Assignment - Anaerobic digestion

Part 1. Lab experience

a) Briefly explain the meaning of COD and VS their importance in anaerobic digestion;

The Chemical oxygen demand (COD) is a measurement of the oxygen required to oxidize organic matter
in a liquid sample, in other words, is a measure of the capacity of water to consume oxygen during the
decomposition of organic matter and the oxidation of inorganic chemicals such as ammonia and nitrite [1].
The COD test is frequently used in water treatment plants to monitor the efficiency of the treatment process.

The main test used to determine the amount of COD, is by adding a strong oxidant agent like potassium
dichromate (K2Cr2O7), so it can react with all the organic material in the sample, after oxidize the 95%-
100% of the substance, the sample will change to a green colour and the quantity of COD is calculated by
determining how much oxidizing chemical was consumed during the test.

In the absence of oxygen, an anaerobic digester converts organic materials into biogas as a natural process,
in this process is fundamental to calculate an accurate mass balance based on the chemical oxygen demand
(COD) entering and exiting the system to analyse the digester performance. Furthermore, it is crucial to
measure the COD so the digester achieves maximum performance efficiency and biogas yield [2].

b) Briefly explain how a GC works and which parameters affect the retention time. Report the calibration
curve for the volatile fatty acids (VFAs) measured and calculate the concentration of the VFAs in the
measured sample. Explain how the concentration was calculated;

Gas Chromatography (GC) (Figure 1), is a technique of separation of components of mixtures with the
purpose of obtaining information about their molecular compositions and amounts [3]. The information
obtained after the data analysis, includes a chromatogram of the sample, that is a graph of the detector
output, showing the different compound in the mixture, also information about the heights and the areas of
the separated peaks and their molecular identity.

Figure 1 Block diagram of a chromatograph

The retention time, is the amount of time a compound spends on the column after its injection, if a mixture
has several components, each will spend a different amount of time in the column, depending on its
chemical composition, therefore each one will have a different retention time. There are four important
factors that affects the retention time, and must be considered to produce an accurate GS separation of the
compounds [4].

• Boiling point
 The most important factor which is going to determine what compound will have a shorter retention
time is the boiling point, if it has a low boiling point, probably will spend more time in the gas
phase, so it will spend less time in the column.

• Column temperature
A high temperature will increase the chance of a poor separation in the GS, because the components
will be more easily converted to gas phase, so you have to control the right temperature for better
results as they have to interact in stationary phase.

• Carrier gas flow-rate

A high flow rate reduces the retention times, but also yields a poor separation.

• Column length
A longer column will provide higher retention times and better separation, but if a compound has
too much time in the column the peak width in the graph will increase, and the results won’t be
correct.

Concentration Area IS
Area Butyric acid(pA*min) Ratio (ABut/AIS) Ratio (%) (ABut/AIS)
(mM) (pA*min)
2.5 0.7771 3.1298 0.248290626 24.82906256
5 0.9059 1.9682 0.460268265 46.02682654
7.5 1.1927 1.6619 0.717672543 71.76725435
10 1.2513 1.3461 0.929574326 92.95743258
X 1.2018 1.0262 1.171116741 117.1116741
Table 1 Butyric acid and IS data obtained from GS in different dilutions

Figure 2 Calibration curve

To calculate the concentration x, we have to use the equation obtained from the calibration curve.
 𝑦 = 9.3869𝑥
Where:

x is equal to the concentration of Butyric acid in the unknown sample.

117.1116741
𝑥=
9.3869

𝑥 = 12.4760 𝑚𝑀/𝑙

Then we can calculate the molecular weight of the butyric acid C4H8O2 to find the concentration in g/l.

𝐶4 𝐻6 𝑂8
𝐶 = 12 ∗ 4 = 48
𝐻 =1∗8=8
𝑂 = 16 ∗ 2 = 48
𝑀𝑊 = 88 𝑔/𝑚𝑜𝑙

1 𝑚𝑀 = 1𝑚𝑚𝑜𝑙/𝑙

𝑚𝑚𝑜𝑙 1 𝑚𝑜𝑙 88 𝑔
𝑥 = 12.4760 ∗ ∗
𝑙 1000 𝑚𝑚𝑜𝑙 1 𝑚𝑜𝑙

𝑥 = 1.0978 𝑔/𝑙

c) Briefly explain why controlling pH is important in anaerobic digestion, what is the optimum pH for
methanogenic microorganisms and give examples of reactions occurring in anaerobic digesters that can
reduce the pH.

