Fuel, Mixture Formation and Combustion Process, Vol. 1 No. 2 (2019) p. 1-8

FMC Fuel, Mixture Formation and Combustion Process

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e-ISSN : 2672-7331

Desalination of Seawater by using Polyamide Reverse Osmosis (RO) Membranes

Rais Hanizam Madon1,*, Nur Hanis Hayati Hairom1, Nor Afzanizam Samiran1, Nik Normunira Mat Hassan1, Zuliazura Mohd Salleh1, Nurasyikin Misdan1, Mas Fawzi2, Mohd Azahari Razali2, MZahar Abd Jalal2, Abdul Wahab Mohammad3

1Department of Mechanical Engineering Technology, Faculty of Engineering Technology, Universiti Tun Hussein Onn Malaysia, Pagoh Education Hub, KM 1 Jalan Panchor, 84600 Pagoh , Johor, Malaysia

2Department of Mechanical Engineering, Faculty of Mechanical and Manufacturing Engineering, Universiti Tun Hussein Onn Malaysia, 86400 Parit Raja, Johor, Malaysia

3Department of Chemical and Process Engineering, Faculty of Engineering and Build Enviroment, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia

*Corresponding Author

Email: [email protected]

Received 02 July 2019; Abstract: This research was focused on the characterization of the seawater’s parameters, Accepted 30 August 2019; flux and salt rejection RS rate, and energy correlation with the RO membrane systems. Available online 30 September The United Nations Environment Programmed (UNEP) reported that from now until 2019 2027, approximately 1/3 of the world’s population will suffer serious water scarcity

problems, due to the rising demand for fresh water caused by world-wide population

growth and industrial and agricultural contamination. The seawater desalination using RO

membrane is believed to encounter the fresh water scarcity. The seawater’s parameters

was characterize using Inductive Couple Plasma Mass Spectrometry. The pure water

permeation and seawater flux, and salt rejection R was determined from the reverse S osmosis (RO) water and seawater samples at room temperature with a Sterlitech dead-end

filtration. The results, showed that the flux and salt rejection rate of the membrane

increased linearly and directly proportional to the net operating pressure. Thus, water

flows in the reverse direction to the natural flow across the membrane, leaving the

dissolved salts behind with an increase in salt concentration. VPSEM characterization

verified that membrane with good pores size formation and interconnectivity show good

permeation of flux and salt rejection. As the TDS goal is 1000mg/l (fresh water), the

Polyamide RO AK membrane is the best membrane performance accordingly to its

highest flux ratio and salt rejection rate compared to the net operating pressure.

Keywords: desalination, RO membrane, flux rate, salt rejection, permeate

Keywords: 1. Introduction

Water is the backbone of the global economy, with sustainable suffer serious water scarcity problems. This is due to the rising high quality supplies being vital for agriculture, industry, demand for fresh water caused by world-wide population growth. recreation, energy production, and domestic consumption. The Hence the contamination from increasing of industrial and U.S. Geological Survey found that 96.5% of Earth’s water is agricultural demands make it becomes worse. The consequences located in seas, 1.7% in the ice caps, 1% represents brackish water of water scarcity felt in arid and semiarid areas of the planet, also and only 0.8% is considered to be fresh water [1-3]. Based on be noticeable in coastal regions undergoing rapid growth, as well United Nations Environment Programmed (UNEP), from now as in the larger cities in the developing [3-6]. Intensive efforts are until 2027 approximately one-third of the world’s population will underway throughout the world to avert this looming crisis, by

