Documente Academic
Documente Profesional
Documente Cultură
process
Table of Contents
1.
Introduction..................................................................................................... 3
2.
Membrane processes....................................................................................... 3
3.
Ultrafiltration process...................................................................................... 4
3.1.
3.2.
3.2.1.
Organic membranes.................................................................................. 5
Polyethersulfone................................................................................................. 5
Polyacrylonitrile.................................................................................................. 5
PVDF (Polyvinylidine Flouride)............................................................................5
Polysulfone......................................................................................................... 5
Cellulose acetate................................................................................................ 6
Polypropylene..................................................................................................... 6
Hydrophilic PVDF................................................................................................ 6
Hydrophobic membranes................................................................................... 6
3.2.2.
Inorganic membranes............................................................................... 6
Ceramic membranes.......................................................................................... 6
3.3.
3.3.1.
Dead-end mode........................................................................................ 7
3.3.2.
3.4.
Recovery...................................................................................................... 9
3.5.
Membrane fouling................................................................................................ 10
3.6.
3.6.1.
3.6.2.
3.7.
3.8.
3.8.1.
Tubular membrane.................................................................................. 14
3.8.2.
3.8.3.
3.8.4.
3.9.
3.10.
Membrane Costs..................................................................................... 21
3.11.
Case studies............................................................................................ 23
3.12.
Reference................................................................................................ 26
1. Introduction
Membrane can be described as a thin layer of material that is capable of separating
materials as a function of their physical and chemical properties when a driving force is
applied across the membranes. In membrane separation processes, the feed is separated
into a stream that goes through the membrane, i.e, the permeate and a fraction of feed that
does not go through the membrane, i.e., the retentate or the concentrate.
2. Membrane processes
Membranes processes can be classified into microfiltration, ultrafiltration, ninofiltration and
reverse osmosis. The classification is based on the membrane pore size or the size of
particle that can be retained by the membrane. Generally microfiltration membranes have
pore size range of 0.1 to 3 m, ultrafiltration has a range of 0.01-0.1m, ninofiltration ranges
from 0.001-0.01m and reverse range from 0.0001 to 0.001m. Error: Reference source not
found shows the different membrane processes, pore size and impurities removed by each
process.
3. Ultrafiltration process
3.1. Different membranes material available and application
Ultrafiltration membranes can be made from organic (polymer) and inorganic materials.
Common polymeric materials used in UF include Polysulfone (PS), Polyethersulfone (PES),
Polypropylene (PP), or Polyvinylidenefluoride (PVDF) and inorganic membranes can be
ceramics, glass, or metals.
The
surface chemistry of these materials allow them to be wetted forming a water film on their
surface. Hydrophilic membranes require less operating pressure than hydrophobic
membranes. It has greater resistance to fouling. It is used for general filtration and
mycoplasma removal. The more hydrophilic the membrane surface is, the easier it is for
water to permeate.
Hydrophobic means water-hating and these membrane materials have little or no tendency
to adsorb water. If the membrane surface becomes more and more hydrophobic it will
essentially stop to provide permeate flux and the process will come to a standstill.
POLYETHERSULFANE MEMBRANE
Polyethersulfane membrane is highly hydrophilic. It has absolute removal of bacteria and
viruses. It is tolerant to solvents and resistant to many ethers and aromatics. These
membranes are mostly used in oil, food and permaceutical processes.
POLYACRYLONITRILE MEMBRANES
Polyacrylonitrile membranes are tolerant to many solvents and oils. They are mostly used in
oil/water separation, treatment of grey water, black water, lignin and textile waste water.
POLYVINYLIDINE FLOURIDE (PVDF)
PVDF (Polyvinylidine Flouride) membranes are highly oxidant tolerant and have moderate
pH operating range. They have moderate temperature limits and exhibit good mechanical
strength. It is a best choice for low pressure, high flux application. It has good heat stability
and is chemically resistant. It is suitable for waste water treatment, oil/water separation and
surface water treatment.
POLYSULFONE MEMBRANES
These membranes are mostly used for Post-Treatment of ultrapure water as well as
Removal of suspended solids.
