Tubular Membrane- Maintenance and Cleaning

1) Need for maintenance:

The RO feed water may contain various concentrations of suspended solids
and dissolved matter. Suspended solids may consist of the following:
- Inorganic particles.
- Colloids.
- Biological matter, which includes microorganisms and algae.
On the other hand, Dissolved matter may consist of highly soluble salts, such as
chlorides, and sparingly soluble salts, such as carbonates, sulfates, and silica.

2) Effects of membrane fouling:

Reduction in the feed water volume during the using of membrane results in
increase of the concentration of suspended particles and dissolved ions. Settling
of the suspended particles or scale formation from the sparingly soluble salts
would result in the following:
- Blocking of the flow channels that would increase the pressure drop in the
feed channels in the membrane module. This would require increasing the
pumping power, which is limited by the original design value that takes into
account clean operation in addition to some finite level of blockage.
- Reducing the permeation rate across the membrane and increase in the
amount of salt passage through the membrane. This is caused by scale
formation on the membrane surface.

3) Membrane Cleaning:
Membrane cleaning is dictated by increase in pressure drop, decrease in
permeate recovery, and decrease in salt rejection. It should be stressed that
normalized data should be used to correct for temperature effects on system
performance. In addition, identification of foulants as well as analysis of feed and
outlet water are important factors in determining the proper cleaning solution.
 The following is a summary of cleaning methods of various fouling and scaling
compounds.
Calcium Carbonate and Metal Oxides Scale: Clean with low pH water. The
water pH is adjusted to 3-4 and sulfuric, hydrochloric, or citric acids are used.
Calcium Sulfate Scale: Clean with a solution that include sodium tripoly
phosphate or sodium salt of ethylene diamine tetra acetic acid.
Silica: Detergents and hydraulic cleaning.
Organics and biofouling: similar solution to calcium sulfate cleaning. In
addition, use of detergents and biocides are recommended.
Animation video: https://youtu.be/ua-W5VVbzvo

4) Membrane Cleaning procedure:

Generally, low pH solutions are used to clean metallic scales while alkaline
solutions are used to clean biological and organic fouling. Relatively high flow
with low pressure is recommended. System cleaning follows the following basic
steps:
- Preparation of the cleaning solution and adjustment of temperature and pH.
- Displacement of the solution in RO modules by pumping the cleaning solution.
- Recycling and soaking of the element. Soaking time may vary from few hours
to overnight depending on the fouling level.
Flushing the unit with RO permeate water. The flushing procedure continues
until foaming disappears and the pH and conductivity of the effluent solution
approach those of the feed water.
Other features of the cleaning process include the following:
- Use of chlorine or other strong oxidants on polyamide membranes can cause
irreversible damage to the membrane.
- Warm water at a temperature of 32 ^C to 37 ^C gives better cleaning results
than lower temperature solutions.
- If the pH of an acid solution increases during recirculation, add more acid to
return the pH back to the target value. This is because of acid consumption in
dissolving inorganic scale.
 - Use of sulfuric acid in low pH solutions may result in forming sulfate scale.
- Permeate water is preferred for mixing cleaning solutions.
- Use of filtered tap water for high pH solutions can result in carbonate fouling
if the water is hard.
Animation Video: https://youtu.be/nqHmW0PawCg
5) Membrane Sterilization:

Membrane sterilization is necessary if the system is shut down for period of more than 2 days.
Sterilization compounds include the following:

- Hydrogen peroxide (0.25 wt %).

- Sodium bisulfite/glycerin (0.2 to 1 wt %/16 to 20 wt %).
- Sodium bisulfite (0.5 to 1 wt %).
- Formaldehyde (0.25 to 1 wt%).
- Copper sulfate (0.1 to 0.5 ppm)
Procedure for membrane sterilization includes: preparation of the
sterilizing solution, initial flushing with RO permeate water, circulation of the
sterilizing solution, drainage, and tight closure during the storage period. Placing
a sterilized unit back into operation requires flushing permeate water. Similar chemical
treatment of membrane has been mentioned in [ CITATION Mur07 \l 1033 ]

6) Cleaning System Specifications:

