Nitrogen and Sulphur in Biogas Plants

Christina Dornack. TU-Cottbus

CONTACT

Name: Christina Dornack

E-mail: christina.dornack@tu-cottbus.de

EXECUTIVE SUMMARY

Different parameters are used to assess the efficiency of biogas plants. The most common parame-
ters used in practice are VS destruction and COD reduction. Both parameters indicate the mass con-
version of organic matter into biogas. During anaerobic operation more parameters need to be bal-
anced e.g. nitrogen and sulphur. The mass flow balance can be used to assess the quality of the op-
eration process based on sampling and analysis. In principle a quantification of mass transfer pro-
cesses is only feasible with regard to mass flow balances. The anaerobic reactor is considered a
"black box" with following interfaces: sewer gas, inlet and outlet (Svardal, 1991). The validation of
measurements is facilitated by applying closed balances. In the following the balances of different
anaerobic systems will be discussed with respect to the parameters nitrogen and sulphur and conclu-
sions will be given for optimizing the operation of biogas plants.

Keywords: biowaste, anaerobic digestion, mass flow balance, trace substances

INTRODUCTION

S - Sulphur
Sulphur participates in the biochemical implementation processes in the anaerobic environment and
plays a special role in balancing anaerobic processes. A separate balance sheet for sulphur is neces-
sary because the end product - hydrogen sulphide - is toxic.
The input substrate fed into the anaerobic reactor contains sulphur compounds like sulphate sulphur
(SO4-S), organic sulphur, sulphite-sulphur (SO3-S) and sulphide-sulphur. Sulphur is also discharged
via the gas phase.

N-Nitrogen
Nitrogen is required during the anaerobic process for building up biomass. In addition, nitrogen in
the form of ammonia and ammonium, has a significant influence on the alkalinity and thus on the
pH value. A review of the implementation processes of the nitrogen is only possible as open bal-
ance. The components nitrogen and ammonia which are contained in the biogas cannot be deter-
mined.

The relevant nitrogen compounds (organic nitrogen and ammonium) are determined by TKN (Total
Nitrogen Kjeldahl). The TKN corresponds to the concentration of total reduced nitrogen. In high
concentrations the ammonium nitrogen can be toxic for the anaerobic degradation process. This
may be adjusted depending on the temperature and the pH caused by a high concentration of the
undissociated component - the ammonia. In general, the nitrogen, which comes as ammonia into the
gas phase, is less than 1%.
MATERIAL AND METHODS

View on the Parameter Nitrogen

Effect of Nitrogen Concentration on the pH

The pH in the anaerobic reactor is calculated as the result of the buffer effect of NH3 / NH4+ and
HCO3- / CO2. It results mainly from the reaction of alkaline or acid reactive metabolites and the
available buffer systems, of which the CO2-HCO3- buffer system is crucial. Carbon dioxide dis-
solves in water to unstable carbonic acid, which decomposes to bicarbonate and H+ (BRAUN,
1987).

The CO2 concentration and pH depend on the reactor height. In the following discussion, the pH-
value for NH4+-N-concentration of 2 g/l in the reactor is calculated (Figure 1). The pH value in-
creases with the temperature.

pH value, when NH4+-N = 2 g/l; CO2=30%

7,6
7,5
7,4
pH

7,3
7,2
7,1
7
0 5 10 15 20
dephts in reactor [m]

Figure 1 pH-value depending on the height of the fermenter in mesophilic and thermophilic operation under
otherwise similar conditions (modified by DORNACK, 2001)

The Ratio Between Ammonium and Ammonia

The ammonia is an end product resulting from the digestion process itself. In a specific concentra-
tion it can be inhibitory or toxic.

In literature it is controversially discussed, which nitrogen concentration inhibits the anaerobic deg-
radation process. After a long adaptation phase, the microorganisms are capable to digest with
much higher concentrations than in the example of RÜCKAUF et al. (1992) where a concentration
of 200 mg/l NH3-N existed (Angelidaki et al, 1993).