CELLULOSE ACETATE
Cellulose acetate is the original membrane used for UF applications. The material has
number of limitations though with respect to pH and temperature. It is hydrophilic which
make it less fouling. This type of membrane can be eaten by microorganism. Polypropylene
membranes operate at wide pH range (2-14). It is resistant to chemicals and has Good
mechanical strength. It is however not tolerant to oxidants.
Inorganic membrane materials are used for extreme conditions such as high temperature,
high or low ph. It can handle solvents and has a long life expectancy. It however has a high
capital and replacement costs. Inorganic materials include aluminium oxide (Al2O3), Zirconia
(ZrO3, Ceria (CeO2), and Stainless steel.
The direction of feed water flow, in relation to the membrane surface, determines the mode
of filtration in a membrane system. The modes of operation can either be a cross flow or a
dead-end mode. The two modes of operation may experience differences in fouling rate, flux
and recovery, and finished water quality.
In a dead-end filtration system the feed water flows perpendicular to the membrane surface.
All the feed water becomes the permeate. The reject is periodically removed from the
system. In dead end operational mode, solids build up in the system, thus it is suitable for
less fouling applications. shows the flow of water in a dead end mode. The flow can be
expresses as follows:
Qfeed = Qpermeate
Where Q = Flow rate
also be operated on a dead end mode by simply closing the discharge valve. Figure 3 show
the cross flow mode of operation. The flow on a cross flow can be expressed as follow:
Qfeed =Qpermeate + Qconcentrate
Disadvantages
highly susceptible to
Cross Flow
Advantages
Low recovery
fouling
due
to
into
filtered
and
rate
separation
Disadvantages
Relatively
high
operating cost.
water
concentrated
water
Frequent
makes
backwash Continuous
continuous
operation impossible
Simple operation
operation
Treatment
of
concentrated water is
required
Large
complicated unit
and
3.3. Recovery
Recovery is a term that is used to describe the amount of water that is treated versus the
amount of filtrate that is produced. It can be expressed as follows:
Recovery = Qfiltrate/Qfeed.
There is no mode of operation that will give 100% recorvery. Even on dead-end mode there
is water that is used during backwashes and flushes. It end up in the drain and it must be
accounted for.
Membrane fouling
Membrane fouling results in a decrease in flux and an increase in energy consumption and
feed pressure. Fouling will occur in any UF system, regardless of the membrane polymer,
system manufacturer, and mode of operation. Fortunately, fouling can be effectively
controlled through the proper use of pre-treatment processes, chemical additions, and
proper system design and operation.
Membranes fouling typically manifests itself as a decline in permeate flux with time of
operation, and consequently, this is often accompanied by an alteration in membrane
selectivity. These changes often continue throughout the process and eventually require
extensive cleaning or replacement of the membrane. It should be noted that the effect of
membrane fouling on the flux can often be very similar to those associated with
concentration polarization. For this reason, it is first necessary to distinguish between
membrane fouling and concentration polarization, although both are not completely
independent of each other since fouling can result from polarization phenomena.
Flux decline can also be caused by changes in membrane properties as a result of physical
deterioration of the membrane and/or change in feed properties. Severe fouling may also be
caused by seasonal algae bloom in the feed water. Occasional pre-chlorination is necessary
for such cases. There are different types of fouling mechanisms. Viz: inorganic, organic,
biological/microbial and colodial/particulate fouling.
Inorganic fouling
Microbial/biological fouling
Microbial/biological fouling is a result of formation of biofilms on membrane surfaces. Such
films grow and release biopolymers as a result of microbial activity. For example, once
bacteria attach to the membrane, they start to multiply and produce extracellular polymetric
substances (EPS) to form a viscous, slimy, hydrated gel.
Organic Fouling
Several studies have shown that natural organic matter (NOM) is a major culprit in UF
membrane fouling, and that different component of NOM causes different forms of fouling.
UF membrane filtration system control is governed by the fouling tendency of the feed. Trans
membrane Pressure (TMP) and Flux are the parameters used to control the UF systems. A
UF system can be operated at constant Trans-membrane and varying flux, or constant flux
and varying Trans-membrane pressure. It can be operated at ambient temperature, even
though at some occasions it is necessary to operate at considerable low temperature to
prevent the growth of microbiological organisms.