The pH of the anaerobic digestion process is an important parameter on the digestion process and its biogas
production efficiency. The optimum pH range in an anaerobic digester is 6.8 to 7.2. However, the process
can tolerate a range of 6.5 up to 8.0 [5].

Acetates and fatty acids produced during digestion, tend to lower the pH in the anaerobic digester, here are
some examples of reactions inside the AD that can reduce the PH:

Glycine conversion to acetic acid

𝐶8𝐻=𝑂8 𝑁 + 𝐻8 → 2𝐶𝐻A 𝐶𝑂𝑂𝐻 + 𝑁𝐻A

Alanine conversion to acetic acid

𝐶8𝐻=𝑂8 𝑁 + 2𝐻8𝑂 → 𝐶𝐻A𝐶𝑂𝑂𝐻 + 𝑁𝐻A + 𝐶𝑂8 + 2𝐻8

Glucine conversion to acetic and butyric acid

𝐶=𝐻B 𝑂4 𝑁 + 𝐻8 𝑂 → 𝐶𝐻A 𝐶𝑂𝑂𝐻 + 0.5𝐶𝐻A 𝐶𝐻8 𝐶𝐻8 𝐶𝑂𝑂𝐻 + 𝑁𝐻A + 𝐶𝑂8

Part 2. Anaerobic digestion of food waste

You will have to obtain from the literature (available through scientific journals or online), or estimate
making reasonable assumptions, the following information:

- Amount of food waste produced per year in the UK;

It is estimated that there are around 10 million tonnes of food and drink waste per year, within UK
households, hospitality and food service, food manufacture, retail and wholesale sectors [6].

- Average chemical composition of food waste in terms of moisture, carbohydrates, proteins, fats, etc.;

Chemical composition assuming we have a carbohydrate rich food waste [7].

Proteins %
Food Waste Moisture % Carbohydrates%(w/w) Fats % (w/w)
(w/w)
Carbohydrate
61.3 16.4 6.6 15.1
rich food waste
Table 2 Chemical composition of food waste [7]

- Typical conversion factors into COD of the various chemical components of food waste;

Compound Theoretical formula COD (kg COD/kg Compound)

Carbohydrates 𝐶D 𝐻B.B= 𝑂= 𝑃F.F= 1.191
Proteins 𝐶4 𝐻D.G 𝑂G.8 𝑁 1.439
Fats 𝐶=H 𝐻GF4 𝑂D 1.7
Table 3 COD of the food waste components [8]

- Typical efficiency of COD conversion into methane for food waste;

Typically, is between 70-80% due to two factors, some fractions of the COD may not be biodegradable
for example lignin and a fraction of the COD is inevitably converted to microorganisms, which decrease
the methane yield.

- Typical efficiency of electrical energy generation from methane;

The energy from methane its converted to electricity with an efficiency of 30-50%. The remaining energy
can be converted into heat.

- Typical electrical energy requirements for UK households;

The average electricity consumption was around 3889 KWh in 2016 [9].

- Typical empirical formula of microorganisms.

The typical empirical formula used is C5H7O2N.

2.1 Estimate the electrical energy that can be generated per year by the anaerobic digestion of this
waste.
To begin the solution, we have to find the volatile solids percentage of the total food waste, that is the real
part of the food waste that will produce methane.

• Volatile solids ratio of the food waste is 26.83 %(w/w) [10].

From the investigation, we found that the total food waste in UK per year is 10 million tonnes, now we
have to convert the total food waste to kg, so it can be compatible with the other data.

𝑇𝑜𝑛𝑛𝑒𝑠 1000 𝑘𝑔
𝐹𝑜𝑜𝑑 𝑤𝑎𝑠𝑡𝑒 = P10 000 000 T∗P T
𝑦𝑒𝑎𝑟 1 𝑇𝑜𝑛𝑛𝑒𝑠

𝑘𝑔
𝐹𝑜𝑜𝑑 𝑤𝑎𝑠𝑡𝑒 = 1𝑥10GF
𝑦𝑒𝑎𝑟

To calculate the volatile solids of the food waste, we have to multiply the food waste total by the volatile
solids.

vs = volatile solids.