The NH4+-N - NH3-N - balance of the liquid phase shifts with increasing pH in favour of the am-
monia (Figure 2). Due to rising temperatures and therefore consequently the rise in pH, inhibition
effects occur more quickly at high temperatures and high pH values.
 100
35°C 55°C
80

NH3-N proportion
60
thermophilic
mesophilic
40

20

0
4 5 6 7 8 9 10 11 12
pH - value

Figure 2 NH3 – proportion in NH4+-N as a function of temperature and pH

Own studies showed the following behaviour of the non-adapted process: The TR-content in the
reactor was less than 1% at the start of the investigation. The substrate had a solid content of 5-8%.
With a solid content of 2% in the reactor, the content of organic acids increased and the biogas pro-
duction decreased significantly (Figure 3).
800 8000
700 7000
Gas yield [lN/kgTSin];

Gas yield [lN/kgTSin]

organic acids [mg/l]

600 6000
NH3-N [mg/l]

500 5000
organic acids [mg/l]
400 4000
300 3000
200 2000
100 1000
NH3-N [mg/l]
0 0
8 13 18 23 28 33 38
TS in reactor [g/kg]

Figure 3 Acid concentration and biogas yield as a function of the TR-growing in the reactor at the non-adapted
process (DORNACK, 2001)

The increase of the organic acids content did not lead to a reduction of the pH value. As the pH-
value depends on the buffer system NH3 / NH4+ and HCO3- / CO2, the increase of the organic acids
concentration had no effect on the pH-value. Increased ammonium concentrations over 1500 mg / l
inhibit the conversion of propionic acid to acetic acid. Ammonia acts as an inhibitor for the for-
mation of methane from H2 and CO2. The reduction of hydrogen consumption leads to an inhibition
of the degradation of propionic acid. An accumulation of propionic acid bacteria inhibits the bacte-
ria, that degrade acetic acid for the methane production and has even a toxic effect on the methane
formation from H2 and CO2.

Due to the adaptation of microorganisms, high ammonium concentrations in the substrate are un-
problematic during the digestion process. The limits of tolerable ammonium concentrations are be-
tween 0.7 g/l and 10 g/l depending on the nature of microorganisms. In adapted cultures an inhibi-
tion was only observed for values of more than 30 g/l at relatively low pH level (including
EDELMANN, 2001 ; Zacchaeus, 1995; MELTING, 2000, Angelidaki and Ahring, 1994).
The Parameter Sulphur

Inhibition Process
Substrates, that contain sulphur, produce H2S during the anaerobic process. This leads to the inhibi-
tion of the process, because H2S acts toxic on methane bacteria and uses up the hydrogen that is
needed by the methane bacteria.

For methane formation, two groups of microorganisms are responsible: the acetogenic and meth-
anogenic bacteria. The first group forms hydrogen and acetic acid, which are consumed by the se-
cond group for methane formation. The conversion of acetic acid by acetogenic bacteria is only
possible if the resulting hydrogen is continuously removed by methane bacteria.

These two groups of bacteria live in symbiosis. But if sulphate-reducing bacteria are present in the
process, the balance is disturbed as molecular hydrogen is also required for sulphate reduction. In
addition, the sulphate reducing bacteria need acetate for producing new cell substance (Brummack,
Polster, 2006).

This results in a competition mainly regarding the available molecular hydrogen. The acetate is
used by the sulphate reducing bacteria only for cell construction and not for methane production.

Odour Problems and Potential Risks for Staff

Even in low concentrations sulphide is extremely toxic to most organisms because it inhibits en-
zymes of the aerobic respiratory chain (BORKENSTEIN, 2006). Table 1 shows the harmful effects
of H2S in dependence of the concentration. The threshold of odour of H2S is between 0.002 and
0.15 ppm, depending on the personal sensitivity. Occupational safety guidelines specify a maximum
allowable concentration (MAK) of 10 ppm. First serious damage to health occurs at a concentration
of 20 ppm.