Pressure difference across the membrane is the indication of the extent of fouling. The TMP
is directly proportional to fouling. UF systems can be operated at constant flux. The fouling of
the membrane will be indicated be an increase in trans-membrane pressure. These systems
have a set high TMP limits which when reached the system requires cleaning. These
phenomena can be automated to protect the membranes from irreversible fouling.
Flux is a term used to describe the filtration rate in membrane treatment. It is the rate of flow
per unit area of membrane, measured in litres per meter squared per hour (LMH). It can be
expressed as follows:
Flux=
Q
A
is not achieved after cleaning, it will be an indication of irreversible fouling. Figure 5 show
flux vs time profile for a constant pressure operation.
Membrane manufactures that have full-scale operating MF/UF membrane drinking water
installations includes but not limited to Hydranautics of Oceanside, California, Koch
industries of Wilmington, Delaware, Norit Americas Inc. of Atlanta, Ondeo-Aquasource of
Richmond, Pall Corporation of Port Washington, N.Y, USF Memcor of Sturbridge, Mass,
Zenon Environment of Oakville, Toronto, Dow Water and Process Solutions,Toray
Membranes. Due to the dynamic and complex market for MF/UF membranes and the almost
continuous development bringing new technologies and new suppliers to the drinking water
market, listed here are few membrane manufacturers that are currently supplying MF and
UF membranes.
There are other suppliers who do not manufacture MF/UF membranes, but they design and
supply MF/UF systems for drinking water applications with successful installations. These
includes F.B. Leopold Company of Zelienople, Ionics of Watertown, PCI Division of ITT
Sanitaire of Milford, Ohio, etc
HYDRANAUTICS
Hydranautics has developed and manufactures both spiral wound elements and hollow fiber
modules, including the HYDRAcap low-pressure UF capillary membrane technology. In
1970, hydranautics began providing reverse osmosis (RO) and nanofiltration (NF)
membrane separation technology to the drinking water industry. Acquired by Nitto Denko
Corporation in 1987, Hydranautics established its corporate headquarters in Oceanside,
California.
Hydranautics continuing commitment to research and technology resulted in the ongoing
development and updating of a range of specialized membrane products. The HYDRAcap
UF modules provide more than 5-log removal of pathogens, are fouling resistant, and are
oxidant tolerant. HYDRAcap systems can be configured as stand-alone treatment, single
stage, or with other types of pre-treatment as well.
HYDRAcap
capillary UF
membrane
fiber
composition is
a hydrophilic
modified
polyethersulfone, a material that is resistant to organic fouling and is excellent barrier for
pathogen and colloidal removal. HYDRAcap modules operate in direct flow or cross flow
modes, providing operational flexibility required for variable feed quality. These membranes
can be applied in groundwater, surface water and waste-water treatment. They are made
from hydrophilic polyethersufones (PES). They operate within pH range of 2-13.
KOCH MEMBRANE SYSTEMS INC.
Koch Membrane Systems (KMS) is one of the largest manufacturers of membranes and
membrane products in the world and have over 35 years of experience as a manufacturer of
RO, NF, UF, and MF membranes in hollow fiber, spiral, and tubular configurations. KMS has
complete capabilities in research and development; process, design, and electrical
engineering; and technical service.
KMS is a leader in large-scale membrane filtration in the municipal and industrial water
markets, with a base of more than 6000 UF and MF systems installed around the world in a
number of different applications.
different polymers, porosities, and configurations. KMSs UF hollow fiber product is known in
the municipal market for its clear housing and adapter. This feature provides the capability
for both automated and visual integrity tests.
Systems designed with DOW Ultrafiltration use an outside-in flow configuration which allows
for less plugging, higher solids loading, higher flow area and easy cleaning. The primary flow
design is dead-end filtration but the module can be operated using a concentrate bleed.
Dead-end filtration uses less energy and has a lower operating pressure than the
concentrate bleed, therefore reducing operating costs.
TORAY MEMBRANE
Membrane Technology for reverse osmosis, nanofiltration, ultrafiltration, and spiral wound
membrane elements have been produced since 1967, starting with cellulose acetate
membrane elements. Today, the product line includes a full range of state-of-the-art
polyamide composite membranes.
The range of ultrafiltration elements, both in pressurized and submerged configurations, is
employing a PVDF hollow-fiber, out-in concept and serves in numerous water treatment
units around the world.
