Chemical compositions

Ultimate analysis

The ultimate analysis involves the determination of the percent values of carbon, hydrogen, oxygen,
nitrogen, sulfur and ash in the sample. The majority of MSW is composed of carbon, hydrogen and
oxygen.

Materials in organic portion of MSW: cellulose, lignin, fats, protein and hydrocarbon polymers.

Content Cellulose Sulfur Nitrogen Chlorine Toxic Non-toxic

metals metals
Type of Paper Building Food Organic: Cadmium Iron
waste materials waste Polyvinyl
Wood Yard Grass chloride(PVC) Lead Copper
waste clippings Vynil
Food Textiles Paper Mercury Magnesium
waste (wool and product
nylon) bleached
with chlorine
Yard Inorganic: Calcium
waste Sodium
chloride
Other type of
salt
sodium
References Masterson et al., 1981, Liu and Liptak, 2000

Table 1:Ultimate analysis of the combustible component in Household MSW (Source:Pitchel ,n.d)

% by Wt (dry basis)
Component Carbon Hydrogen Oxygen Nitrogen Sulfur Ash
Organic
Paper 43.5 6.0 44.0 0.3 0.2 6.0
Plastics 60.0 7.2 22.8 - - 10.0
Food wastes 48.0 6.4 37.8 2.6 0.4 5.0
Yard wastes 47.8 6.0 38.0 3.4 0.3 4.5
Textiles 55.0 6.6 31.2 4.6 0.15 2.5
Rubber 78.0 10.0 - 2.0 - 10.0
Wood 49.5 6.0 42.7 0.2 0.1 1.5

Inorganic
Glass 0.5 0.1 0.4 <0.1 - 98.9
Metals 4.5 0.6 4.3 <0.1 - 90.5
Dirt, ash 26.3 3.0 2.0 0.5 0.2 68.0
MSW 15-30 2-5 12-24 0.2-1.0 0.02-0.1 -

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Example: Estimate the chemical composition of the organic fraction of a sample of MSW. Some data on
waste properties is shown below.

Wet weight (kg) Dry weight(kg)

Paper 19 16
Plastics 3.7 3.5
Food wastes 5.1 1.9
Yard wastes 8.4 2.6
Textiles 1 0.8
Rubber 0.22 0.22
Wood 1.3 0.9

Step 1: Determine the percentage distribution of C,H,O,N and S occurring in the waste sample. Use the
percent values of these elements from Table 1(ultimate analysis)

Percentage by weight (Dry basis)

Wet Dry C H O N S Ash
weight (kg) weight(kg)

Paper 19 16 43.5 6.0 44.0 0.3 0.2 6.0

Plastics 3.7 3.5 60.0 7.2 22.8 - - 10.0
Foodwastes 5.1 1.9 48.0 6.4 37.6 2.6 0.4 5.0
Yard wastes 8.4 2.6 47.8 6.0 38.0 3.4 0.3 4.5
Textiles 1 0.8 55.0 6.6 31.2 4.6 0.15 2.5
Rubber 0.22 0.22 78.0 10.0 - 2.0 - 10.0
Wood 1.3 0.9 49.5 6.0 42.7 0.2 0.1 1.5

Step 2: Determine the percentage distribution of the elements in the sample.

(Example: C = 43.5/100 *16= 6.96, H= 6/100*16= 0.96, O= 44/100*16= 7.04, N=0.3/100*16= 0.048)

Composition (kg)
Wet weight Dry C H O N S Ash
(kg) weight(kg)
Paper 19 16 6.96 0.96 7.04 0.048 0.032 0.96
Plastics 3.7 3.5 2.1 0.252 0.798 0 0 0.35
Foodwastes 5.1 1.9 0.912 0.122 0.714 0.049 0.008 0.095
Yard wastes 8.4 2.6 1.243 0.156 0.988 0.088 0.008 0.117
Textiles 1 0.8 0.44 0.053 0.249 0.036 0.001 0.02
Rubber 0.22 0.22 0.172 0.022 0 0.004 0 0.022
Wood 1.3 0.9 0.446 0.054 0.384 0.002 0.001 0.014
Total 25.92 12.27 1.618 10.174 0.227 0.05 1.578

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 Composition Weight (kg)
C 12.27
H 1.618
O 10.174
N 0.227
S 0.05
Ash 1.578

Step 3: Determine the molar composition of the elements. Ignore the data for ash.