𝑘𝑔 𝑓𝑜𝑜𝑑 𝑤𝑎𝑠𝑡𝑒 𝑘𝑔 𝑣𝑠 𝑤𝑎𝑠𝑡𝑒

𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑒 𝑠𝑜𝑙𝑖𝑑𝑠 𝑓𝑜𝑜𝑑 𝑤𝑎𝑠𝑡𝑒 = P1𝑥10GF ∗ T ∗ P0.2683 T
𝑦𝑒𝑎𝑟 𝑘𝑔 𝑓𝑜𝑜𝑑 𝑤𝑎𝑠𝑡𝑒

𝑘𝑔 𝑣𝑠 𝑤𝑎𝑠𝑡𝑒
𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑒 𝑠𝑜𝑙𝑖𝑑𝑠 𝑓𝑜𝑜𝑑 𝑤𝑎𝑠𝑡𝑒 = 2.683𝑥10B
𝑦𝑒𝑎𝑟

Now we multiply the values of the volatile solids of the chemical composition (table 1), by the volatile
solids food waste, to calculate the mass of each component in the food waste, and then by the COD of each
(table 3) to calculate the total COD of the compounds, this will help us later to calculate the total energy
produced.

𝐶𝑎𝑟𝑏𝑜ℎ𝑦𝑑𝑟𝑎𝑡𝑒𝑠 𝐶𝑂𝐷
𝑘𝑔 𝑣𝑠 𝑤𝑎𝑠𝑡𝑒 𝑘𝑔 𝑐𝑎𝑟𝑏𝑜ℎ𝑦𝑑𝑟𝑎𝑡𝑒𝑠
= P2.683𝑥10B T ∗ P0.164 T
𝑦𝑒𝑎𝑟 𝑘𝑔 𝑣𝑠 𝑤𝑎𝑠𝑡𝑒
𝑘𝑔 𝐶𝑂𝐷
∗ P1.191 T
𝑘𝑔 𝑐𝑎𝑟𝑏𝑜ℎ𝑦𝑑𝑟𝑎𝑡𝑒𝑠

𝑘𝑔 𝐶𝑂𝐷
𝐶𝑎𝑟𝑏𝑜ℎ𝑦𝑑𝑟𝑎𝑡𝑒𝑠 𝐶𝑂𝐷 = 5.2405𝑥106
𝑦𝑒𝑎𝑟

𝑘𝑔 𝑣𝑠 𝑤𝑎𝑠𝑡𝑒 𝑘𝑔 𝑝𝑟𝑜𝑡𝑒𝑖𝑛𝑠 𝑘𝑔 𝐶𝑂𝐷

𝑃𝑟𝑜𝑡𝑒𝑖𝑛𝑠 𝐶𝑂𝐷 = P2.683𝑥10B T ∗ P0.066 T ∗ P1.439 T
𝑦𝑒𝑎𝑟 𝑘𝑔 𝑣𝑠 𝑤𝑎𝑠𝑡𝑒 𝑘𝑔 𝑝𝑟𝑜𝑡𝑒𝑖𝑛𝑠

𝑘𝑔 𝐶𝑂𝐷
𝑃𝑟𝑜𝑡𝑒𝑖𝑛𝑠 𝐶𝑂𝐷 = 2.5481𝑥106
𝑦𝑒𝑎𝑟

𝑘𝑔 𝑣𝑠 𝑤𝑎𝑠𝑡𝑒 𝑘𝑔 𝑓𝑎𝑡𝑠 𝑘𝑔 𝐶𝑂𝐷

𝐹𝑎𝑡𝑠 𝐶𝑂𝐷 = P2.683𝑥10B T ∗ P0.151 T ∗ P1.7 T
𝑦𝑒𝑎𝑟 𝑘𝑔 𝑣𝑠 𝑤𝑎𝑠𝑡𝑒 𝑘𝑔 𝑓𝑎𝑡𝑠
 𝑘𝑔 𝐶𝑂𝐷
𝐹𝑎𝑡𝑠 𝐶𝑂𝐷 = 6.8872𝑥106
𝑦𝑒𝑎𝑟

Compound COD per year (kg COD/year)

Carbohydrates 5.2405𝑥106
Proteins 2.5481𝑥106
Fats 6.8872𝑥106
Total COD 𝟏𝟒. 𝟔𝟕𝟓𝟖𝒙𝟏𝟎𝟖

Assuming we have 75% of efficiency of COD transformation to methane.

