Venice 2012

Fourth International Symposium

On Energy From Biomass And Waste
San Servolo,
Venice (Italy)
12-15 November 2012
Use of complex effluent streams as a potential source of
Volatile Fatty acids (VFA)

Dr. Myrto-Panagiota Zacharof

Dr. Robert William Lovitt
Swansea University, Wales
United Kingdom
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Introduction
Low Carbon Research Institute

Swansea University Group

(LCRI) Project H2 Wales

Swansea University Group is
involved in Liquid/Solid Separations

from Complex Effluent Sources

Development of a number of process
to recover useable materials in solid

or liquid form

and chemical

intermediates from waste sources.

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CWATER

Volatile Fatty Acids (VFA)

VFA are fatty acids with a carbon chain of six or fewer carbons
,straight chain and branched.
Also known as carboxylic acids due to the carboxylic group they have.
Also named low molecular weight (LMW) organic acids due to their
small molar mass.
They are of great industrial importance applied in the field of food and
beverages and in the pharmaceutical and chemical fabrication field.
They play a central role in the metabolism of carbon in the environment
especially in acidogenic fermentations

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Industrial and Commercial

Application of VFA
Formic
acid
Antibacterial
agent

Acetic acid

Lactic acid

Butyric acid

Vinyl acetate
monomer
(polymers,
adhensives, dyes)

Anti acne agents

Esters used food

industry as aroma
additive

Tanning
Pharmaceutica

Skin lightning agents

Solvent

Food-Beverage
additive

Pharmaceuticals

Chemical

Animal feed
supplement

Vinegar
Ester production

manufacturing

Food additive,
flavoring

Food additive

Rubber
processing

Moisturizers

Chemicals

Monomer for
biodegradable
polymers

Pesticides

Buffering agent

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Fishing bait
additive

Propionic
acid
Animal and
Human food
additive
Chemical
intermediate
Solvent
Flavouring
agent

Commercial Value of VFA

Carboxylic

Chemical formula

Market

size

Price per tonne

(tonnes/ year)

Acids

(USD, $)

Formic

HCOOH

30.000

800-1200

Acetic

CH3COOH

3.500.000

400-800

Propionic

CH3CH2COOH

180.000

1500-1650

Butyric

CH3 (CH2) 2COOH

30.000

2000-2500

Caproic

CH3 (CH2) 4COOH

25.000

2250-2500

Lactic

CH3CHOHCOOH

120.000

1000-1800

Table 1: Commercial Value of Industrially Important VFA

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Methods of Production of VFA

Carboxylic
Acids

Chemical Synthesis
Methods

Bioprocess

Formic

Oxidation of Alkanes
Hydrogenation of Carbon
dioxide
Methanol carbonylation

Oxidative Fermentation
Anaerobic
Fermentation

Acetic

Methanol Carbonylation
Acetaldehyde Oxidation
Ethylene Oxidation

Oxidative Fermentation
Anaerobic
Fermentation

Propionic

Hydrocarboxylation of
Ethylene
Aerobic oxidation of
Propionaldehyde

Anaerobic
Fermentation

Butyric

Chemical Oxidation of
Butyraldehyde

Fungal Fermentation of
Glucose

Caproic

Ethylene Oxidation

Anaerobic
Fermentation

Lactic

Chemical Synthesis
Fermentation

Anaerobic
Fermentation

Table 2: Methods of Production of Industrially Important VFA

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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 and
anaerobic digestion.

Biological Synthesis of VFA Products

Fermentation, of carbohydrates,
in other words, the breakdown and
re-assembly of biochemicals under
the presence of a microorganisms,
in anaerobic growth conditions

Several waste and non waste

materials can used as substrate,
solid and liquid waste sludge
deriving from agricultural or food
sources
other complex effluent streams
such as municipal or industrial
wastewater.

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Fig 1:Schematic diagram of fermentation

process

Industrial Fermentation Process

Fig 1:Schematic diagram of industrial fermentation process

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The Anaerobic Digestion Waste

Treatment

VFA, H2

Valuable Chemicals
Platform Chemicals,
Plastics

Source: HOLLIGER (2008)

Fig 4:Schematic diagram of AD related processes and

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applications

Anaerobic Digestion, a source of

VFA?
Anaerobic digestion (AD), or
acidogenic fermentation,

Traditional treatment, it can be

performed on various solid or
liquid substrates, such as silage or
manure leading to the production of
biogas, methane CO2 used in
energy generation.

Acidogenesis represents one of the

stages towards methanogenesis.
VFA are the main soluble
compounds generated
VFA could represent a sources of
valuable carbon materials for
chemicals products provided they
can be recovered economically.

Source: SCHUER(2008)

Fig 3:Schematic diagram of AD process

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Other Sources of VFA

VFA though, can also be recovered is aqueous waste discharged from
chemical plants.
Typically contain, at different levels, organic compounds such as
carboxylic acids, alcohols, amines and acetaldehydes.
Aqueous effluents deriving from petrochemical plants and wood pulping
mills have been found containing particularly acetic acid.
Reduced water contamination reduced impact of waste streams
These streams are complex both in chemical composition and in fluid
properties,
being relatively dilute making the cost effective recovery of VFA a
major challenge.