The tubular membrane cleaning system is formed of a tank, 5 jam cartridge filter,
pumping unit, and instrumentation. Fig. 1. Cleaning solution is pumped from the tank
through the cartridge filter to the RO array. Solution is then recycled back to the tank.
The volume of solution should be sufficient to fill the volume of the vessels, filters and
piping. Instrumentation includes pH, temperature, flow rate, pressure, and level
controllers.[ CITATION Iga10 \l 1033 ]
Choice of the construction material for the cleaning system includes the following: -
Tank: Fiberglass reinforced plastic or polypropylene. Tank should have a removable
cover. - Piping: PVC schedule 80 or Nylon reinforced flex hose. - Valves: Stainless Steel.
- Pump: Stainless Steel or Non-metallic composite polyesters. Pump should be
 centrifugal type. Material selection should be made to withstand extremes in pH,
temperatures up to (45 oC), and electrical sources/switches should be protected and well
grounded. Recent advances video: https://youtu.be/yg7HSs2sFgY

Fig 1: Membrane Cleaning process

Recent Advances in the field of Tubular Membrane:

1) Applications of tubular silicone membrane for gas monitoring in CO2 – CH4 hydrate
exchange experiments [ CITATION Bet20 \l 1033 ]:
Introduction to application:
Present Paper has application in Method for Production of Methane from Gas Hydrate.
Gas hydrates are ice-like crystalline minerals that form when low molecular weight gas
(such as methane, ethane, or carbon dioxide) combines with water and freezes into a solid
under low temperature and moderate pressure conditions. Most gas hydrates are formed
 from methane (CH4), which has led to the terms “gas hydrate” and “methane hydrate”
often being used interchangeably. On Earth, gas hydrates occur naturally in some marine
sediment and within and beneath permafrost. Extraction of Methane from Gas Hydrate
can be used in Natural gas, which primarily consists of methane, is the cleanest burning
fossil fuel. Methane provides a great environmental benefit, producing more heat and
light energy by mass than other hydrocarbon, or fossil fuel, including coal and gasoline
refined from oil, while producing significantly less carbon dioxide and other pollutants
that contribute to smog and unhealthy air. Methane is also greenhouse gas so if we use
current technology to capture methane we also one step forward in terms of sustainable
and green environment.
Process Followed in Experiment:
For a given process Tubular polydimethylsiloxane (PDMS) membranes were utilized to
monitor the spatial and temporal gas distribution in a large-scale experimental simulation
on CO2–CH4 gas hydrate exchange. This is one of the important membranes utilized for
gas separation application.
An outer diameter of 6.4 mm and a wall thickness of 0.8 mm.
Tubes are filled with glass beads (diameter between 0.25 and 0.5 mm, Carl Roth®)
3 Step of Experiments were performed and reported
a) The permeation of pure CO2 gas, pure CH4 gas and mixed CO2–CH4 gas through the
PDMS tubing was verified in a small scale lab experiment
b) The permeation of dissolved pure CO2, dissolved pure CH4 and dissolved mixed CO2–
CH4 through the PDMS tubing was tested with an extended lab-scale experiment
c) An application test was performed. Here, several tubular PDMS membranes were
installed at defined positions in LARS to monitor spatial and temporal changes of the gas
composition in the course of a CO2–CH4 hydrate exchange experiment
Set Up used for Above Experiments
 Explanation of procedure followed in each Set up to determine Permeation Rates of
Methane
a) Volume of pressure vessel used is 1L, given system is open system.
Initially the vessel was filled with the feed gas to a defined pressure, then starting by
flushing to remove air and subsequent stepwise pressure increase (1 MPa every 10 min)
to the desired starting condition. Inside of the membrane tubing was permanently flushed
with 50 ml/min Ar gas to carry the permeating gas to a mass spectrometer for continuous
analyses. This measured gas concentration was used to calculate the gas flux through the
membrane. The concentration gradient between feed and permeate persisted and no
equilibrium was accomplished. Decreased in pressure throughout the process were
observed from pressure sensor reading.
b) Volume of pressure vessel used is 1L
A gas-water mixing chamber to prepare a gas saturated aqueous solution.
First, three quarters of the vessel were filled with degassed, de-ionized water and the
head space was filled with the feed gas of interest. The membrane-containing vessel was
completely filled with the same water. Constantly stirring the water in the gas-water
mixing chamber and water circulation between the two vessels, water with dissolved gas
was continuously transported to the membrane. Here, the dissolved gas phase permeated
through the membrane. Same as in above set up measurement of gas flux and Ar passed
continuously
c) PDMS membranes were assembled for the operation within LARS (Large Reservoir
Simulator) simulation of CO2–CH4 hydrate exchange.
LARS has a total volume of 425 L and can hold a sediment-filled reservoir volume of
210 L
Two membranes, one close to the bottom (M5) and one at the top (M1) of the LARS
vessel, were coupled to a continuous measurement system, capturing the permeated gas
in an Ar stream and leading it to a mass spectrometer for analyses of the gas
concentration
Three membranes (M2, M4, M7) were positioned in the upper part as well as the
marginal and central bottom-near area. They were used to obtain data on gas flux
variations only.
The missing membrane numbers M3 and M6 are related to membranes incorporated in
LARS but not reliable working.