Example: C = 12.27 / 12.01 = 1.022

Composition Weight (kg) Atomic Weight (g/mol) Mole

C 12.27 12.01 1.022
H 1.618 1.01 1.602
O 10.174 16.0 0.636
N 0.227 14.01 0.016
S 0.05 32.07 0.002
Ash 1.578

Step 4: Calculate an approximate chemical formula. Determine normalized mole ratios (sulfur = 1)

Example: C = 1.022 /0.002 = 511, S = 0.002/0.002 = 1

Composition Mole ratio

C 511
H 802
O 318
N 8
S 1.00

Step 5: The chemical formula for the waste mixture given above is C511H802O318N8S

 If with H2O – use wet weight

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 PROXIMATE ANALYSIS

Proximate analysis tests:

 Moisture content, determine by loss of moisture after heating at 105°C for 1 h.

 Volatile combustible matter*, the additional loss of weight after ignition at 950°C for 7 min in a
covered crucible (oxygen is excluded)
 Fixed carbon*, the combustible residue left after volatile matter is removed; ignition at 600 to
900°C
 Ash, the weight of residue after combustion in an open crucible

*prefer as indicator for combustion capability of MSW

Fixed carbon calculation:

% fixed carbon = 100%- %moisture - %ash-%volatile matter

Typical Proximate Analysis of MSW and MSW components (Source: Kiely,G.1997)

Proximate analysis (% by weight)

Waste Type Moisture Volatiles Fixed Carbon Noncombustible(ash)
Food mixed 70.0 21 3.6 5.0
Paper mixed 10.2 76 8.4 5.4
Newspapers 6.0 81 11.5 1.4
Cardboard 5.2 77 12.3 5.0
Plastics mixed 0.2 96 2 2
Polyethylene 0.2 98 <0.1 1.2
Polystyrene 0.2 99 0.7 0.5
PVC 0.2 87 10.8 2.1
Textiles 10 66 17.5 6.5
Yard wastes 60 30 9.5 0.5
Wood mixed 20 68 11.3 0.6
Glass 2 96-99
Metals 2.5 94-99
Domestic MSW 10-40 30-60 3-15 10-30

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Energy value

Heat generated by combustion of material in a calorimeter is determined by measuring the temperature

rise that occurs upon its combustion:

U = Cv ∆T/ M

U – heat value (cal/g) of unknown material, ∆T the rise in temperature (°C), M the mass (g) of unknown
material, Cv the heat capacity (cal/°C)

Example:

A 10 g sample of mixed MSW is combusted in a calorimeter having a heat capacity of 8850 cal/°C. The
temperature increase on combustion is 3.35°C. Calculate the heat value of the sample.

U = Cv ∆T/ M

(8850 x 3.35) / 10.00 = 2965 cal/g = 5278 Btu/lb (British Thermal Unit/pound)

*Paper, plastics, food and yard wastes will provide the highest heat release.

Heat values for the individual waste material is calculated using modified Dulong formula :

MJ/kg = 337C + 1419(H2 – 0.125O2) + 93S +23N

Where C,H2,N,O2,S are given in percent by weight.

Energy content from MSW is calculated using Khan et al.(1991)

E = 0.051[F + 3.6(CP)] 0.352(PLR)

E = energy content MJ/kg. F the percent by weight food in waste, CP the percent cardboard and paper,
PLR the percent plastic and rubber.

