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[1]

Recovery of volatile fatty acids (VFA) from complex waste effluents


using membranes
M.-P. Zacharof*a,b , R.W. Lovitt*a,b
a

Centre for Complex Fluid Processing (CCFP), College of Engineering, Swansea University, Talbot building, Swansea, SA2 8PP, UK
(myrtozacharof1981@yahoo.com, r.w.lovitt@swansea.ac.uk)

Centre for Water Advanced Technologies and Environmental Research (CWATER), College of Engineering, Talbot building, Swansea
University, Swansea, SA2 8PP, UK (myrtozacharof1981@yahoo.com, r.w.lovitt@swansea.ac.uk)

Abstract:
Waste effluents from anaerobic digesters of agricultural waste were treated with a range of membranes including
microfiltration and nanofiltration to concentrate volatile fatty acids. Microfiltration was applied successfully to produce
sterile, particle free solutions with a VFA concentration of 21.08 mM of acetic acid and 15.81 mM of butyric acid. These,
were further treated using a variety of nanofiltration membranes (NF270, (Dow Chemicals, USA), HL, DL, DK, (Osmonics
, USA), LF10 (Nitto Denko, Japan) achieving retention ratios, up to 75% giving retentates up to 53.94 mM acetate and
28.38 mM butyrate. DK and NF270 membranes were identified as the best candidates for VFA separation and concentration
from these multicomponent effluents, both in terms of retention and permeate flux. When the effluents are adjusted to alkali
conditions highest productivity, retention and flux was achieved at pH 7 at higher pH there was a significant reduction in
flux.
Keywords: acetic acid; butyric acid; effluents;nanofiltration; volatile fatty acids; retention

INTRODUCTION
Volatile fatty acids (VFA) have important uses, as chemical intermediates and are central to the organic
carbon cycling on the planet (Zacharof & Lovitt, 2013). Most of the environmental organic carbon is
metabolised through VFA intermediates either to carbon dioxide (CO2) and methane (CH4)
anaerobically, or CO2 and water in oxidative systems (Rittman & McCarty, 2001). Either way, these
acids, especially acetic, are key intracellular and extracellular metabolic intermediates. Consequently, if
carbon could be recovered in the form of VFA, this could represent an alternative, sustainable source of
carbon based chemicals for industrial use, as these can be generated and recovered from organic
degradation processes, such as fermentation and anaerobic digestion. Furthermore, these acids can be
used as a substrate for a number of interesting biotransformations for sustainable production of
chemicals (Popken et al. 2000).
The extensive industrial development of petroleum based fuels and chemicals has significantly
contributed in environmental pollution and climate change, as well as to intensive use of non-renewable
natural resources. Driven by a low carbon economy, dedicated to reduce carbon emissions and develop
sustainable process for manufacturing and production of chemicals, processes such as anaerobic
digestion (AD) and fermentation, represent a feasible, sustainable carbon neutral method of production
of acids. AD and fermentation process can be carried on several materials used as substrates, deriving
of various different sources including waste (Masse et al. 2008, Masse et al., 2010).
The use of these streams has multiple benefits, including avoiding the consumption of potentially
important food carbohydrates as feedstock, 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 (Zacharof & Lovitt, 2012). The chemical based industry
becomes uncoupled of fossil carbon and its increasing cost as the fixation for carbon as chemicals
rather than their release as CO2 consequently reduces the economical and environmental impact of
waste treatment and valorisation of waste carbon (Zacharof & Lovitt, 2013).

[2]