Gas hydrate was formed In the course of the exchange experiment; pressure and
temperature were kept constant at 13 MPa and 284 K, respectively.
The subsequent CO2–CH4 hydrate exchange presented here, run for one day by injecting
50 L of liquid CO2 into the sample reservoir
 Results and discussion:

sys compo ph perm R2 average relat

tem nent as eate permea ion
e flux bility betw
to [barrer] een
feed CO2
press flux
ure and
(P) CH4
relati flux
on
pur CO2 ga flux= 0. 3000 flux
e s 0.18 98 CO2
0 *P 5 =
CH4 flux= 0. 900 3.75
0.04 99 *
8 *P 1 flux
CH4
CO2 di flux= 0. 1500 flux
s 0.07 98 CO2
6*P 8 =
CH4 flux= 0. 400 3.80
0.02 99 *
0 *P 1 flux
CH4
mi CO2 ga flux= 0. 2300 flux
xed (40 s 0.12 99 CO2
Vol%) 8 *P 9 =
CH4 flux= 0. 1.00
 (60 0.12 99 *
Vol%) 8 *P 6 flux
CH4
CO2 di flux= 0. 450 flux
(40 s 0.02 94 CO2
Vol%) 4 *P 1 =
CH4 flux= 0. 0.78
(60 0.02 99 *
Vol%) 3*P 6 flux
CH4

Results for testing the suitability of PDMS tubes in LARS

The results of CO2 and CH4 permeate flux at the top M1 membrane and lower M5
membrane of the inner LARS reservoir are shown in blue and red dots, respectively. Data
are compared to CO2 and CH4 concentrations (blue and red triangles, respectively)
analysed by GC at the gas release/outlet valve.
 The higher the feed gas pressure, the higher the permeability and the permeate flux.
  The permeate flux of pure water-dissolved CO2 and CH4 decreases nearly equally by
more than 50% compared to the flux of the pure gas phase due to water adsorption onto
membrane surface which hinders the permeation of CO2 and CH4 gas molecules. The
very different water solubilises of the gases are negligible. Gas permeability of this
system hindered by water
 For the mixed CO2–CH4 (40 vol%-60 vol %) feed, the permeate flux and permeability of
both components merge to nearly identical values for both, gaseous and water-dissolved
feed. Compared to pure gas, the permeate flux of CH4 increases and the permeate flux of
CO2 decreases
 Effects of membrane plasticization caused by CO2 increase the CH4 permeation through
the membrane. This, in turn, reduces the CO2 flux due to competing effects between CO2
and CH4 during diffusion
 Membranes, installed at various positions in the LARS, improved the time resolved
monitoring of CO2 migration in the course of a CO2–CH4 hydrate exchange experiment

2) Recovery of lignin from water and methanol using low-cost kaolin based tubular
ceramic membrane[ CITATION Pre20 \l 1033 ]

