4th International Conference on Engineering for Waste and Biomass Valorisation

September 10-13, 2012 Porto, Portugal

USE OF COMPLEX EFFLUENT STREAMS AS A POTENTIAL SOURCE OF

VOLATILE FATTY ACIDS

M.P.ZACHAROF *& R.W. LOVITT

College of Engineering, Multidisciplinary Nanotechnology Center, Swansea University, Singleton Park,
Swansea, SA2 8PP, UK*
College of Engineering, Center of Complex Fluids Processing, Multidisciplinary Nanotechnology Center,
Swansea University, Singleton Park, Swansea, SA2 8PP, UK
* Corresponding author: myrtozacharof1981@yahoo.com Tel: +44(0)74135441769
Keywords: volatile fatty acids, wastewater treatment, mixed effluent streams, separation ,anaerobic
digestion, biofermentation

Abstract
The removal of Volatile Fatty Acids (VFA) , from wastewater deriving from numerous sources such as chemical
plants has been an area of research interest for more than a century. With the global petroleum resources facing
scarcity and the constantly rising awareness of the environmental impact the carbon based economy has created ,
research has been focused in developing alternative methods of their production, such as biofermentation. In
biofermentation, the hydrolysis of target solid wastes followed by the microbial conversion of them to biodegradable
organic content results in the production of intermediate organic acids, specifically VFA. VFA are detected at high
concentrations in the effluent streams and mixed liquors of anaerobic membrane reactor systems, because of sudden
variations in hydraulic and organic loading rates. Several studies have shown possible environmental and commercial
benefits using filtration as a source separation process in comparison to integral wastewater treatment. These benefits
include the relief of municipal treatment plants, the use of favourable nutrients and the composition of urine free
wastewater for biotreatment. and insufficient capacity of microfiltration and ultrafiltration systems for their rejection,
mainly due to their low molecular weight. Anaerobic effluents need to be treated with a more advanced treatment
process such as nanofiltration and reverse osmosis.

4th International Conference on Engineering for Waste and Biomass Valorisation

September 10-13, 2012 Porto, Portugal

Introduction
Volatile fatty acids (VFA) such as butyric, acetic, formic and propionic are extensively used in the industry nowadays.
VFA are fatty acids with a carbon chain of six or fewer carbons, C 2 to C 6 straight chain and branched. They are also
,
known as carboxylic acids due to the carboxylic group they have or as low molecular weight (MW) organic acids due
to their small molar mass, commonly applied in the field of food and beverages as acidifiers but also in the
pharmaceutical and chemical fabrication field [1].
Volatile Fatty

Chemical formula

Molecular
Mass

Density

Melting point
point (C)

Boiling point
(C)