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Advantages and Commercial Benefits of VFA

Recovery
Obvious commercial benefits include

The reduced demand on municipal treatment plants as reduced carbon is

extracted so reducing costs and energy requirements of oxidation and the
release of CO2

The extraction of reduced carbon (as VFA) for reuse and substitution of
acetate and other VFAs derived from petrochemicals so reducing reliance
on fossil carbon for chemicals of favourable nutrients
Chemical based industry becomes uncoupled of fossil carbon and its
increasing cost
Valorisation of waste carbon
Fixation of carbon as chemicals rather that their release as CO2 Reduces
economical and enviromental impact of waste treatment.
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Composition of Complex Effluent Streams

Parameter

Range

Mean

Standard Deviation (2)

pH

6.2-7.1

6.5

0.3

TS (Total Solids) (g L-1)

4.520-12.350

5.600

312

VS ( Volatile solids)( g L-1)

3.616-10.490

4.3680

278

3.960

235

VSS (Volatile Suspended solids)( g 3.220-9.750

L-1)
TOC (Total organic carbon)( g L-1)

1.130-3.110

1.820

254

VFA (Volatile fatty acids)

2-12

0.5

(Ammonia-Nitrogen)( g L-1)

14-47

19

Carbohydrate (%)

31.2-38.7

34

0.5

Protein (g L-1)

25.1-28.2

26

1.2

Lipids (g L-1)

7.6-11.7

0.9

Fibber (g L-1)

20.3-30.7

25

1.5

(g L-1)

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Table 4: Physicochemical composition of coagulated
sludge
(Kim, Simiya, Shin, Kim & Kim, 2005)

Downstream Processing Methods for VFA Recovery

Separation methods

Description

Advantages

Disadvantages

Precipitation

Calcium salts are added in the

medium , to neutralize the acids.
The resulting calcium
carboxylate solutions, can be
concentrated by evaporation, then
crystallized and separated of the
mother liquor
Ammonia is used to neutralize
the acids reacting to form
ammonia carboxylate, which is
then mixed with alcohol to form
esters , to be separated by
distillation
Ion exchange resins used to
exchange to adsorb carboxylate
ions of the feeds

Higher product yields, low

capital costs, products of high
purities

Generating solid wastes as

sulfuric acid is used to release
carboxylic acids from the
calcium carboxylates.

Highly pure products, byproducts

can be used as fertilizer

High energy and capital costs

related to distillation that is used
to separate the alcohol from
carboxylic acids after the formed
esters are hydrolyzed.

Easily operable

Negatively charged carboxylate

ions move through an anion
exchange membrane towards the
anode in the electrodialyzer
through electric current
Organic acids use to extract
carboxylic acids from the stream

Carboxylate is concentrated in
aqueous solution , does not
require acid treatment to adjust
pH

High resin costs, High energy

demand due to resin
regeneration, low adsorption
capacities, separation is not
highly selective
The products have high
impurities , further purification
might be required , difficulties in
scaling up , high energy demand

Distillation

Adsorption

Electrodialysis

Solvent Extraction

Membrane Separations

Higher product yields, suitable

for carboxylate salt production,
lower costs

Use of membrane filters of

High product yields, suitable for
various pore sizes to treat the
a wide range of applications,
mixed effluents for solids
economic , easy to scale up
removal and fractionate the
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The feed needs to be acidified foe

efficient extraction , extractants
needs to be regenerated by
distillation or back extraction.
Membrane fouling , clogging

Membrane Separation
Now well established in the
food and pharma industries
More recently industrial waste
streams , municipal , domestic
and industrial wastewater.

A complete range of membrane

filtration technologies.

Microfiltration (MF)
Ultrafiltration (UF)
Nanofiltration (NF)
Reverse Osmosis (RO)

Employed
to
clarify,
concentrate,
desalt
and
fractionate, components from
waste such as whey and other
substances.

Fig 5:Separation efficiency of membrane

processes
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Membrane Separation Advantages

Several beneficial features lay in membrane processing, including the
ability to recover the acids and concentrate them

Has been applied to many simple (well defined) waste systems

Reuse or more economical disposal of waste
Low pressure operation
Simple scale-up using commercial modules
Ease of in-situ separation of VFA.

The process has shown treatment feasibility for several types of aqueous
waste streams. The main problem that develops is membrane fouling which
needs to be avoided and may requires frequent cleaning of the membrane to
manage the process effectively.

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Membrane Separation of Organic acids

Nanofiltration
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

Fig.6.: Nanofiltration efficiency

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Membrane Separation of Organic acids

Nanofiltration
The surface of the NF membrane
is easy disrupted so care has to
taken in the pre-treatment of the
system to create a robust
separation process
Investigating of these systems now
underway, i.e.
Membrane selection,
separation and optimisation studies
of model solutions,
Filtration pre-treatment studies of
AD sludge using MF
MBR design for in situ VFA
recovery from acidogenic reactors .
Fig.7.:Sterlitech HP4750 stirred cell unit
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Conclusions
VFA are substances of great importance and wide use in the industry
nowadays. Their use expands in almost every field of manufacture and
recovery of chemical substances and products. As though most of them are
currently produced from petrochemical feedstock, serious efforts have been
made to develop alternative, economical methods of production.

Fermentation and Anaerobic digestion of liquid or solid media have have a

great potential.
To meet the challenge of separation, nanofiltration is a pressure driven
separation process, which is easy to implement and relatively costeffective. That can be applied to AD fluids and in situ VFA recovery.

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Questions

Aknowledgments
Dr. Robert William Lovitt

M.Zacharof@swansea.ac.uk

Mr. Michael Gerardo

Dr. Paul Williams
Dr. Darren Oatley

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