Introduction -
This study investigated the performance of low-cost tubular ceramic membranes fabricated using
kaolin, quartz and calcium carbonate as inexpensive raw materials following the extrusion
method for lignin recovery from water and methanol. The use of additives in ceramic membrane
preparation is attractive as it improves the membrane properties such as mechanical strength and
chemical stability, etc. The additives can be categorized as binders, plasticizers, solvents,
dispersants, lubricants and wetting agents based on their functions. Binders connect precursor
materials in ceramic membranes by forming bridges, thereby enhancing their mechanical
strength. Several researches reported the use of carboxymethyl cellulose (CMC) as a binder due
to its excellent binding properties. In this work, kaolin based tubular ceramic membranes were
employed to investigate the recovery of lignin from solvents. The effect of different binder
(CMC) concentration on the properties of the tubular ceramic membrane was investigated, and
based on the characterization results, the most suitable membrane was chosen.
Materials and Method-
1) Membrane Preparation
Different batches of membranes with varying concentrations of carboxymethyl cellulose (1, 2
and 3 wt% solution) were prepared and tested in the present study. In this work, tubular
membranes were prepared with the outer diameter, inner diameter and length of 11.5, 5.5 and
100 mm, respectively. For making tubular shaped ceramic membranes, the inexpensive clay
powders were mixed manually until a homogenous mixture is obtained. A required amount of
CMC was weighed accurately and dissolved in 300 mL Millipore water with continuous stirring
to form a homogeneous solution. The solution was then slowly added to the mixture of the clay
powders and mixed properly until a dough type paste of desired consistency was obtained. The
paste was subsequently fed into an extruder, in which a piston was forced through a die to get
green tubular membranes. these extruded membranes were then subjected to four steps of heat
treatment for its continuous drying. In the first step, the membranes were air dried for 12 h at an
ambient room temperature (25 ◦C). In the second step, the membranes were dried at 100 ◦C for
12 h in a hot air oven. The third step involved drying of the membranes at a temperature of 200
◦C for 12 h in a box furnace. Following this heat treatment, the membranes were sintered in the
box furnace at 950 ◦C for 6 h at a heating rate of 0.5 ◦C/min. These controlled drying processes
decreased any possibility of thermal stress and maximized the removal of moisture. This sort of
confined heat treatment further reduces the formation of bends and cracks in the membrane. The
membranes thus obtained after the sintering process are hard and porous. These membranes were
then cut into 10 cm length and polished using abrasive paper of grade 220 to make its surface
smooth. For removing any free particles adhered onto the membrane surface during polishing,
the membranes were immersed in an Ultrasonic bath (Elma T460, India) with water for 15 min.
Finally, the obtained membranes were dried at 100 ◦C and used for further characterization.
2) Characterization of ceramic membranes- Various tests were performed to characterize
the sintered ceramic membranes prepared with 1, 2 and 3 wt% of CMC concentration.
3) Preparation of lignin solutions -Lignin-water solution (1000 mg/L) was prepared by
dissolving one gram of alkali black kraft lignin in one liter of Millipore water. Dissolution
of lignin present in the carob pods thus yielded the lignin-methanol solution in this study.
4) Microfiltration of lignin solution - For microfiltration of lignin-water/lignin-methanol
solution, experiments were conducted using the setup detailed earlier and by passing the
solution through the fabricated membrane at a constant cross flow rate of 50 LPH.
Permeate passing through the membrane was collected in the permeate tank, and the
permeate flux for all the five applied pressures (34􀀀 172 kPa) was calculated by
collecting the permeate samples after every 2 min. All the tests were carried out at room
temperature (25 ± 2 ◦C) and the following equation was used to calculate the percentage
rejection of lignin [3]:

Result
 1) Microfiltration of lignin solutions- An increase in the permeate flux with
increasing pressure has been reported by other authors using ceramic membranes. As

observed previously in the case of pure methanol flux, a higher permeate flux is observed
with lignin-methanol solution than with lignin-water solution at all the applied pressure
values, which is due to a low viscosity of methanol. The percentage of lignin retention
decreased along with an increase in the applied pressure. In the case of lignin-water
solution, the percentage of lignin retention is found to be 82.8 % for an applied pressure
of 34 kPa. And for the lignin-methanol solution, it was 80 % for the same applied
pressure. It is to be noted that the average pore size of the membrane used for lignin
separation is 0.180 μm. Hence, it is clear that the lignin separation by the prepared
membrane is primarily due to sieving mechanism, by which the lignin particles with a
size greater than the pore size of the membrane are retained by the membrane and the
remaining particles enter into the permeate stream.

Conclusion-

With an increase in the CMC concentration, porosity of the membranes decreased,

whereas the results of mechanical stability analysis portrayed an increase in its
compressive strength. In the microfiltration of the lignin-water and lignin-methanol
solutions, the flux declines due to membrane pore blocking by the lignin particles.
Percentage lignin retention was above 80 % from both the solutions at a very low applied
pressure followed in the study.