The separation of organics acids from digested or fermented effluents or the discharged waste streams
of these processes is not a straightforward process considering the complex physicochemical nature of
these streams and the concentration of the acids in them. Often these effluents demand extensive pretreatment to make further processing workable (Masse et al., 2008)
Within this context, membrane filtration can offer a feasible option towards a cost effective
fractionation and recovery of VFA. Nowadays, there is a complete range of membrane filtration
technologies covering microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse
osmosis (RO) which are employed to clarify, fractionate , desalt and concentrate salts and organics
(Bellona et al., 2004). The low molecular mass and the chemical properties of the VFA (Bouchoux et
al., 2005, Choi et al., 2008), makes NF represents an attractive choice. NF employs numerous
mechanisms of separation including size (molecular weight), electrical interactions (Donnan effect) and
dependence of pressure (Pronk et al., 2006) while RO can be used to concentrate these valuable
substances.
A diverse range of NF membranes made of different materials, are commercially available. These are
in several membrane arrangements, possessing different pore size, membrane charge; permeability and
productivity in terms of permeate flux and retention of substances. Therefore selecting a suitable
membrane for waste effluent filtration and recovery of acids is not a straightforward process (Han &
Cheryan, 1995). The complex nature of effluents, in terms of viscosity, solids content, and chemistry
can influence the electrical charge of the membrane surface. The choice of the appropriate NF
membrane is therefore an engineering challenge. This can be addressed by testing the membranes
suitability for the selected process at first instance in bench scale.
Consequently, this paper reports on the investigation of the performance of five NF membranes on
enrichment and concentration of VFA, namely acetic and butyric acids from pretreated complex waste
effluents (agricultural sludge) (Figure 1).These were tested using characterising solutions and treated
digested agricultural sludge to select the most appropriate membrane that would have simultaneously
high permeate flux and acids retention (filtration productivity). The waste effluents were pretreated by
dilution, sedimentation and sieving for the removal of large particulate material such as straw or stones.
Further removal of these particulates and formulation of a sterile effluent suitable to be further
processed using NF, was achieved using MF. The microfiltered effluent was then nanofiltered. The
influence of pH on the separation of VFA was then investigated and the efficiency of NF and as a
separation and concentration method was evaluated in terms of VFA retention and permeates flux.
MATERIALS AND METHODS
Materials
Waste Effluents
Effluent streams samples from anaerobically digested cattle slurry were used. The digester effluents
were collected from Farm Renewable Environmental Energy Limited (FRE), Wrexham, Wales, United
Kingdom. 25 litre samples were taken from the output line of the sedimentation tank, prior to filtration.
Effluents Pre-Treatment Schemes
The effluent was rich in solids, mostly comprising of coarse particles i.e. straw and other large
particles. A pre-treatment scheme was developed to remove these, combining dilution with tap water
(50% v/v), thorough manual mixing for one hour using a rod, twenty-four hour sedimentation in a
settling tank and treatment of the supernatant with a series of coarse filters varying in pore size between
1.045 mm to 0.5 mm.

[3]

