolved hydrocarbons and other gases are even more difficult
to estimate unless one also monitors the oxygen content starting with the “feed
stocks” or original material, including oxygen analyses of all the interim products up
to the final ash materials. It is evident that if oxygen is monitored during all stages
of moisture determination, any gross discrepancies between moisture calculated as
H2O and the equivalent oxygen loss as compared with oxygen retained in the solid
product will signal to the analyst and the engineer that either significant volatile
hydrocarbons are lost or, if more oxygen is found in the solids than expected, that
oxidation has occurred and the “moisture” results thus must be low. It is for this
purpose that we have mentioned industrial processes. The same considerations used
by us in monitoring moisture should apply to a greater extent to industrial processes,
even though these industrial interim steps do not constitute nor require at present
moisture determination as such.

The complexities and difficulties of “moisture” determination and of the interpre-

tation of results, as well as the existence of a multitude of different methods, have
prompted us to attempt to simplify and further quantify the coal analysis by the
use of FNAA determined oxygen data (see Chapter 47) before and after drying (“as
received” and “dried” 105°C) coal. This approach can be applied irrespective of the
method of drying. It consists of calculating the theoretical quantity of water (H2O)
lost during the drying of coal, based on the total loss of oxygen between the steps,
and assuming that all of the loss was water. The equation for this calculation is

(1)

where Oar is the percent oxygen determined by FNAA on the coal sample as received
by the laboratory, and Od is the percent oxygen determined on the dried sample
(Miller and Volborth, 1976). In Table I six lignites from the Wyoming Wyodak Bed,
kindly supplied to us by Gary B. Glass of the Wyoming Geological Survey, have been
analyzed and recalculated in this manner. The moisture determination, repeated at
our laboratories at the University of California at Irvine (UCI) and compared with
the U.S. Bureau of Mines (USBM) report data, and oxygen are determined on wet
samples “as received” as well as on samples “dried” at 105°C. This compilation shows
that the assumption that all of the weight loss was water (H2O) is probably correct
in all of these lignites within about 1%. It also shows that by performing the two
oxygen determinations on coals that do not contain considerable light hydrocarbons
and do not markedly oxidize, one can estimate the “moisture” in terms of water,
which is more informative for the coal chemist. In the last listed lignite K-46430,
the UCI-determined “moisture” is proven to be more correct on this sample than
that reported by the USBM [The fact the USBM report may include a printing error
(21.9 = 27.9?) does not alter this demonstration of our ability to detect serious
discrepancies when they appear in coal analysis reports and this is not meant as
a criticism of the U.S.B.M. Rather, the data further demonstrate the high accuracy
of these U.S.B.M. coal analyses.] Extending this approach to coals dried at higher
temperatures should produce larger discrepancies and enable a rough estimate of
the percentage of nonoxygen containing gases, despite the fact that evolution of
such gases as CO2, CO, N, and SO2, with concurrent oxidation complicates the
calculation, requiring a study by gas chromatography or mass spectroscopy of the
evolving gas compositions. That considerable discrepancies between the “moisture”
based on oxygen determination and moisture based on the old methods exist is
shown on some HVA and medium volatile bituminous coals kindly supplied to us
by A. Davis of The Pennsylvania State University (Miller and Volborth, 1976, Table II).
Further work to explain the nature and reasons for these differences is needed and
is presently in progress.

TABLE I. Comparison of Moisture Calculated Based on FNA Analyses for Oxygen

with Moisture by the Classical Methods in Six Wyoming Lignites

Lignite, Wyoming Wyo- % Moisture % Oxygen

dak bed coal no.
USBM Report UCI (±0.1) As received Dried (105°C) % Moisturea cal-
culated
K-46565 29.9 31.1 43.64 22.99 31.37
K-46566 27.2 27.5 42.83 23.23 29.89
K-46216 22.6 21.1 36.38 21.48 22.13
K-46217 21.4 21.1 36.10 22.20 20.86
K-46218 21.1 20.9 35.90 22.02 20.79
K-46430 21.9 27.4 42.23 25.10 26.92

a See text and Eq. (1).

TABLE II. Comparison of Oxygen by Difference with Oxygen Determined by FNA

and Oxygen Calculated Assuming 46% Oxygen in Ash

Coal No. Odiff (wt.%) as re- Oxygen Deter- Odiff calc. (ash Ash (wt.%)
ported USBM “as mined FNA 46% O)
received”
K-46566 36.6 42.34 44.34 7.70
K-46218 32.3 35.90 37.82 5.50
K-46217 31.7 36.15 37.89 6.20
K-46216 33.2 36.85 38.13 4.90
K-46565 38.8 43.28 44.19 5.40

> Read full chapter

Fundamental Theories of Torrefaction

by Thermochemical Conversion
Stephen Gent, ... Evan Almberg, in Theoretical and Applied Aspects of Biomass
Torrefaction, 2017

3.4.4 Proximate Analysis

A proximate analysis of each sample using a thermo-gravimetric analyzer (TGA) gives
information on the percentage of moisture, volatiles, ash, and fixed carbon. Analyz-
ing raw corn stover fractions in the TGA will allow for simulation of torrefaction on
a micro-scale and provide specific information on optimum temperatures to avoid
mass loss that is not compensated by an increase in energy content. Performing
a proximate analysis on the initial raw biomass will quantify moisture and ash
levels, which affect the biochar product yield, composition, and storability. Fixed
carbon levels determined by the TGA provide information on the heat of combustion
for each sample; an increase in fixed carbon results in an increase in the heat of
combustion [12].

Biomass is a very promising resource for energy production and biofuels due to:
 • The wide array of conversion methods,

• Abundance,

• Availability, and

• Government mandates on lignocellulosic biofuels production.

Despite the aforementioned advantages, biomass often must be upgraded before

cofiring at high blend ratios or other thermochemical applications. Torrefaction
offers a very promising solution for biomass because it produces a solid with:

• lower ash, sulfur, and nitrogen content,

• increased energy density,

• increased hydrophobicity, and

• lower ratio of volatiles to fixed carbon.

There are challenges with industrial scale torrefaction, which are mostly associated
with lack of scientific knowledge and data on the process, but also due to the
composition of biomass feedstock.

> Read full chapter

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