pKa

Log Kow

Log D
pH 7.0

Formic

HCOOH

46.03

1.22

8.4

100.8

3.77

-0.54

-3.79

Acetic

CH3COOH

60.05

1.04

16

118

4.79

-0.17

-2.41

Propionic

CH3CH2COOH

74.08

0.99

-21

141

4.87

0.33

1.8

Butyric

CH3(CH2)2COOH

88.11

0.96

-7.9

163

4.82

0.79

1.02

Caproic

CH3(CH2)4COOH

116.6

.93

-34

205

4.88

0.45

3.375

Lactic

CH3CHOHCOOH

90.08

1.20

53

122

3.86

-0.72

-3.76

Acids

Table 1: Volaltile fatty acids chemical Properties

Acetic, propionic and butyric acid are also attracting attention as potential candidates for fabrication of biodegradable
polymers of plastics production [2,3] replacing petrochemical feedstock. Certainly one of the most important VFA
commercially is acetic acid, consumed worldwide, with about one third of its consumption occurring in United States
[4].Global production of acetic acid is approximately 6.5- 7 million tons per year, with the United States demand alone
being 1.9 million tons per year at a price of $600-800 per tonne. Of the global demand of acetic acid,1.5 Ut/A(Unit of
millions of tonne/ Annum) is met by recycling; the remainder is manufactured from petrochemical feedstock,
produced by oxidation of acetaldehyde, the oxidation of liquid phase hydrocarbons or the carbonisation of methanol
[5]or from biological sources [6,7].
With the global petroleum resources facing scarcity and the constantly rising awareness of the environmental impact
the carbon based economy has created, research has been focused in developing alternative methods of their
production, such as biofermentation. Biofermentation, in other words, the breakdown and re-assembly of biochemicals
under the presence of a microorganisms, often in anaerobic growth conditions, can be done on several materials used
as substrate, such solid and liquid waste sludge deriving from agricultural or food sources or other complex effluent
streams such as municipal, agricultural or industrial wastewater [8,9]. VFA though, can also be recovered is aqueous
waste discharged from chemical plants. These, do typically contain, at different levels, organic compounds such as
carboxylic acids, alcohols, amines and acetaldehydes[10,11].
Nevertheless, these streams are quite complicated both in nutrient composition and in fluid properties which constitute
the recovery of VFA a challenge. This, has been addressed using numerous downstream processing methods, based on
the physicochemical characteristics of the substances[12,13]. Liquid-liquid extraction ,[11,14] permeation of the acids
in a hybrid system composed of liquid and anion membranes, adsorption, distillation, membrane separation,

4th International Conference on Engineering for Waste and Biomass Valorisation

September 10-13, 2012 Porto, Portugal

precipitation, solvent extraction [2]and electrodialysis, have been explored for the selective recovery of low molecular
weight organic acids from industrial wastewater streams and fermentated broths[11].

Complex effluent streams as a commercial source of Volatile fatty acids

Biofermentation generates a broth containing a dissociated form of the acid of interest, salts such as sodium,
ammonium or calcium and different impurities such as residual sugars and mineral salts[2]. Numerous sources can be
used as fermentation substrate, such as agricultural and municipal waste, renewable sources such as corn or maze and
silage. Anaerobic digestion (AD), has also been proposed, as it can be performed on various solid or liquid substrates
solid or liquid, such as silage or manure, [16] with acitogenesis represents one of the stages towards the production of
methane, which is mainly used for the production of electricity[17].VFA are the main soluble compounds generated
during the acidogenic fermentation of coagulated sludge [11].Identification of the individual acids formed during the
acid phase fermentation of coagulated raw sludge is of great importance, providing valuable information on the
stability and dynamics of the system . The most abundant component of volatile fatty acids is acetic acid with the
other VFA being produced such as, propionic acid, butyric acid and valeric acid [9].VFA can also be recovered, by
aqueous effluents deriving from petrochemical plants and wood pulping mills containing particularly acetic acid [8].
Industrial Fermentation Complex Effluent Streams
Numerous chemical industries (pharmaceuticals, agrochemicals, food processing, and biofuels) use fermentation
production processes that generate mixed organic and inorganic waste streams. These can often be produced by salt
generating reactions , followed by neutralisation . When operated for maximal productivity per unit reactor volume
typically generates highly concentrated (up to 20% w/v salt) mixed streams. For producing VFA by fermentation,
favourable conditions for the growth and maintenance of a healthy population of acid producing bacteria should be
established in order to reach a steady production rate. It might be possible though for the production rate be relatively
small, partially due to the conversion of soluble VFA to gaseous products [8, 9].
Reuse of the components and conventional biodegradation usually requires separation of organics from the salt as the
great majority of the microorganisms used in biotreatment cannot withstand the osmotic stress at high salt levels. The
current alternatives treatment solutions, for example incineration , is quite more expensive than biodegradation and
the cost of treatment can eventually be undermined the economic viability of the whole process with progressing
tightening of environmental regulations.
Anaerobic Digestion Complex Effluent Streams
Stabilisation of the suspended organic material (sludge) at large wastewater treatment plants is usually carried out by
AD [19,20].Water quality legislation has increased the standards regarding nutrient removal in order to overcome
entrophication problems in receiving waters. During AD organic matter is transformed into methane gas and carbon
dioxide by the action of different groups of bacteria, with main advantages being the reduction in the volume of waste
sludge and the production of methane gas for power generation [19]. In AD, the hydrolysis of target solid wastes
followed by the microbial conversion of them to biodegradable organic content results in the production of
intermediate organic acids, specifically VFA. The VFA are detected at high concentrations in the effluent streams and
mixed liquors of anaerobic membrane reactor systems, because of sudden variations in hydraulic and organic loading