Methods
Microfiltration of agricultural sludge
The pre-treated effluent was then processed through a cross-flow microfiltration unit, employing a
Membralox ceramic filter element (-Al2O3) -with 19 channels of 3.70 mm diameter each and length of
1016 mm- monolith microfiltration (pore size 0.2m, effective membrane area 0.22m) membrane, able
to withstand a pH range between 0 to14, fitted in stainless steel module, commercially available from
Pall (Portsmouth, UK). The filtration unit consisted of a 100 L stainless steel vessel linked via 5 m of 1
inch stainless steel piping arranged in two fluid loops each powered by a centrifugal pumps. A detailed
description of the unit can be found elsewhere (Gerardo et al., 2013). The membrane was characterised
using tap water.
Analysis of dry matter content and physicochemical characteristics
Total solids (TS, g/L) and total suspended solids (TSS, g/L), were determined according to standard
methods for the examination of water and wastewater published by APHA, AWWA and WPCF 20th
Edition, 1998. Particle size distribution (PSD) of sludge samples was determined by light scattering
technique using Mastersizer 2000 (Malvern, UK), the zeta potential was determined by the Zetasizer
(Malvern, UK), the conductivity and salinity of the samples were measured used a conductivity meter
(Russell systems) calibrated with a standard solution of 0.1M of KCl. Acetic and butyric acid were
analysed using head space gas chromatography, VARIAN ProsStar GC-3800 (USA) fitted with flame
ionization detector (FID) , connected with a hydrogen generator (UHP-20H NITROX, Swan Hunter,
UK), with air supplied and helium used as a carrier gas, equipped with a Nukol, fused silica highquality coated polymide capillary column 15 m x 0.32 mm I.D., 0.25 m column, using the following
protocol, of a total holding time of 15 minutes, a gas flow rate of 30ml/min and a pressure of 10 psi and an
FID temperature of 220 C as described by Sigma-Aldrich GC Supelko-Nukol columns manual.
Nanofiltration agricultural sludge and synthetic solutions
The membranes used in this study are described in Table 1 with details provided by the manufacturers.
A bench membrane apparatus (stainless steel stirred cell unit, Sterlitech HP4750, Kent, WA, USA) was
used for the filtration of the solutions operated batchwise using high pressure nitrogen gas (Figure 2).
The system was comprised of a stirred cell unit of 200 ml maximum process volume, a magnetic stirrer
and a membrane filter with an effective area of 14.6 cm. Each membrane was characterised under a
range of different pressure conditions varying between 0 to 2000 kPa, using sterilised distilled water
(Millipore RiOs) and 10mM phosphate buffer (KH2PO4) (pH 6.5) (Sigma-Aldrich, UK). Permeate flux
was determined over a range of pressures. During the experimental trials with characterising solutions
and waste effluents, the cell unit was pressurized by compressed nitrogen up to 1500 kPa the stirrer
speed was set at 300 rpm. The samples were filtered each time using a virgin membrane sample,
minimizing fouling and avoiding problems associated with cleaning and reusing of the membranes.
The permeate was collected in a graduated vessel (100 ml) placed on an electronic scale (Santorious
PLS303, UK), connected to a personal computer equipped with logging software. This was used to
obtain the permeate flow rate over time progress. At the end of each experimental process, the
dissembled components of the unit cell system were placed into an ethanol solution (50% v/v) for 24
hours to achieve effective cleaning and sterilisation. Prior to each experiment, the membranes (Table 1)
were rinsed with distilled water and sterilised with 25% v/v ethanol solution. pH adjustment of the
filtered solutions was achieved by 1M NaOH or HCl solutions. The samples, were filtered to give 10
ml retentate and 90 ml permeate deriving from the same batch of microfiltration processing.

[4]

Determination of Permeate Flux


The permeate flux (J, L/m2 h) was defined experimentally for each membrane is calculated according
the following formula
dV

Qf

dt
J
=
=
permeate A A
m m

where Qf is the volumetric flow fate, Am is the membrane area (m2) , V is the volume feed (L) and t is
time (h) (Marcel , 1996).
Determination of Retention
The retention percentage (R%) of acetic and butyric acid by each membrane is calculated according the
following formula

where Cp,i is the observed concentration (mM) of the acid in the permeate and Cr,i is the observed
concentration (mM) of the acid in retentate (Van der Bruggen et al. 1999).
RESULTS AND DISCUSSION
Pretreament and microfiltration of agricultural sludge
The agricultural waste digester effluent was found to contain a significant amount of acetic and butyric
acid (Table 2) however, being rich in solid particulates, it was pre-treated using dilution and
sedimentation described above. The pretreatment enhanced the removal of the larger solids in the
sludge (<100 m) and facilitate their filterability through the ceramic crossflow microfilter, reducing
the total solids content by 20.75% (from 15.13 g/L to 11.99 g/L), while the mean particle size dropped
by 48.58%, (from 27.17 m to 13.97 m). Significant reduction was observed in the TSS content by
58.75%, (from 612.50 mg/L to 252.60 mg/L) thus the pretreated fluid could be easily processed.
However, the amount of VFA was reduced as these are loosely bound to the solids contained in the
effluents (Kimura et al., 2009). In an effort to formulate an effluent that would contain a significant
amount of VFA, which could be further separated using NF, the effluent was mechanically treated
using MF. The amount of VFA was found almost as high as in the untreated sludge in the resulting
permeate (Table 2), suggesting that MF successfully separated the organics contained in the feed.
The effective pretreatment allowed high membrane productivity is terms of permeate flux determined
as 134.28 L/m2 h and a cross-flow velocity of 2.05 m/s. This flux rate permitted the operation of the
system at low pressures (TMP 5 to 20 psi), for long periods of time (8 to 14 h) without interruptions
contributed to irreversible membrane fouling or for cleaning. This was due to the use of a ceramic
membrane and the cross flow filtration of arrangement, that allowed good circulatory flow over the
system, reducing the levels of permeable compressible cake formed, hence maintaining membrane
permeate the flux.