3) Recovery of microalgae from its broth solution using kaolin based tubular
ceramic membranes prepared with different binders[ CITATION Mad20 \l 1033 ]

Microalgae based products are useful as a feedstock for biofuels and value-added
products like protein, starch, nutraceuticals, carbohydrates, cellulose lipids, pigments and
antioxidants etc. however it has been discovered that the cost of microalgae harvesting
and dewatering along with the equipment used for same comprise of maximum cost as
compared to total biomass production cost which is main bottleneck for application of
microalgae based products on commercial scale. Hence there is need for cost-effective
and efficient method for separation of microalgae from its broth solution.

The traditional techniques which includes sedimentation, coagulation, flocculation and

centrifugation can effectively separate algae from highly concentrated broth solutions but
uses high cost in terms of energy in case of diluted broths containing < 0.5 kg/ m3 of dry
algal biomass. Additionally, these methods use additives and coagulants which in turn
may cause contamination of final product and unnecessarily increase purification step.
Generally ceramic membranes are expensive, but low-cost raw material can be used in
order to keep the membrane cost low. Also, binders play important role in altering
properties of membrane such as mechanical strength, porosity, morphology and chemical
stability. Binders used can be both organic or inorganic.

The tubular ceramic membranes were prepared using low cost clay material such as
kaolin with different types of organic binders such as gaur gum (GG), carboxymethyl
cellulose (CMC), hydroxypropyl methylcellulose (HPMC) etc by extrusion method.
These tubular ceramic membranes were used for algal separation from its broth solution.
Binders are biodegradable, biocompatible and require only low concertation.

The characteristics like porosity, average pore size, pure water permeability, mechanical
strength, chemical and thermal stability, high corrosion resistance and selectivity were
evaluated. Considering the membrane properties, fabrication ease and separation
performance the best suited tubular membrane is used for algal separation.

4)Slurry loop tubular membrane reactor for catalyzed aerobic oxidation of benzyl
alcohol:[ CITATION Bal19 \l 1033 ]
Flow synthesis, it is common to find heterogeneous catalytic processes that involve the us
e of packedbed reactors .However, the use of a suspension of fine catalyst particles in a li
quid medium offers better temperature control, the possibility of 
reducing mass transfer resistances and improving catalyst performance .Catalyst use can 
be reduced by retaining a fixed amount of catalyst inside the reactor undergoing intense 
mixing.
In these works, 1 wt% Au- Pd/TiO2 catalyst was packed in a tubular Teflon AF-2400 me
mbrane, with an inner and outer diameter of 0.8 and 1.0 mm re- spectively, and inside a r
ectangular microchannel with a 0.07 mm thick flat membrane on one side of the channel.
Results indicated the presence of mass transfer resistances and limited supply of oxygen f
or the very active catalyst utilised.
In order to address these issues, a novel reactor that benefits from having a Au-Pd/TiO2 c
atalyst in a slurry form, flowing inside a loop configuration that contains a tubular membr
ane was developed in this work.
A crossflow filter inside the loop was employed to ensure the catalyst remained within th
 e loop, allowing for the continuous withdrawal of the reaction mixture.
Under aerobic conditions various reactions can take place on the catalyst surface and exte
nsive work on the reaction mechanism of benzyl alcohol aerobic oxidation on supported 
gold and palladium catalysts exists in the literature. 

References
Baldassare Venezia, M. D. (2019). Slurry loop tubular membrane reactor for catalyzed aerobic oxidation
of benzyl alcohol:. Chemical Engineering Journal, 378-382.

Bettina Strauch, K. U. (2020). Application of tubular Silicone membranes for gas monitoring in CO2 and
CH4 hydrate exchange experiments. Marine and Petroleum Geology, 122-125.

Liberman, I. (2010). RO membrane cleaning method. Tel Aviv: United States Patent.

Madu Purnima, N. M. (2020). Recovery of microalgae from its broth solution using kaolin based tubular
ceramic membranes prepared with different binders. Seperation and Purification Technology,
250-256.

Murtaza Ali Syed, N. W. (2007). Chemical Cleaning for membranes. New York City: United States Patent
Application.

Preeti Singh, N. A. (2020). Recovery of lignin from water and methanol using low-cost kaolin based
tubular ceramic membrane. Journal of water process Engineering, 38-44.