Addition

of Iron
in ADs
Proposal to test if Ferric/Ferrous chloride is considered a benecial
additive as a strategy for an odor mitigation, not to mention more
efcient digestion under anaerobic conditions.

Quasar energy group

Table of Contents

Contents
Abstract ______________________________________________________ 1
Literature _____________________________________________________ 2
Lab testing proposal ____________________________________________ 6
Economics and Usage ___________________________________________ 8

FeCl2/FeCl3 usage

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NYSERDA Report
states that: For
every 1 mg/l
Sulphur 5 mg/l
iron addition
results in atleast
50% reduction of
H2S.

Abstract
A demand was made recently, to evaluate the usage of FeCl2 (Ferrous chloride)
/FeCl3 (Ferric chloride) in Anaerobic digesters.

The dialogue was started after Alan Johnson, visited Lucas county Anaerobic
digester plant and the dewatering operations had little to no odor emanating
out. After conversation with Lucas county plant official it was informed that
FeCl3/FeCl2 is added to digester.

This document outlines the science, reasoning, and logic behind the usage of
Iron and It will be upto the management to decide whether it is worth
experimenting with Iron chloride. To aid the management some economics of
the process are also explained in the last section.

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Literature
Typically, biogas produced by anaerobic digesters is used to generate energy
for farm use and sale to the power grid. One of the main difficulties associated
with biogas utilization in different form is the presence of relatively high
hydrogen sulfide (H2S) concentrations in the biogas stream. Hydrogen sulfide
present in biogas corrodes engine parts in the combustion chamber, exhaust
system, and in various bearings throughout an engine. The presence of water
vapor in the biogas stream along with hydrogen sulfide exasperates this
problem by producing pure hydrogen, which accelerates cracking and blistering
of steel parts. Furthermore, combustion of biogas with hydrogen sulfide
generates sulfur dioxide which, upon reaction with water droplets, forms
sulfuric acid. Like hydrogen sulfide, sulfuric acid is also highly corrosive to
biogas handling equipment. In general, the operational hydrogen sulfide
concentration limit for most biogas utilization systems is below 800 parts per
million on a volumetric basis (ppmv) in the gas stream.
Hydrogen sulphide (H2S) is also toxic gas/Odor which is dangerous for the
personal of WWTP. When concentration of H2S in biogas produced increases
above 500 ppm risk of respiratory and central nervous system paralysis occurs.
Hydrogen sulphide is also corrosive for the equipment, as quasar has
experienced in past with gas lines getting corroded. Hence H2S should be

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physically or chemically removed from biogas. Removal of hydrogen sulphide

by activated carbon, addition of iron salts or using oxidants is very expensive.
Activated Carbon costs ~$5,000/yd3.
One of the technique for removal of H2S from digester is addition of Fe. Iron
oxide could be directly added to the digesters which will result in efficiency
There are several form of iron that could be used however Fe2+ (In the the
form FeCl2) and Fe3+ (in the form of FeCl3) are most common. The chemical
reaction used to estimate the theoretical iron amount needed is as follows:
FeCl2 + H2S FeS + 2 HCl
FeCl2 + SO4 2- FeSO4 + 2Cl Based on this reaction, 1.63 mg/L of iron (Fe) is needed to react with 1 mg/L of
hydrogen sulfide.
FeCl2 also aids in digestion process. The main end-product of the sludge
anaerobic digestion process is digested sludge. Digested sludge is dark
colored suspension, which usually containing large quantities of gas bubbles. If
sludge has strong smell it means problems in digestion process.

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Following table shows experimental Sulfide and sulfate reduction in AD

digestate after addition of different concentrations of H2S 1.

New York State Energy Research and Development Authority (NYSERDA)

Assessment of Biochemical Process Controls for Reduction of Hydrogen
Sulfide Concentrations in Biogas from Farm Digesters Final Report
February 2012

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Based on following table it can be seen that at 250 mg/l of Fe addition to the
digester approximately >50% of total Sulfide and sulfate reduction is observed.
From An initial conc of 50 PPM of sulfur.
This table could be used as reference for testing this pilot digesters in lab. This
experiment was conducted on dairy manure feedstock, hence actual
concentration required probably might be different on different kind of
feedstocks. However one thing which is noticeable in the plot, is during addition
of little Fe, Sulfide and sulfate reduce steeply before achieving a plateau which
means it became unavailable for further reaction with, and reduction of, H 2S.
Same experimental results could be used for designing lab scale testing.
Depending upon availability of FeCl2 or FeCl3 dosing will be different.

However from the previous tested results, it is clear that Field testing results
showed that for 1 mg/l h2S, 5 mg/L H2S has to be added for ~50% H2S
reduction.

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Lab testing proposal

1. Measure initial Sulfur concentration in the feedstock.
2. Have two parallel digesters, one test and other control.
3. Let initial sulfur concentration be X mg/l.
4. Add Fe concentration which is 5*X= mg/L in the test digester.
5. FeCl3 addition will be higher than FeCl2 because heavier mass due to
presence of additional chlorine.
6. Observe H2S is gas, Ideally H2S should be approximately 50% of
Control reactor H2S.
7. Gather the results.

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Eg. For a lab scale digester of 25 gallon and 25 day retention time, with initial S
conc of 100 mg/l, FeCl2 required will be 0.009lbs/day and FeCl3 required will
be 0.012 Lbs/day. Digestate could be recirculated for dilution of powdered Fe
Powder.
Intial S conc.

100.00 mg/l

Add either of these

FeCl2
FeCl3
0.009 lbs/day
0.012 lbs/day

Digester Vol
Feed Rate

25.00 Gal
1.00 GPD

Feedstock
50.00 mg/l (Gas+Liq)

If this experiment is successful the actual setup could look very similar, with
FeCl2 required/day around 283.607 Lbs/day, and FeCl3 required 362 lbs/day.
Intial S conc.

100.00 mg/l

Add either of these

FeCl2
283.607 lbs/day

FeCl3
362.883 lbs/day

Digester Vol
Feed Rate

750,000.00 Gal
30,000.00 GPD

Feedstock
50.00 mg/l (Gas+Liq)

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Economics and Usage

Usage of this chemical could be controlled by Operator checking feedstock
sulfur content by following graphs.

I) For a typical 30,000 GPD of feeding rate in a digester, using the following
plot based on the concentration of S, Dosing rate of Iron could be established.

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II) Once Dosing rate of Fe is established and depending upon different

chemicals present, (FeCl2 or FeCl3), The dosing rate or feeding rate could be
evaluated also.

Doing this 50% of H2S reduction could be expected.

Pg. 10

FeCl2/FeCl3 usage
III) Assuming it is decided FeCl2, is chosen as chemical for preference, Daily
cost of FeCl2 ($0.3/lb) usage could be evaluated from following table:

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IV) Finally this plot shows estimated cost of Iron Chloride ($/Gallon) of
feedstock based on different Sulphur concentrations. Final H2S
concentration, is expected to be 50% of the initial concentration atleast.

Final comments
Direct addition of ferric chloride and ferrous chloride to anaerobic digesters is
an effective method for reducing the hydrogen sulfide concentration in the
biogas produced from the digesters. Further investigation into minimizing the
effects of iron sinks/binding in the digester bulk liquid matrix, such as enhanced
delivery and digester mixing, offer the potential to further improve performance.
Formation and precipitation of iron sulfides did not result in a measurable
increase in the total solids concentration in the digester, thus there is minimal
potential for digester plugging due to this process.