[5]

Nanofiltration of characterising solutions and pretreated agricultural waste effluents


The driving force in NF separation is the pressure difference across the membrane, causing a liquid flux
through the membrane. In first instance, the mechanism governing the separation function of this process,
can be explained as follows, molecules having sizes larger than the pore size of membranes cannot
permeate through the membrane and are consequently rejected or retained, while smaller solutes can
permeate through the membranes. Prior to the use of the selected NF membranes, for separation and
partial concentration of the acids from the agricultural sludge, they were tested for membrane permeability
using distilled water and phosphate buffer (10mM, pH 6.5) solution, in an effort to analyze the behavior of
the membranes when incorporated in the stirred cell unit. For all membranes, flux values increased linearly
with increasing pressure.1500 kPa where selected as the operating pressure for the experimental trials
achieving high flux (Table 3). Each membrane though gave different flux values for the characterizing
solutions (deionised water and phosphate buffer), with highest flux being achieved by HL and smallest by
LF10. For all the membranes, highest flux was achieved with deionised water than phosphate buffer,
suggesting that the use of ions might enhance the negative electrical charge on the membrane surface,
consequently reducing the flux (Mandale & Jones, 2008).
Several studies have investigated the separation of acids from mixtures using NF, mainly from
synthetic binary and tertiary solutions of hexoses, salts and acids (Bouchoux et al. 2005) or fermented
broths (Gonzalez et al. 2008), while limited research has been conducted on anaerobic digestates (Kim
et al. 2005). Digested waste effluents are expected to provide a significant amount of VFA, in this case
being 21.08 mM of acetic acid and 15.81 mM butyric acid have been identified.
The pretreated microfiltered effluents (pH 8.25) were filtered using all the five membranes at 1500 kPa
pressure. Highest flux is found in DK membrane (Table 3), while the permeate flux was significantly
lower when compared with the flux achieved during the behaviour characterisation of the membranes
(Table 3). This phenomenon can be attributed to the sludge content of insoluble particulates (Table 2),
colour and negative charge. The alkali pH of the effluents enhanced the electronegativity of the
membrane surface as well as possibly influencing the charge of the acids.
Retentate solutions were enriched showing higher concentration than the starting solutions suggesting
that the membranes do successfully reject the acids. The retention of acids varies between 24.40% to
72.23% (Table 4), with HL having the smallest retention, while highest retention for acetic acid is
achieved with LF10 and for butyric acid with NF270. Among the five membranes, promising results
are achieved with NF270, DK and LF10; however LF10 offers significantly small flux, consisting its
use, ineffective and uneconomical due to the high energy demand to maintain the high pressure
necessary for processing the effluents.
Effect of pH on retention of organic acids
Previous researches have highlighted the possibility of enhancing the retention process by altering the pH
of the solutions (Gonzalez et al. 2008). This, can be explained by the importance of electrical interactions
in NF, that have a strong effect in the membranes surface charge, influencing the retention of acetic and
butyric acids in the solutions (Van der Bruggen, 2002). Taking advantage of these mechanisms the
pretreated agricultural waste effluents pH was adjusted to investigate the influence of pH on flux and acids
retention. Considering the fact that the membrane surface charge is negative charged, enhancing the
negative charge of the acids could possibly enhance their retention on the membrane consequently
separating them effectively from the complex solutions.
For all the membranes, the flux becomes smaller (Table 5) when the pH of the solutions is increased to
alkali (7 and above) implying an existing relationship between flux of the solution and the electrical

