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New technique for validation of UF

membrane processes

Alice Antony and Greg Leslie

Overview
Background
Project outline
Results

Nanoparticles development
UF challenge tests

Conclusions & Future Work

Membrane validation
What is membrane validation?
Process of demonstrating that the system can produce water of the required
microbial quality under defined operating conditions and the system can be
monitored in real time assure the water quality objectives are continuously
met.

How is this performed?


Through challenge test and operational integrity monitoring tests.

What guidance do we have?


1. Membrane filtration guidance manual (MFGM)1
2. Guidelines for validating treatment processes for pathogen reduction
Supporting Class A recycled water schemes in Victoria2

1MFGM,

USEPA, 2005

2Department

of Health, Victorian Government, February 2013

New techniques for real time monitoring of membrane


integrity for virus removal - Project outline

Phase 1 - Review of literature, identification of


knowledge gaps and recommendation of novel
integrity tests (completed in 2009)
Critical Reviews in Environmental Science and Technology 42(9), 2012, 891-933.

Phase 2 Development and testing of novel


integrity test (Completed in 2013)
Journal of Membrane Science 454, 2014, 193-199

Phase 1 outcomes / Phase 2 Objectives


o Challenge test using MS2 bacteriophage, by plaque forming unit
enumeration, PFU is presently considered the best process indicator for
virus removal. However, the MS2 bacteriophage challenge test is difficult in
on a full scale plant on a regular basis1 (for revalidation)

Developing a non-microbial indicator for challenge testing and challenge


testing on ultrafiltration membranes

o Existing integrity test methods are for breaches 1 m; Identifying direct or


indirect integrity testing for detecting breaches less than virus-sized
particles (0.01 0.04 m)is a necessary

Testing size exclusion chromatography and fluorescent spectroscopy for


their sensitivity to detect membrane breaches in UF and RO membranes

1Water

Research, 2002, 36(17): 4227-4234

Ablity to cultivate in high concentration


sensitivity as high as 6LRV
Impractical in full scale high cost and effort
Long turnover time, 24 h
Physicochemical retention vs. inadvertent biological inactivation
Particle aggregation may enhance the filtration capacity
PFU does not provide tools to control denaturation and aggregation
1Journal

Hep A
Norwalk

MS2 as a surrogate1,2,3 Why and Why not?

Rotavirus

Testing with native Viruses (NV)


Low conc. in real scenario
Assay of NV is complex, time consuming, definite analysis
methodology is not available in some cases
Issue of possible contamination

Poliovirus

MS2 challenge testing

of Applied Microbiology , 2007, 103(5): 1632-1638, 2Journal of Membrane Science, 2009, 326(1): 111-116
3Critical Reviews in Environmental Science and Technology, 2012, 42,891-933.

Non-microbial alternative
MS2 Phage

Non-microbial substitute
Citrate stabilized
silver (zerovalent)
nanoparticle

Diameter 24 nm
Icosahedral
Isoelectricpoint (pI) - 3.5-3.9, net
negative change above pH 3.9

Virus sized
Spherically shaped
Negatively charged at pH 7
Stable during filtration

Synthesis of nanoparticles
Silver nitrate solution

Boil
1% sodium
citrate solution
423 nm

Constant stirring for 1 hr)


spherical or roughly
spherical silver
nanoparticles1,2

Centrifuge, redisperse in water


1The
2The

Journal of Physical Chemistry B, 107 (2003) 6269-6275.


Journal of Chemical Physics, 116 (2002) 6755-6759.

Characterisation of Nanoparticles
concentration, size, charge & stability
Concentration of the finished
nanoparticles Inductively
coupled plasma Optical
emission spectroscopy
Size - as average
hydrodynamic size & charge by
a dynamic light scattering,
Brookhaven 90 Plus particle
sizer

Eff. diameter (hydrated) : 50 nm


Charge: -25 mV (negatively charged)
Particle properties stable over 3 days

Characterisation of Nanoparticles
Transmission electron microscopy

Near spherical shape, size ranging from 20 50 nm


Crystal lattice pattern, d-spacing of 0.24 nm, characteristic of zerovalent
silver

Challenge testing
Membrane - PVDF, UF membranes, average pore size - 0.04 m
Effective membrane area - 0.025 m2
Flux - 30 or 50 L m-2 h-1
Feed solution Clean water with 5, 10 & 20 mg L-1 of silver
nanoparticles
Parameters measured and/or compared Clean water flux, TMP
Change in TMP as a function of time, due t fouling of nanoparticles

Challenging compromised membranes with nanoparticles


Physical compromise through punctures and cuts
SEM images
of the
punctures
made with a
100 m
diameter
needle

Chemical damage
o Exposure to hypochlorite solutions (Ct) of 2,500, 5,000, 10,000,
15,000 and 20,000 mg L-1.h
o Equivalent to a total exposure of 3.5, 6.9, 13.9, 20.8 and 27.8
months at 1mg/L concentration over multiple uses

Challenge testing contd.,


LRV and TMP change during the testing of intact UF membrane

Flux,
(L m2 h-1)

Nanoparticle
concentration,
(mg L-1 of Ag)

LRV

30
30
30
50
50
50

5
10
20
5
10
20

2.340.09
2.610.10
2.940.09
2.310.10
2.610.10
2.830.10

-0.3
0.5
0.5
0.0
0.5
0.3

LRV ranging from 2.3 to 2.9 was demonstrated without any impact on the
operating flux
Slightly high LRV could be established with high nanoparticle concentration

Challenge testing contd.,


One puncture,
compromise ratio was
0.00003% and the LRV
decreased from 2.8 to 1.5
Four successive holes, the
LRVs reduced to 1.1, 0.6,
0.5 and 0.3, respectively
After three cuts, rejection
was 7.1 % and LRV <0.1

Challenge testing contd.,


Realistic representation of the
impairment taking place in an
operational plant with routine
use of chemicals
At 2500 and 5000 mg L-1.h, the
membrane resistance (Rm)
decreased to 19 and 38%, but
the rejection capacity was
almost unaffected
Exposure to high concentrations
seem to affect both the
resistance and rejection

Summary MS2 vs silver nanoparticles


Criterion

Microbial indicators, bacteriophages

Analysis, lead
time

Long, 24 h to measure the integrity


breach

Citrate stabilised silver


nanoparticles
Small, using onsite measurement
techniques

Generation

labour intensive, needs PC2

Relatively low labour requirements

Plant
Preparation

High levels of disinfection of sample


points and preventative measures to
avoid contamination

Non-microbial, very little risk of


contamination by outside sources

Safety/hazards

Host bacteria require microbial safety


procedures

Minimal PPE

Background
interference

Potential chances of interference from


background virus and bacteria

Low Ag conc. In background

Measurement
limitations

PFU method may suffer from limitations


due to viral aggregation

No known limitations

Indicator
rigidity

Potential to deform under high pressure


and pass through the membrane

Unlikely to deform under high


pressure

4 Key Conclusions
Demonstrated the suitability of new
citrate stabilised silver nanoparticles as
virus surrogates in terms of shape, size,
rigidity, charge and ease of detection
Demonstrated close to 3 LRV of virus
removal for intact UF membranes
Demonstrated the sensitivity of the
system to differentiate intact membrane
fibres from those with a low number of
physical breaches or chemical
degradation
Demonstrated the potential for the
validation of UF membranes in recycled
water applications

Project is complete..however..
Would like to work
with a water utility to use these particles in
the field
on the recovery of silver nanoparticles

Acknowledgements

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