Toray's PVDF hollow fiber membrane module effectively removes suspended solids and
microorganisms such as pathogens, when used for various types of water treatment. This
innovative membrane module was developed with polymer science and the membrane
fabrication technologies accumulated in Toray Industries, Inc. for more than 30 years.
The material of Torays Hollow Fiber (HF) Pressurized Ultrafiltration (UF) / Microfiltration
(MF) modules is PVDF (Polyvinylidene fluoride). This best grade HF membrane material
provides high mechanical strength and chemical resistance (oxidation, pH). Two HF
membranes with different nominal pore size are available:
The filtration mode is an Outside in & Dead-End Filtration. This filtration method offers
simple operating control and low energy consumption.
The possibility of the filtration of Ground Water, Surface Water, Sewage Secondary Effluent
and Seawater allows a wide range of different applications.
INGE GmbH
The company Inge GmbH develops innovative ultrafiltration technologies used in the
treatment of drinking water, process water, sea water and waste water. Our systems purify
water by reliably removing bacteria, viruses, particles and suspended solids. inge is
constantly reaffirming its goal of ensuring consistently high quality for both our existing,
satisfied customers and potential future clients.
Inge GmbH was founded in the year 2000 and is headquartered in the town of Greifenberg
near Munich in Bavaria. Its German headquarters houses all the company's main operations
including development, production, marketing and sales. Since August 2011 inge has been
part of BASF, the worlds leading chemical company.
Efficient and effective water treatment generally requires a combination of different methods
and technologies. This combination depends on the intended purpose of the cleaned water
(e.g. drinking water, industrial process water for power plants, etc.) as well as on the quality
and degree of contamination of the original water.
The dizzer modules produced by Inge transform water into clean water. Optimum flow
distribution, top-notch purification efficiency and variable operating modes at low pressure
ensure consistently high quality.
The costs associated with a new membrane treatment facility can be grouped into four
categories i,e Project management and administrative costs, Membrane procurement costs,
Construction costs as well as operational and maintenance costs.
Pilot testing
Environmental assessment
Regulatory permitting
Membrane procurement
Engineering design.
Construction
administration
(services
during
construction
and
construction
management)
Cost for concrete that would be used to construct a membrane treatment basin
Operational costs
Operational costs are those costs that capture the annual expenses associated with the
operation of a membrane treatment facility. These costs include energy (feed/permeate
pumps, backwash pumps, process air, compressed air, cleaning and heating solutions),
chemical(Pre-treatment,
backwashing,
cleaning
in
place),membrane
replacement,
3.10.
Case studies
Case Study 1: (Brazos River Authority, Lake Granbury Surface Water Advanced
Treatment System- Ultrafiltration/ Reverse Osmosis Integrated Membrane System).
The Brazos River Authority (BRA) owns and operates a surface water treatment plant near
Granbury, Texas. The source of water to the Lake Granbury Surface Water Advanced
Treatment System (LGSWATS) plant is from Lake Granbury, characterized by relatively high
concentrations of chlorides and dissolved solids. Further complicating the applicable
advanced treatment technologies is a background concentration of barium in the raw water
of up to 0.15mg/L. Another important consideration is the consideration is the existence of a
high silt density index (SDI).
UF were selected as the unit processes preceding the RO process (pre-treatment) to
sufficiently reduce the barium and SDI in the RO feed. Because of limited experience
throughout the US with this process alternative, pilot testing was performed to confirm the
application and optimize the treatment process prior to design. Pilot plant testing was
conducted during a 2-month period to determine the softening reactions and sludge
production, along with barium removal efficiency.
The softened/settled was fed to two pilot-scale UF units and one MF unit to optimize the flux
rates through the membranes. Filtrate from the MF/UF units fed a two-stage RO pilot system
using thin-film, composite polyamide, spiral-wound membranes. The pilot testing showed
that softening and membranes are not mutually exclusive and in fact, softening can
significantly increase the recovery rate for the membrane process. The pilot testing also
showed that up to 70 percent removal of barium can be achieved through the lime-soda ash
softening process and that the MF/UF units effectively reduced the SDI below 1.5, which is
unacceptable level for RO. The pilot testing also confirmed the levels of antiscalant for the
RO membranes.