[6]

interactions between the solutes (Figure 3), with LF10 is being the tightest membrane, offering the
smallest flux regardless the pH conditions and could be correlated with higher retention of acids
achieved for both acids when the pH is adjusted above 7.0. (Figure 4 a, b).
Figure 2, shows the effect of pH on the retention of acetate and butyrate using the five different
membranes. As the pH becomes more alkali, the retention of the acids is increasing. For both acids in
all the membranes, at pH 7 and above retention becomes strongly positive varying between 13.36 to
72.23% for acetic acid (Figure 4 a) and 27.67 to 71.36% for butyric acid (Figure 4 b). The varying
positive retention ratios between each membrane when the same conditions are used can be possibly
attributed to the different characteristics each membrane acquires in terms of pore size and material of
fabrication. The variations in the retention can be attributed due to differences in molecular weight as
well as to the different chemical properties of each acid for example its disassociation constant. Several
researchers (Manttari et al. 2004, Manttari& Nystrom, 2006) have correlated the disassociation ability
of each acid with its electrical charge in this case becoming highly negative consequently being
repelled by the negatively charged membrane and consequently being better retained (Han & Cheryan,
1995). Taking into account that the concentration of the acids in the solutions might be a decisive factor
on the separation behaviour of the membranes (Bellona et al. 2004), if the concentration of the acids in
the feed is higher possibly the retention of the acids would be higher, if the same alkaline treatment
during filtration is applied.
Although size exclusion was definitely a determining factor on the separation behaviour of the
membranes, retention of organic molecules is not only caused by steric interactions but also by
electrostatic effects including convective transport through the membrane and by adsorption on the
membrane surface and diffusive transport through the membrane matrix. For charged components an
electrostatic interaction takes place between the molecules, described by the Donnan effect, known also
as Donnan exclusion mechanism (van der Bruggen et al., 1999)
These phenomena could be of interest in the biotechnological production of VFA, since commonly, the
acids occur in a relatively dilute mixture of salts, proteins and carbohydrates (Danner & Braun 1999,
Bouchoux et al. 2005, Gonzalez et al. 2008). If a concentrating and separating treatment step can be
applied for example UF, acids can be successfully separated from the salts and concentrated in a semipurified form with an important reduction in cost.
Interestingly, the phenomenon of negative retention is observed in acidic pH (4.0, 5.5) for butyric acid,
for DL membrane. Negative retention is a phenomenon often occurring in nanofiltration especially
when solutions containing salts are filtered such as brines (Mandale & Jones, 2008). In such a system, a
strongly negatively charged solute is better repelled from negatively charged membrane; those divalent
ions will be better retained than monovalent ions. Possibly this phenomenon is occurring in this system
with acetic acid being strongly charged.
DK and NF270 membranes were identified as the best candidates for VFA separation and
concentration from these multicomponent effluents, especially when the effluent are adjusted in alkali
conditions achieving high productivity, both in terms of retention and flux. Although LF10 offered high
retention results for both acids, the very low flux rate consist this membrane unattractive for use as a
separation step, however it can be used as a concentration step (Figure 4).
Conclusions
This study investigates spent digester fluids and developing a recovery strategy solely devoted on the
recovery of VFA from anaerobic digestates, might not be as easy as from an acidogenic digester where
the VFA concentration will be substantially higher, up to 100 mM.

[7]

In the current use of anaerobic digestion in the industry, considering the fact that the acids are used as
intermediates to produce methane consequently therefore their concentration might not be as high as if
they were produced biotechnologically, their recovery could be combined with the caption of other
useful platforms chemicals such as ammonia and phosphate (Zacharof& Lovitt 2012, Gerardo et al.
2013) is also possible. It has been pointed out that farming waste effluents do represent an
environmental hazard as well as a good source virtually in abundance of useful nutrients and metals.
Developing a complete recovery strategy for these substances, with a waste treatment system placed in
situ could be of great benefit for the industry.
NF can be used as a method of isolation and recovery of VFA from complex effluent streams, provided
a pretreatment scheme that will remove coarse particles, so the effluents can be easily filtered. Alkali
conditions enhance the isolation and retention of VFA, with DK and NF270 representing the best
option among the five membranes tested. These findings show potential and could be applied to the
biotechnological production of VFA and their recovery.