*Corresponding author: [email protected] 2019 FAZ Publishing. All right reserved. Madon R.H. et al., Fuel, Mixture Formation and Combustion Process, Vol. 1 No. 2 (2019) p. 1-8 improving the effectiveness and efficiency of water purification fouling) caused by salt precipitation. The main items need to be technology in order to produce clean water and protect the concern is that RO still hampered by at least three key obstacles environment in a sustainable manner. This conservation of the membrane fouling, high energy consumption and limited water existing limited fresh water supply is available from seawater recovery [10,11,13]. In the last 20 years a lot of improvements through various desalting technologies [5-7]. have been made in the RO process, which are reflected in the Desalination processes significantly contribute solving the dramatic reduction of both capital and operation costs. Most of the problem of water shortage by supplying water for municipal, progress has been made through improvements in membranes tourist, agricultural and industrial uses. Hence the desalination themselves. These typically include better resistance to plants preserve and extend natural water resources freeing up compression, longer life, higher possible recovery, improved flux, water for agriculture, riverbed reclamation, recreational areas and and improved salt passage. forest [2-3,6-8]. Today, some countries depend on desalination The early research was directed towards the development of technologies for the purpose of meeting their fresh water a satisfactory membrane, initially for brackish water and later requirements. In the Middle East, seawater desalination is a vital seawater. The development work was undertaken by companies and dependable fresh water resource in countries such as Saudi specializing in membrane manufacturing [7,8]. Malaysia as one of Arabia, United Arab Emirates, and Kuwait [9-12]. Furthermore, it the rapid develop country also needs to investigate the is likely that desalination will continue to grow in popularity in desalination by using RO membrane as precaution methods if the Middle East [5-7]. Basically, desalination can be defined as a there is any risks for lacking of fresh water resources due to process of removing salt from water to produce fresh water. Fresh community demands and pollutions. This is reliable since there water is defined as containing less than 1000 mg/L of salts or total are a lot of seawater sources and also there was no data shown for dissolved solids (TDS) [1-3]. The desalination processes can be these studies. categorized into two major types, phase-change thermal and membrane process separation. Some of the phase-change 2. Experimentals processes include multi-stage flash, multiple effect boiling, vapor compression, freezing, humidification/dehumidification and solar 2.1. Characterize the Seawater’s Parameters stills. Membrane based processes include reverse osmosis (RO), The sea water sample used in this study were obtained from the membrane distillation (MD) and electro dialysis (ED). The Melaka Straits and focusing on coastal region (Pulau Besar required pressure depends on the salt concentration of the resource Island). of saline solution, it is normally around 55 till 70 bar for seawater desalination [6-8]. The concepts of osmosis and reverse osmosis 2.1.1 Total suspended solid (TSS) have been known for many years. In fact, studies on osmosis were The Total Suspended Solid is determined through this method. carried out as early as 1748 by the French scientist Nollet, and The Whatman Nylon Membrane Filters (0.45µm) with diameter many researchers investigated these phenomena over the next two 47mm is dry in oven at 105 C for one hour. In order to ensure the centuries. However, the use of reverse osmosis (RO) as a feasible membrane filters is free from moisture, it’s located into dessicator separation process is a relatively young technology. In fact, only for 30minutes. Then the membrane filter is weight for every 10 in the late 1950’s did the work of Reid show that cellulose acetate minutes interval until it gives constants reading. By using suction RO membranes were capable of separating salt from water, even pump, 100 ml of RO water is filter, passing through the membrane though the water fluxes obtained were too small to be practical. filter. Finally, 100 ml of sea water is filter through membrane Then, in the early 1960’s, Loeb and Sourirajan developed a filter. The TSS reading is in mg/l and the result is obtained based method for making asymmetric cellulose acetate membranes with on this equation. relatively high water fluxes and separations, thus making RO separations both possible and practical [9-12]. Reverse osmosis W −W TSS = ( a b) × 1000 (RO) membrane is regarded as the most economical, energy L efficiency process and popular desalination way for water (1) production mainly due to the advancement of membrane technology [10-13]. The RO can be defined as a pressure-driven Where Wa is weight after (gm), Wb for weight before (gm) and L process that separates two solutions with different concentrations is represent 0.1 liter (L). across a semi-permeable membrane. In the RO process, a semi permeable membrane is used for separation of particles sizes of 2.1.2 Inductive Couple Plasma (ICP) equipment test 5×103–1×104 μm, including single charge ions such as Na+ and Cl- parameters . The separation is driven under high pressures, not more than 7.0 The analysis is done for sample before and after desalination MPa and should be higher than the transmembrane osmotic process and only sample at maximum operating pressure (20 bars) pressure [11-14]. is analyzed. This analytes is obtained from Inductive Couple Furthermore, in the Reverse Osmosis (RO) membrane Plasma Mass Spectrometry ELAN 9000 / Perkin Elmer Sciex [15]. process, the osmotic pressure is overcome by applying external pressure higher than the osmotic pressure on the seawater. Thus, 2.2. Characterize the RO Membrane for Membrane water flows in the reverse direction to the natural flow across the Permeability membrane, leaving the dissolved salts behind with an increase in salt concentration and no heating or phase separation change is 2.2.1 Standard Sodium Chloride (NaCl) solution as control necessary. Hence the only major energy required for desalting is For control spec of the sea water sample TDS, a standard Sodium for pressurizing the seawater feed [7-9]. There is a major problem Chloride (NaCl) solutions as control is prepared accordingly 0 g/l, related to RO applications, it is membrane fouling mechanism that 5 g/l, 10 g/l, 15 g/l, 20 g/l and 25 g/l. The sea water TDS reading negatively affects the performance efficiency in RO plants. is done by using Mi306 EC/TDS/naCl/Temp Meter, Martini Fouling is caused by solute adsorbing irreversibly or reversibly Instruments. The pure Sodium Chloride (NaCl) is dissolved into onto the surface of the membrane or within the pores of the pure RO water accordingly to the ratio of weight over volume in membrane [13-15]. It usually causes serious decline in the flux order to yield the TDS in unit of g/l. and quality of the permeate, ultimately resulting in an increase in the operating pressure with time. [5-7]. Hence in the seawater 2.2.2 Membrane preparation desalination, it is also known as membrane scaling (or inorganic Three different membranes to be used is obtained from Sterlitech 2 Published by FAZ Publishing http://www.fazpublishing.com/fmc