𝑘𝑔 𝐶𝑂𝐷
𝑅𝑒𝑎𝑙 𝐶𝑂𝐷 = (. 75) ∗ P14.6758𝑥106 T
𝑦𝑒𝑎𝑟

𝑘𝑔 𝐶𝑂𝐷
𝑅𝑒𝑎𝑙 𝐶𝑂𝐷 = 11.006𝑥106
𝑦𝑒𝑎𝑟

We know by the lectures that:

• ΔH of CH4 is 890 KJ/mol
• COD of Methane CH4 is 4 kg COD/kg CH4
• Molecular weight of Methane of CH4 is 16 kg CH4/kmol

𝑘𝑔 𝐶𝑂𝐷
11.006𝑥106 𝑦𝑒𝑎𝑟
j 𝑘𝑔 𝐶𝑂𝐷 k
4 𝑘𝑔 𝑚𝑒𝑡ℎ𝑎𝑛𝑒 l
𝑀= 𝑘𝑔 𝑚𝑒𝑡ℎ𝑎𝑛𝑒
P16 𝑘𝑚𝑜𝑙 T

𝐾𝑚𝑜𝑙
𝑀 = 1.7198𝑥10H
𝑦𝑒𝑎𝑟

𝑚𝑜𝑙
𝑀 = 1.7198𝑥10GF
𝑦𝑒𝑎𝑟

Now we can calculate the power.

P = ΔH*M
1KWh = 3600KJ

𝐾𝐽 𝑚𝑜𝑙
𝑃 = P890 T ∗ P1.7198𝑥10GF T
𝑚𝑜𝑙 𝑦𝑒𝑎𝑟
𝐾𝐽
𝑃 = 1.5306𝑥10GA
𝑦𝑒𝑎𝑟
𝐾𝐽 1𝐾𝑊ℎ
𝑃 = P1.5306𝑥10GA T∗P T
𝑦𝑒𝑎𝑟 3600𝐾𝐽
 𝐾𝑊ℎ
𝑃 = 4.2517𝑥10B
𝑦𝑒𝑎𝑟

Assuming the efficiency of the methane to electricity conversion is 40%.

𝐾𝑊ℎ
𝑃 = P4.2517𝑥10B T ∗ (0.40)
𝑦𝑒𝑎𝑟

𝐾𝑊ℎ
𝑃 = 1.7007𝑥10B
𝑦𝑒𝑎𝑟
opq
The total electricity generated by the UK food waste its 1.7007𝑥10B rstu

2.2 Estimate the number of typical UK households that can be powered by the electrical energy
generated by the anaerobic digestion of food waste.

We know that the consumption per household of the UK is 3889 KWh per year, so we can calculate the
number of households dividing the total electricity generated per year it between the consumption per home.

𝐾𝑊ℎ
w1.7007𝑥10B x
𝑦𝑒𝑎𝑟
# ℎ𝑜𝑚𝑒𝑠 =
𝐾𝑊ℎ
w3889 x
𝑦𝑒𝑎𝑟

# ℎ𝑜𝑚𝑒𝑠 = 437312.41 ℎ𝑜𝑢𝑠𝑒𝑠

That means we can power 437313 typical UK households in a year with the electrical energy generated by
the anaerobic digestion using the UK food waste as feedstock.

2.2 Estimate the total mass of microorganisms (typically used as fertiliser) that can be produced from
the anaerobic digestion of this waste.

Assuming 10% of the total COD of the digester is converted to microorganism.

Total digester COD = 14.6758𝑥106
MO = Microorganisms
1 kg MO = 1.42 kg COD
𝑘𝑔 𝐶𝑂𝐷
𝐶𝑂𝐷 𝑀𝑂 = P14.6758𝑥106 T ∗ (. 10)
𝑦𝑒𝑎𝑟

𝑘𝑔 𝐶𝑂𝐷
𝐶𝑂𝐷 𝑀𝑂 = 1.4675𝑥106
𝑦𝑒𝑎𝑟

𝑘𝑔 𝐶𝑂𝐷 1 𝑘𝑔
𝑀𝑂 𝑚𝑎𝑠𝑠 = P1.4675𝑥106 T∗P T
𝑦𝑒𝑎𝑟 1.42 𝑘𝑔 𝐶𝑂𝐷

𝑀𝑂 𝑚𝑎𝑠𝑠 = 1.0335𝑥106 𝑘𝑔
Therefore, the estimate total mass of microorganisms that can be produced from the UK food waste is
1.0335𝑥106 𝑘𝑔

References:

[1] CHEMICAL OXYGEN DEMAND

In-text: (Science.jrank.org, 2017)
Your Bibliography: Science.jrank.org. (2017). Chemical Oxygen Demand. [online] Available at:
http://science.jrank.org/pages/1388/Chemical-Oxygen-Demand.html [Accessed 22 Nov. 2017].