Pretreatment and microfiltration of digester effluents consist the digester effluents able to be
processed through nanofiltration membranes and recover VFA
The use of alkali treatment, especially at points of 8.5 and 9.0 of the digester effluents during
nanofiltration enhanced the retention of the VFA for all the 5 membranes,
Among the membranes tested, LF10 had the highest retention results for acetate and butyrate
with of 72.23% and 69.74%, respectively at pH 8.5, followed by NF270 of a 57.23% and
69.74% and DK of a 57.23% and 45.18%.
NF270 and DK have a flux rate of 15.40 and 16.49 L/m2h at pH 8.5 while LF10 has a flux rate
of 6.40 L/m2h, being unsuitable for separation of VFA at this stage. LF10 could be possibly
used to further concentrate VFA after these have been successfully separated by NF270 and
DK.

Acknowledgements
This project was supported by Low Carbon Research Institute (LCRI) project grant title Wales H2
Cymru. The authors would like to thank Dr. Paul M. Williams and Dr. Stephen J. Mandale for their
excellent advice during the experimental trials of this project.
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during NF/RO treatment-a literature review Water Res. 38, 2795-809.
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solutions: Variations of retention between single- & mixed-solute solutions. J.Mem. Sci. 258, 123-32.
Choi J.-H., Fukushi K. & Yamamoto K. 2008 A study on the removal of organic acids from
wastewaters using nanofiltration membranes Sep. Purif. Tech. 59, 17-25
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from anaerobically digested dairy farm sludge using cross-flow microfiltration. Water Res.
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fermentation broths & artificial solutions by nanofiltration. Desal. 228, 84-96.

[8]

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membranes. Water Res. 43, 3751-8.
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volatile fatty acids from liquid organic sludge, Desal, 172, 119-127.
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219, 262-71.
Manttari M. & Nystrom M. 2006 Negative retention of organic compounds in nanofiltration. Desal.
199, 41-2.
Manttari M., Pekuri T. & Nystrom M. 2004 NF270, a new membrane having promising characteristics
& being suitable for treatment of dilute effluents from the paper industry. J. Mem. Sci. 242, 107-16.
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reverse osmosis membranes. J.Mem. Sci. 325, 914-9.
Masse L., Masse D. I., Pellerin Y. & Dubreuil J. 2010 Osmotic pressure & substrate resistance during
the concentration of manure nutrients by reverse osmosis membranes J.Mem.Sci. 348, 28-33.
Popken T., Gotze L. & Gmehling J. 2000 Reaction kinetics & chemical equilibrium of homogeneously
& heterogeneously catalyzed acetic acid esterification with methanol & methyl acetate hydrolysis.
Indust. Eng. Chem. Res. 39, 2601-11.
Pronk W., Palmquist H., Biebow M. & Boller M. 2006 Nanofiltration for the separation of
pharmaceuticals from nutrients in source-separated urine. Water Res. 40, 1405-12.
Rittmann B. E. & McCarty P. L. 2001 Environmental Biotechnology, Principles & Applications.
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Van der Bruggen B., Braeken L. & Van de Casteele C. 2002a Evaluation of parameters describing flux
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Van der Bruggen B., Schaep J., Wilms D. & Van de Casteele C. 1999 Influence of molecular size,
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[9]

Table 1: Membranes characteristics provided by the manufacturers

Characteristics
Manufacturer
Model
Distributors
Material

Applications
Geometry
Effective Membrane area (cm2)
Flux rate (L/m2h) @689 kPa
Charge (at neutral pH)
pH
Ion rejection (%)
MWCO
Maximum Operating
Temperature (C)

Membranes
General Electric Dow FilmTech USA
Nitto Denko Japan
Osmonics USA
HL
DL DK
NF 270
LF10
Sterlitech Corporation
Desal Supplies
SOMICON AG WKL
http://www.sterlitech.com
http://www.desal.co.uk http://www.somicon.com
Thin film composite
Thin film compositeThin film composite
piperazine based
Aromatic polyamide
Polyvinyl alcoholpolyamide microporous
aromatic cross linked
polysulfone
polyamides
Water Softening, Acid Purification, Detergent removal, Heavy metal removal
Flat Sheet
Flat Sheet
Flat Sheet
14.60
14.60
14.60
66.3 52.7
37.4
122.0
11.9
Negative
2-10
2-11
3-10
2-10
98
96
98
97
99.5
150-300
150-200
<150
50
45
40

[10]

Table 2: The effect of pretreatement and microfiltration on the physical characteristics and chemical composition
of the anaerobically digested agricultural sludge. The collected samples were diluted 100 times with deionised water
and measured in a 1 cm light path