Fuel, Mixture Formation and Combustion Process Vol. 1 No. 2 (2019) p. 1 -7 Corporation and manufacture by GE Osmonics. This membrane Microscope (VPSEM) LEO 1450 is used and magnifying 1000 was selected due its material superior selectivity, good thermal times. resistance and high mechanical strength. This membrane is keep inside dry clean container to avoid any contamination. The 3. Results and discussions membranes are Polyamide RO AD, Polyamide RO AG and Polyamide RO AK. 3.1. Characterization of the Seawater

2.2.3 Total dissolved solids determination procedure 3.1.1 Total suspended solid (TSS) Sterlitech Dead End Permeation Cell,Model P/N HP4750 from The Total Suspended Solid standard control of the locations is Sterlitech Inc.with a capacity of 300 ml was used for this shown as in Table 2. The reading of 135 mg/l is quite low and experiment. Conducted at different pressures range from 5 to 20 significantly not gives a big impact to the membrane fouling rate. bar with an effective area of about 14.6 cm2. The procedures apply as stated [14]. Membrane to be used is soaked in the RO water for 3.1.2 Inductive Couple Plasma (ICP) equipment test overnight before can be used in order to remove any glycerin parameters attached on active surface area. Then each membrane was From the Table 3 show data of analytes reading for sea water pressurized at 10 bar for 30 minutes before the permeation sample of Pulau Besar and its represent of the feed and permeate experiments. The feed solution was stirred at the speed up to 400 sample and only been taken from 20 bar operating pressure. For rpm to minimize the concentration polarization effect. For the pure each RO membranes type, clearly shown that analyte in permeate water permeation (PWP) and salt permeation was measured by sample is reducing. This is due to the solute diffusion crossing the using RO water and seawater sample, respectively. Salt RO membrane is mainly filtered, lead to the reducing of analytes permeation was determined using a TDS meter (Mi306 concentration in permeate sample. RO membrane acts as a semi- EC/TDS/NaCl/Temp Meter, Martini Instruments). Data obtained permeable barrier that allows selective transport of a particular are the average of at least three replications to ensure that the species (solvent, usually water) while partially or completely results are reproducible and been run at operating pressure of 5, blocking other species (solutes, such as salt). It’s capable to 10, 15 and 20 bar. Finally, the pure water permeation and sea separate particles sizes of 5×103-1×104 μm, including single water sample fluxes were calculated with the following equation charge ions as such Na+ and Cl-. Rejection performance membrane of Flux. was better for all anionic and cationic pollutants. V J = (2) 3.2 Characterize the RO Membrane for Membrane AΔt Permeability Where the V is the volume of permeate (L), A is the membrane surface area (m2) and Δt is the permeation time (h). 3.2.1 Standard Sodium Chloride (NaCl) solution as control For the Salt rejection RS of RO membrane systems were From the Table1 shows the result of standards NaCl solution as calculated with the following equation of RS. control specification for probe meter reading during experimental progress, this was use as a standard reference controlled data Cpermeate during experimental. RS = (1 − ) × 100% (3) CFeed Where the Cfeed is the ion concentration in the feed solution, Table 1 : Standards NaCl solution as control specification Cpermeate is the ion concentration in the permeate. For each sample was tested accordingly to the types of NaCl Concentration actual TDS probe meter membrane and variety of net operating pressure 5 to 20 bar with No. interval of 5 bar. (g/l) (g/l)