At the time of this case study, the UF system completed a 2-day performance test and was
concluding a 30-day acceptance test. During the performance testing, the turbidity of the UF
permeate was continuously recorded below the guarantee of 0.10 NTU, minimum
throughput and recovery requirements were exceeded, and a guaranteed maximum energy
consumption was not exceeded.
The UF/RO integrated membrane system (IMS) is one of the largest drinking water
production facilities in North America to use the lime-soda ash softening and recarbonation
pre-treatment processes upstream of UF and RO. Based on preliminary performance data of
the two systems following start-up, the LGSWATS now provides a reliable source of highquality drinking water for the BRA customers.
There were also concerns regarding the 250 to 300 percent overall increases in demand
during the summer months, surface water influences, and the need to achieve a prolonged
cleaning interval. Pilot tests were performed with the Zenon ZeeWeed 500 immersed UF
process to confirm its performance in comparison to three pressure filtration processes and
for approval by the state. The UF system proved to be the most successful at meeting the
quality goals of 0.03mg/L of manganese and 0.01mg/L of iron and demonstrated the ability
to achieve the highest recovery (>99%). Thus, a new immersed UF facility was constructed
and has been operational since April 2001.
The UF membrane plant is effective in reducing iron and manganese to undetectable levels.
The UF membranes also provide a positive physical barrier to microorganisms. This
characteristic allowed the Seekonk Water district to return to operation two well supplies that
were determined to be under the influence of surface water; one had not been used since
1989 and another had suffered surface water contamination in 1998.
The plant operates at a net flux of 42.44 L/m 2.hr. Cleaning frequency has successfully been
prolonged to 2-3 times per year and consists of a citric acid soak at 350mg/L to control
inorganic fouling and a chlorine soak at 250mg/L to control organic fouling. While the
recovery of the membrane filtration system is 95 percent, the combined recovery including
the reclaim tank is greater than 99 percent. Online particle counters are used for indirect
monitoring of membrane integrity, and a pressure decay test is performed twice per year as
a direct method to test the integrity of the membrane system.
Case Study 3: (Lyonnaise Water, Bernay Water Treatment Plant, Bernay, France)
The plant is designed to produce a maximum of 3.028 mL/day year-round, regardless of
feed water temperature or turbidity. Raw water flow is pumped from the spring to two 16module UF membrane skids, each rated at 1703 LPM per unit. Filtrate from the units flows
by gravity to a clearwell for distribution. Before entering the membrane modules, the spring
water
passes
through
200-micron
prefilter
mounted
at
each
skid
to
retain
macroparticulates that could damage the membranes or cause flux loss. Chlorine is the only
chemical routinely used in the process- for finished water disinfection and as an oxidant in
the membrane backwash.
The UF system is designed to operate in dead-end mode the majority of the time. During
peak turbidity events, the skids automatically switch from dead-end to cross flow
recirculation mode. This increases the velocity of water across the inner surface of the
membrane fibers to control the accumulation of solids, reduce fouling, and allow for
continued filtrate production at rated capacity without excessive increase in transmembrane
pressure (TMP). Instrumentation and automation at the plant is typical for a membrane
facility with all major operating parameters (flows, temperature, and pressures) monitored
along with feed and filtrate turbidity and particle counts.
The UF units have operated for more than 12 years on a continuous basis with little or no
downtime and in 2003 were in the process of being replaced. During this period, the
membrane modules had been cleaned on the average of every 6 to 12 months, primarily
using an alkaline surfactant. The plant was operational year-round during that period with
finished water flows varying from 757 to 2271 LPM, producing consistent finished water
quality.
3.11. Reference
WIESNER, M.R., AND J.-M. LAINE. (1996). Coagulation and membrane separation.
MALLEVIALLE, J., P.E. ODENDAAL, M. R. WIESNER. Water Treatment Membrane
Processes. American Water Works Association Research Foundation.
ZEMAN, L.J. AND A.L. SYDNEY. (1996). Microfiltration and Ultrafiltration: Principles and
Applications, 1st edition. Marcel Dekker Inc., New York
MALLEVIALLE, J., P.E. ODENDAAL, M. R. WIESNER. Water Treatment Membrane
Processes. American Water Works Association Research Foundation.