Anaerobic treatment of crude glycerol from biodiesel production

Nina Kolesárová, Miroslav Hutňan, Viera Špalková

Biodiesel is an ecological alternative of the fuel based on methyl esters of long chain fatty acids (LFCAs) designated for diesel vehicles. Biodiesel is usually produced by the process of trans-esterification of vegetable oils, animal fats or
wastes fats. In Slovak Republic biodiesel is most frequently produced from the rape seed oil with a base catalyst and a methanol. In the process of biodiesel production is formed a heavier separate liquid phase, so called
glycerol phase (g-phase). The portion of the g-phase represents approximately 16 – 18 % of the weight of the input of the oil/fat and its composition is influenced by several factors. It contains 50 – 60 % of the glycerol, 12 – 16 % of the
alkalies especially in the form of alkali soaps and hydroxides, 15 - 18 % of methyl esters, 8 – 12 % of the methanol, 2 –3 % of the water and further components.
Production of biodiesel rapidly increases in the world and so does the production of crude glycerol. Having a high content of organic substabces, this glycerol is a suitable feedstock for anaerobic degradation.
In the work results of crude glycerol treatment in the laboratory mixed reactor and in the laboratory UASB reactors are described. Results from long-term co-digestion of maize silage and crude glycerol in full scale anaerobic reactor at biogas
plant are also discussed.

Mixed laboratory anaerobic reactor with suspended sludge UASB reactor

Selected characteristics of crude glycerol in the laboratory models Scheme of the laboratory UASB
reactor for anaerobic treatment of
crude glycerol
Paramete COD BOD5 Total N Total DIS Densit pH
r P y Crude glycerol was processed in
Measured 1 600 912 000 2 060 720 21 1052 10,4 laboratory UASB reactors with
volume 3,7 litres, which contained
values 000 mg/l mg/l mg/l 300 kg/m3 suspended or granulated biomass.
mg/l mg/l The reactor operated at temperature
Scheme of the laboratory scale model of in mesophilic range (37°C). In this
anaerobic treatment of crude glycerol case the same glycerol as in mixed
with suspended sludge with effective reactor was used.
volume of 4 litres which was operated
under the temperature of 37 °C.

Crude glycerol dosing course during long-

term anaerobic operation of reactor.

The range of doses of g-phase during the

long-term operation varied between 1 ml/l.d
and 5 ml/l.d which correspond to the
volumetric loads from 1,6 kg/m3.d up to
maximal value of 8,0 kg/m3.d.
Crude glycerol dosing and cumulative Crude glycerol dosing and cumulative
production of biogas in UASB reactor with production of biogas in UASB reactor with
suspended biomass. granulated biomass.

Average specific production of biogas was
0,725 l per 1 ml of glycerol, which is quite
high. Despite this fact we state that
inoculation of UASB reactor with suspended
sludge is not very suitable for processing of
the crude glycerol, because the sludge had in
some periods a tendency to flotate.
Maximum organic loading rate achieved
was 6,486 kg/m3.d. Specific production of
biogas increased with ascending dose of
glycerol. Maximum specific production of
biogas was achieved at glycerol dose of 15
ml/d and it reached 0,840 l per 1 ml of
crude glycerol.

Biogas and specific biogas production during

long-term operation of reactor. COD and VFA concentration during long- Crude glycerol in the full scale biogas plant
term operation of reactor.
The average specific biogas production during Selected characteristics of crude glycerol in the biogas plant
the whole anaerobic reactor operation was 906 The sudden increase of COD and VFA
ml per 1 ml of crude glycerol. Methan represented concentration indicated inhibition of Paramete COD BOD5 Total Total P DIS Densit pH
61,1 % of biogas. Increased amounts of specific methanogenic processes in reactor. It was r N y
biogas production can be explained by gradual caused by the increase of dose and after
adaptation of the anaerobic biomass to the given decreasing the dose, processes have Measured 1 870 1 085 1 690 192 5 150 1080 9,03
substrate. impoved again. 000 000
values mg/l mg/l mg/l kg/m3
mg/l mg/l Scheme of the biogas station in Hurbanovo
Crude glycerol was treated in biogas plant
which as the main substrate used maize silage.
For various technical reasons, are processed in
biogas plants also other substrates. Effective
Cofermentation of crude glycerol with maize silage volume of a full scale anaerobic reactor was
Two laboratory models of a volume of 6 litres were fed by maize silage and mixture of maize silage with crude 2450 m3. Reactor was operated at 37 °C.
glycerol and operated under mesophilic conditions. In this case the same glycerol as in mixed reactor was
used. Portion of biogas from crude glycerol
represented 14,82 % of total production, while
During the operation period, no negative influence of supplementation of the feed with crude glycerol was
the portion of the total dry matter added was
observed. Biogas production as well as sludge water quality were similar in both reactors.
11,46 % and portion of the total weight of dosed
raw materials only 5,21 %. Calculated specific
biogas production per 1 kilogram of crude
Maximum portion of g-phase added formed 41,5 % of glycerol was 0,887 m3.
total daily COD dose (together with maize silage).
Specific biogas production achieved was
approximately 0,40 m3/kg COD in the case of both
sole maize silage and a mixture of maize silage with
g-phase, meaning that both the maize silage and g- Dosing of different substrates at
phase had similar specific biogas productions per unit biogas plant
quantity of COD.

Biogas production and

cumulative production of
biogas in reactors

Course of biogas production at

biogas plant

Results
On the basis of long-term operation of the laboratory scale model of anaerobic treatment of crude glycerol the following conclusions can be stated:
• The operation of mesophillic anaerobic degradation of crude glycerol as the only organic substrate is feasible. The process operation is very sensible to organic over-loading of reactor and process operation requires addition of small
amounts of nutrients.
• Crude glycerol represents the material with high content of organic substances that can be easily decomposed with the very high specific biogas production.
• The laboratory anaerobic mixed reactor achieved stable operation at the organic loading rate of 4 kg/m3.d (COD) with ca 980 ml of biogas production per ml of dosed glycerol.
• The laboratory UASB reactor inoculated with granular sludge achieved stable operation at the organic loading rate of 6,5 kg/m3.d with ca 840 ml of biogas production per ml of dosed glycerol.
• Inoculation of the UASB reactor with suspended biomass showed that this type sludge is not suitable for this purpose because of sludge flotation during reactor operation.
• Comparison of long term performance of anaerobic laboratory models processing maize silage and mixture of maize silage and g-phase indicated, that g-phase is a suitable cosubstrate in biogas plants, which has been processing maize
silage as a major feedstock.

Long term processing of crude glycerol in the full scale biogas plant for anaerobic treatment of maize silage showed that crude glycerol is suitable co-substrate. Evaluated specific production of biogas from crude glycerol was about 0,89 m3
per 1 kg of crude glycerol added. Dose of crude glycerol which represents only 5,2 % of overall dose to biogas plant produces almost 15 % of overall biogas production. Use of this co-substrate has significant influence on positive economical
balance of biogas plant.

This work was supported by grant from Norwegian Financial Mechanism, Financial Mechanism of EEA and State Budget of the Slovak Republic (grant SK 0023) and by project VEGA
1/0145/08.