Example:

Determine the energy content of the MSW sample

*The chemical formula for the waste mixture given above is C511H802O318N8S

Using Dulong formula:

MJ/kg = 337C + 1419(H2 – 0.125O2) + 93S +23N

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 Composition Mole ratio Atomic Weight Weight contribution of %
(g/mol) each element
C 511 12.01 6137.11 50.4
H 802 1.01 810.02 6.6
O 318 16.0 5088 41.8
N 8 14.01 112.08 0.92
S 1.00 32.07 32.07 0.26
Total 12,179.28

Total energy content , MJ/kg = 337C + 1419(H2 – 0.125O2) + 93S +23N

= 337(50.4) + 1419(6.6-(0.125 x41.8)) +93(0.26) +23(0.92)

= 18981.265 MJ/kg

Estimate the energy content using the Khan equation

Component Percent by Weight

Paper products 37
Plastics 7
Glass 9
Metals 6
Food waste 24
Textiles 2
Misc. 15
Total 100

Total energy, E = 0.051[F + 3.6(CP)] 0.352(PLR)

= 0.051[24+3.6(37)]+0.352(7)

= 10.48MJ/kg

Reaction of combustion: (C6H10O5)n +6nO2  6nCO2 +5nH2O

High heat value, HHV (MJ/kg) 0.339( C) +1.44(H)-0.139(O)+0.105(S)

Low heat value, LHV = HHV (in MJ/kg) -0.0244(W+9H)

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The typical value of inert residue and energy content of residential MSW

Inert residue* (%) Energy content (kJ/kg) Energy content (Btu/lb)

Component Range Range Range
Organic:
Food waste 2-8 3350-6700 1500-3000
Paper 4-8 11200-18000 5000-8000
Cardboard 3-6 13400-16800 6000-7500
Plastics 6-20 26800-35750 12000-16000
Textiles 2-4 14500-17900 6500-8000
Rubber 8-20 20125-26800 9000-12000
Leather 8-20 14500-19000 6500-8500
Yard wastes 2-6 2225-17900 1000-8000
Wood 0.6-2 16770-19000 7500-8500
Misc.organic - - -

Inorganic:
Glass 96-99+ 110-225 50-100
Tin cans 96-99+ 225-1100 100-500
Aluminium 90-99+ - -
Other metal 94-99+ 225-1120 100-500
Dirt, ashes 60-80+ 2230-11175 1000-5000
8950-13400 4000-6000
MSW

 AFTER COMPLETE COMBUSTION

 Source: Tchobanoglous , G et al.(1993)

Btu/lb(dry basis) = Btu/lb(as discarded) ( 100 / 100-%moisture)

On dry ash free basis

Btu/lb (dr ash-free basis) = Btu/lb (as discarded) (100 / 100 - %moisture -%ash)

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Nutrients and others substrates

The organic fraction ( example: food wastes, yard waste, paper products, textiles) can be classified
according to the degree of biodegradability as follows:

 Sugars
 Starches and organic acids
 Proteins and amino acids
 Hemicellulose
 Cellulose and lignocellulose
 Lignin
 Fats, oils, and waxes

Carbohydrates (CH2O)x

The main sources are putrescible garbage and yard wastes.

Elemental analysis of organic materials used as feedstock for Biological Conversion Processes

Component Newspaper Office Paper Yard waste Food waste

K(%) 0.35 0.29 2.27 4.18
Ca(%) 0.01 0.10 0.42 0.43
Mg(%) 0.02 0.04 0.21 0.16
NH4N(mg/kg) 4 61 149 205
NO3N(mg/kg) 4 218 490 4278
SO4S(mg/kg) 159 324 882 855
P(mg/kg) 44 295 3500 4900
B(mg/kg) 14 28 88 17
Zn(mg/kg) 22 177 20 21
Mn(mg/kg) 49 15 56 20
Fe(mg/kg) 57 396 451 48
Cu(mg/kg) 12 14 7.7 6.9
Ni(mg/kg) - - 9.0 4.5
(Source: Tchobanoglous , G et al.(1993))

Homework:

1. Find out the structure of carbohydrate molecule, glucose molecule, cellulose, lignin, protein and
lipid.
2. Find example on how to calculate biodegradability factor.
3. How does total moisture content affect overall management of MSW? Are there environmental
or other implications to high-moisture content waste stream?

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