Parameters

Total Solids (TS, g/L)


Total Suspended Solids
(TSS, mg/L)
Conductivity (mS/cm)
Zeta Potential (mV)
Sizing (m)
Optical Density (580nm1)
Concentration
Acetic Acid
Butyric Acid

Agricultural Sludge
Untreated
Sludge

Treated
Sludge

Microfiltered
(0.2m)Sludge
Retentate

Microfiltered
(0.2m)Sludge
Permeate

15.13
612.50

11.99
252.60

10.40
258.00

5.15
190.00

9.37
-33.25
27.17
0.86
mg/L
1650.17
1781.58

9.11
-30.06
13.97
0.34
mg/L
1464.02
1666.16

9.01
-29.60
13.49
0.27
mg/L
1083.30
1163.93

8.3
-24.2
4.93
0.10
mg/L
1265.85
1393.02

mmols/L

27.48
19.22

mmols/L
24.38
18.91

mmols/L
18.04
13.21

mmols/L
21.08
15.81

[11]

Table 3:The influence of membrane type on permeate flux of deionised water, phosphate buffer solution and
standardised anaerobically digested fluid using a variety of nanofiltration membranes at 1500 kPa operating
pressure.

Permeate Flux (L/m2h)


Solutions
pH
Membranes

DK
DL
HL
NF270
LF10

Deionised
Water

Dihydrogen Orthophosphate
Solution (10mM)

7.2
69.61
84.04
121.43
61.66
15.95

6.5
27.54
34.43
82.97
20.21
06.78

Microfiltered
(0.2m) Sludge
Permeate
8.25
16.49
14.91
14.37
15.40
06.00

[12]

Table 4: The effect of membrane type on acetate and butyrate from standardised permeate derived from
microfiltered digested agricultural sludge (see Table 2) at 1500 kPa. Initial concentration in the feed (pH 8.25) is
21.10 mM and 15.81 mM of acetic and butyric acid respectively.

Membranes

Acids
Acetic Acid

DK
DL
HL
NF270
LF10

Permeate
Concentration
(mM)
17.27
14.25
20.09
14.00
14.98

Butyric Acid
Retentate
Concentration
(mM)
40.38
26.49
26.57
29.56
53.94

Retention
(%)
57.23
46.22
24.40
52.64
72.23

Permeate
Concentration
(mM)
10.86
13.61
8.58
8.03
10.74

Retentate
Concentration
(mM)
19.81
20.76
14.28
26.54
28.38

Retention
(%)
45.18
34.44
39.92
69.74
62.16

[13]

Table 5: The effect of pH on permeate flux of standardised anaerobically digested fluids using a variety of
nanofiltration membranes. The filtration fluids were derived from microfiltered sludge (see Table 2)

Permeate Flux (L/m2h)


Microfiltered (0.2m) Sludge Permeate

Solution
pH
Membranes

4.0

5.5

7.0

8.5

9.0

DK

21.48

21.42

17.64

16.49

02.09

DL
HL
NF270
LF10

18.33
25.48
21.70
12.09

17.92
22.55
20.75
13.35

16.78
20.04
19.05
05.44

14.91
14.37
15.40
06.00

05.06
11.42
03.04
04.14

[14]

Figure 1:Processing scheme for the recovery of VFA from pretreated complex waste effluents (agricultural sludge)

[15]

Figure 1: Schematic representation of the high pressure stirred cell unit [1] nitrogen cylinder, [2] pressure regulator valve, [3] pressure indicator, [4] stirred
cell unit equipped with membrane disc, [5] magnetic stirrer [6], stirring plate [7], permeate collection vessel [8] electronic scale,, [9] personal computer

[16]

Figure 3: Nanofiltration using a variety of membranes of permeates derived from microfiltration of agricultural sludge (see Table 2)

[17]

Figure 4 [a, b]:The effect of pH on VFA retention (a) acetic acid (b) butyric acid of a variety of NF membranes using standardised anaerobically digested
fluids. The filtered fluids are permeates derived from microfiltration of agricultural sludge (see Table 2)

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