Table 1 Harmful effects of H2S to humans (BORKEN STEIN, 2006)

H 2 S [ppm] Effect
0.002 to 0.15 Odour threshold
3-5 Distinct odour
10 Maximum allowable concentration (MAK value)
20 Visual disturbances
50-100 Serious damage to eyes
50-250 Loss of smell
300-500 Serious damage to the respiratory tract
500 - 1000 Danger

Reduction of Durability of Combined Heat and Power and Exclusion of Alternative Use of Biogas
During the fermentation of sulphur containing compounds, a significant proportion of hydrogen
sulphide is formed in the reactor. During combustion the toxic sulphur dioxide (SO2) develops. Ad-
ditionally, H2S and SO2 contribute to the corrosion of valves and engine components and lead to an
accelerated acidification of the engine oil.

Balance in Anaerobic Systems

On base of the balance sheet the quality of the plant operation concerning sampling and analysis
were assessed. With help of selected examples the balance sheets of the biogas processes - in labor-
atory and technical scale - will be shown.
TKN-Balance of a Biogas Plant
The balance sheet of TKN of the biogas plant Plauen / Zobes is shown. It is a co-fermentation plant.
The substrates used are chicken manure with organic waste from separate collection, brewery
waste, including fat separator ferments.

The balance sheet was developed over a time of one year on the input and output of TKN (Figure
5). TKN in the anaerobic environment is mainly composed of organically bound nitrogen (4.5% -
share in VS) and of ammonium-nitrogen. The ratio in the digester was about 2.3:1 (NH4+-N - org.
N). Because the presence of other nitrogen compounds could be excluded, the input of TKN has to
be found in the output in that period. The proportion of degassed ammonia (about 3% of ammonium
are ammonia at T = 35 °C and pH = 7.5) was disregarded.

The effluent concentration from reactor 3 was obtained by measurements. The feed load of TKN
consisted of the load by the concentration of TKN of the incoming substrate minus the trash. The
difference between this flow and the yearly flow rate at 12 days hydraulic retention time could be
looked at circulation water.
BIOGAS
TKN  0

ASSUMPTION
MANURE: Q = 4607.5 M³/A
TKN = 8,6 KG/M³
TKN = 39,4 T/A
RESIDUES: Q = 13.212,5 M³/A
TKN = 9.0 KG/M³
TKN = 119.2 T/A
OUTPUT
Anaerobic Reac- TKN = 5.94 KG/M³
tor TKN = 158.6 T/A
BALANCE TKN Q = 26.025 M³/A
359 DAYS
QCIRCLE = 13465 M³/A

SUM: TKN = 158.6 T/A

SLUDGE
TKN = 3.9 T/A
Figure 5 TKN balance sheet of the biogas plant Plauen / Zobes

The TKN balance sheet shows the pathways of nitrogen in the system of the biogas plant. The water
cycle has kept approximately 80 tonnes of nitrogen in the system. The circulating water is used for
homogenisation and liquefaction of the organic waste. It was detected that about 67% of the nitro-
gen load of input substrate (with the biowaste) come from the water recirculation.

Knowledge of these mechanisms is especially important if a change in the operation, for example,
the thermophilic operation is to be modelled and implemented. Under thermophilic conditions, the
equilibrium between NH4+-N and NH3 shifts towards a NH3 surplus (see Figure 5)which can reach
toxic concentrations for the microorganisms.

THE BIOLOGICAL STAGE OF AN MBT ON THE SULPHUR

The balance sheet of the biological stage of an MBT plant bases on extensive measurements. This
system was not presented as a black box like the other two balance sheets. Samples were taken from
several places in the system.
The aim of the investigations was the detection of sulphur sources and discharges in the system.
Household waste, industrial waste and bulky waste are processed in the MBT plant. These fractions
have different sulphur potentials. For the biological treatment the household waste and industrial
waste that is similar to household waste are interesting, because only these fractions contain the
organic fraction which is used for fermentation.

In all the organic fractions of residual waste, sulphur is found in the form of salt and sulphur amino
acids. Organic sulphur is estimated at a percentage of about 0.25 m.-% (Weigand and Marber
(2005). The sulphur output of the plant occurs at the following stages:

Minerals Output from the Sand Trap, Mainly as Sulphate - Sulphur

 Dried digestate as sulphate sulphur

 Biogas as hydrogen sulphide
 Exhaust air from hydrolysis as hydrogen sulphide
 Concentrate from reverse osmosis as sulphate - sulphur

For the balance sheet, both the solid and the liquid samples were analyzed regarding the following
parameters: total Sulphur, sulphate sulphur, organic sulphur and pyrite sulphur.