4th International Conference on Engineering for Waste and Biomass Valorisation

September 10-13, 2012 Porto, Portugal

rates. The generation of acetogenesis related products in AD can be influenced greatly by operational parameters such
the hydraulic retention time (HRT)[16,19], which can act selectively encouraging the growth of acid formers and
concurrently suppress the growth of membrane producers [22].Current research has mainly been focused on the
methane-production phase of the process. In consequence, relatively little attention has been paid to the recovery and
reuse of fermentation permeates [9]including the VFA.

Downstream Processing of Volatile fatty acids from Complex Effluent Streams

Product and process waste streams contain small molecular weight components that can be concentrated, desalted or
in some cases fractionated with membrane filtration technology. Membrane filtration as a standalone process can offer
50 to 90% removal of the liquid phase with evaporation can be achieved [18]. Substantial capital and operating cost
benefits together with selective separation can be derived by use of low energy consumption membrane technology as
a complete stand alone process step in or in conjunction with evaporation enabling product recovery and water in
use[24]. The cost of treatment of waste streams containing acetic acid using a commercial activated sludge biological
treatment system is between 4 to 10 cents/ kg depending on the concentration and sludge disposal system[8,23].
Membrane coupled anaerobic digestion processes have been employed in the wastewater treatment field, as a liquidsolid separation tool [25].Most of them have been applied to stabilise the suspended organic materials and to produce
methane [15]. Dairy industry has utilised membrane technology to drive high value products from whey, which was
historically the cheese manufacture waste stream. Today there is a complete range of membrane filtration technologies
covering microfiltration , ultrafiltration and nanofiltration which are employed to clarify, concentrate , desalt and
fractionate , whey component. Microfiltration and ultrafiltration systems have insufficient capacity systems for VFA
rejection, mainly due to their low molecular weight , can though be used as pretreatments for solids removal. Complex
stream effluents need to be treated with a more advanced treatment process such as nanofiltration and reverse osmosis
[26]. Nanofiltration (Figure 1) can be used for the recovery of valuable products while reverse osmosis offers the
recovery of high quality water from the process reuse [24]. Of all pressure-driven membrane processes, nanofiltration
is the best candidate process to deal with the problem as neither reverse osmosis or ultrafilration can separate salts
from relatively small organic molecules. Nanofiltration may have another advantage of exploiting Donnan charges
exclusion as most nanofiltration membranes possess fixed charges.

Figure 1 Priciples of Nanofiltration: where

is the flux of the ion through the membrane , which is independent of x in the steady state, t is time, D is the

diffusivity of the chemical species, c is the concentration of the species, and u is the velocity of the fluid, z is the valence of ionic species, e is the elementary
charge, kB is the Boltzmann constant and T is the temperature. The contribution of volume flux to ion transport is included, since volume flux caused by applied
pressure is not negligible in the calculation of solute flux in nanofiltration [31],[32]

4th International Conference on Engineering for Waste and Biomass Valorisation

September 10-13, 2012 Porto, Portugal

Benefits of Volatile fatty acids Recovery from Complex Effluent streams

The removal of VFA from wastewater deriving from numerous sources such as chemical plants has been an area of
research interest for more than a century [27]. Obvious commercial benefits include, the relief of municipal treatment
plants, the use of favourable nutrients and the composition of urine free wastewater for biotreatment. The VFA could
be either removed from the sludge and reused in the industry, in other words recycled, avoiding the current practice of
sludge is neutralsation, leading to the loss of a valuable source [28].
Treatment of effluent streams containing significant amount of VFA ,to meet current and future water quality
standards has been recognized as alkali metal salts of these compounds are totally soluble in water and insoluble in
hydrocarbon media causing environmental pollution [11]is therefore, important to remove VFA both for pollution
control reasons but also for their use in the industry[29,30].

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