[2] HARNADEK, C. M. W., GUILFORD, N. G. AND EDWARDS, E. A.

Chemical Oxygen Demand Analysis of Anaerobic Digester Contents
In-text: (Harnadek, Guilford and Edwards, 2015)
Your Bibliography: Harnadek, C., Guilford, N. and Edwards, E. (2015). Chemical Oxygen Demand
Analysis of Anaerobic Digester Contents. STEM Fellowship Journal, 1(2), pp.2-5.

[3] POOLE, C.
Gas Chromatography
In-text: (Poole, 2012)
Your Bibliography: Poole, C. (2012). Gas Chromatography. Burlington: Elsevier Science, pp.19-78.

[4] WHAT IS RETENTION TIME? CHROMATOGRAPHY TODAY

In-text: (Chromatographytoday.com, 2017)
Your Bibliography: Chromatographytoday.com. (2017). What is Retention Time? Chromatography Today.
[online] Available at: https://www.chromatographytoday.com/news/gc-mdgc/32/breaking-news/what-is-
retention-time/31159 [Accessed 23 Nov. 2017].

[5] CIOABLA, A., IONEL, I., DUMITREL, G. AND POPESCU, F.

Comparative study on factors affecting anaerobic digestion of agricultural vegetal residues
In-text: (Cioabla et al., 2012)
Your Bibliography: Cioabla, A., Ionel, I., Dumitrel, G. and Popescu, F. (2012). Comparative study on
factors affecting anaerobic digestion of agricultural vegetal residues. Biotechnology for Biofuels, 5(1), p.39.

[6] ESTIMATES OF FOOD SURPLUS AND WASTE ARISINGS IN THE UK

In-text: (Estimates of Food Surplus and Waste Arisings in the UK, 2017)
Your Bibliography: Estimates of Food Surplus and Waste Arisings in the UK. (2017). 1st ed. [ebook] The
Waste and Resources Action Programme (WRAP), pp.3-6. Available at:
http://www.wrap.org.uk/category/materials-and-products/food [Accessed 23 Nov. 2017].

[7] INFLUENCE OF FOOD WASTE COMPOSITION AND VOLUMETRIC WATER DILUTION ON

METHANE GENERATION KINETICS
In-text: (Influence of Food Waste Composition and Volumetric Water Dilution on Methane Generation
Kinetics, 2017)
Your Bibliography: Influence of Food Waste Composition and Volumetric Water Dilution on Methane
Generation Kinetics. (2017). International Journal of Enviromental Protection, 2(9), pp.22-29.
[8] DONOSO-BRAVO, A., PÉREZ-ELVIRA, S., AYMERICH, E. AND FDZ-POLANCO, F.
Assessment of the influence of thermal pre-treatment time on the macromolecular composition and
anaerobic biodegradability of sewage sludge
In-text: (Donoso-Bravo et al., 2011)
Your Bibliography: Donoso-Bravo, A., Pérez-Elvira, S., Aymerich, E. and Fdz-Polanco, F. (2011).
Assessment of the influence of thermal pre-treatment time on the macromolecular composition and
anaerobic biodegradability of sewage sludge. Bioresource Technology, 102(2), pp.660-666.

[9] ENERGY CONSUMPTION IN THE UK

In-text: (ENERGY CONSUMPTION IN THE UK, 2017)
Your Bibliography: ENERGY CONSUMPTION IN THE UK. (2017). 1st ed. [ebook] UK: Department for
Business, Energy & Industrial Strategy, pp.7-8. Available at:
https://www.gov.uk/government/uploads/system/uploads/attachment_data/file/633503/ECUK_2017.pdf
[Accessed 23 Nov. 2017].

[10] VALORISATION OF FOOD WASTE TO BIOGAS

In-text: (Valorisation of food waste to biogas, 2017)
Your Bibliography: Valorisation of food waste to biogas. (2017). [ebook] p.9. Available at:
http://www.valorgas.soton.ac.uk [Accessed 23 Nov. 2017].