As an example, solid analyses are shown in Figure 6:

solid analyses
sulphurconcentration [g/kg]

50
total sulphur
40
organic sulphur Pyrite
30 Sulphate-sulphur
20
10
0
Hydrolysis
Pulper
Output Digester

Aeration tank
organics before the

Sand

Digester 1

Digester 2
pulper

position of sampling

Figure 6 Sulphur sources and sinks and the sampling points

The concentrations of sulphur in the input are subject to strong fluctuations. The data shown in Fig-
ure 6 provide that the values for: organics before the pulper, effluent of the pulper, sand and hydrol-
ysis are only snapshots, from which no conclusions can be drawn regarding the sulphur input into
the system.

The highest concentrations of total sulphur were measured in the solids of the decanters, in the pro-
cess water and in the concentrate of the reverse osmosis. Like the reverse osmosis the solid residue
of the decanter is ejected from the system. The process water, however, is used for the mashing of
the substrate before the pulper and contributes significantly to the sulphur concentration in the sys-
tem.
Looking at the data from the measurements of fluid samples (Figure 8) there is to be seen that the
sulphate concentrations in the aeration tank, in the liquid phase of the effluent of the decanter and in
the process water in the pulper were very high. The concentrate of the reverse osmosis is a sink and
can therefore only be considered concerning the calculation of circulation water. During the aerobic
stage sulphur compounds are oxidised to sulphate. The sulphate is lead back into the process via the
process water.

fluid analyses
sulphurconcentration [mg/kg]

8000

6000

4000

2000

0
Hydrolysis

Circulation
Pulper

Concentrate
Decanter
Aeration
Digester 1

Digester 2

tank

reverse
water
position of sampling

Figure 8 Sulphate concentrations in the fluid samples

Based on the data obtained, a sulphur balance sheet (Figure 9) of the whole plant was carried out
under the following conditions:

 12 m% Separation of contraries in the sand trap, of which 8% screenings and 4% heavy ma-
terials,
 55 m-% Water
 28 m-% Solid waste
 15 m-% Biogas

The balance sheet was done regarding the hourly rate resulting from operations diaries of the plant.

 2.6 Mg / h biological input

 12 m3 of water from the process water

To simplify the calculation the process water density was estimated being 1 Mg/m3. Every hour
2600 kg of the organic fraction is homogenised with about 12000 kg of process water in the pulper.
Because the flow rate of the reverse osmosis could not be calculated, it was determined by an itera-
tive approach. The indicated amounts of sulphur in the balance sheet were removed from the re-
verse osmosis system.

On the basis of the presented balance sheet, sulphur sources in the biological system and sulphur
sinks can be detected. In this example, the sulphur loads resulting from the circulation water are
very high and amounts about 60% of the total sulphur load in the biological system of the MBT
plant. For example, if the sulphur output of the reverse osmosis increases to 20%, the sulphur load
from the circulation water can be decreased by more than 6% or 2.2 kg / h. Another way of reduc-
ing the sulphur load in the system is the reduction in the hydrolysis. The hydrolysis was considered
as "black box" because of missing data.
 Input

26.99 kg Plastics and others

36.81 kg
2.16 kg
Grit chamber

61.26 kg
Inert material bunker
Hydrolyses
0.38 kg

59.06

Biogas Digester
0.48 kg 58.58 kg

Aeration basin

58.58 kg

Centrifuge Digestate buffer

38.09 kg 20.49 kg
Circulation water Concentrate reverse osmosis

1.27 kg
Figure 9 Sulphur balance per hour in the MBT plant on the basis of samples analyzed

CONCLUSIONS

Using two examples of material flow analysis, the possibilities and problems of balancing (TKN)
can be identified. In a material flow analysis, which was based on the sulphur flows in the MBT,
just mass flows can be identified. The material flow analysis allows a review of the capability of
measurements of plants on to be converted into plant-related material balances.

For this reason, sources and discharges of substances are determinable. Based on this approach,
optimization measurements can be identified and developed.

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