2.3 RO Membrane Characterizations by using SEM 1 0 0.00222 Membrane samples used for the morphological structure analysis 2 5 4.5 are soaked into liquid Nitrogen, and cracked it. Then coated with gold powder to ensure all electrons is direct accumulate and 3 10 8.32 focusing to target area when the electron gun is running. The 4 15 12.44 sample was placed on the sample stand and stick to it by using 5 20 16.8 carbon tape. For this RO membrane cross sectional area characterization, Variable Pressure Scanning Electron 6 25 20.8

Table 2 : Total suspended solid for sea water sample Pulau Besar

Readings (gm) Sample a b c d e TSS (mg/l) Before 23.2236 23.2231 23.2218 23.2209 23.2222 1 136 After 23.2345 23.2354 23.2351 23.237 23.2355 Before 23.2215 23.222 23.2223 23.2228 23.223 2 132 After 23.2355 23.2347 23.2361 23.236 23.2352 Before 23.2227 23.2219 23.221 23.2217 23.2224 3 138 After 23.2361 23.2356 23.235 23.2348 23.236

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Table 3 : Analytes parameters for Pulau Besar’s sea water sample

Seawater Sample : Pulau Besar Membrane RO AD RO AG RO AK No. Parameter Unit Feed Permeate Feed Permeate Feed Permeate 1 TDS g/l 24.1316 15.4199 24.4537 7.3321 25.1381 6.8128 2 pH 7.91 7.87 7.96 7.11 7.86 6.18 3 Sodium Na mg/L S S S S S S 4 Potassium K mg/L 8.217 6.611 7.789 3.005 8.903 3.127 5 Calcium Ca mg/L 10.381 7.994 9.82 0.946 11.342 2.691 6 Magnesium Mg mg/L 527.751 400.637 490.082 15.73 573.734 40.88 7 Strontium Sr mg/L 0.18 0.145 0.171 0.017 0.205 0.043 8 Barium Ba mg/L 0.002 0.002 0.001 0.001 0.001 0.001 9 Chloride Cl mg/L 1061.49 799.93 1221.274 335.853 1067.202 344.835 10 Fluoride F mg/L 0 0 0 0 0 0 11 Iron Fe mg/L 0.027 0.027 0.031 0.027 0.025 0.026 12 Manganese Mn mg/L 0 0.001 0 0.001 0 0.001 13 Aluminium Al mg/L 0.038 0.008 0.016 0.003 0.032 0.011 14 Boron B mg/L 1.483 1.297 1.083 1.411 1.284 1.06 15 Bromide Br mg/L 2.066 4.369 2.308 2.509 2.209 2.385 16 Copper Cu mg/L 0.066 0.048 0.084 0.015 0.068 0.032 17 Nickel Ni mg/L 0.017 0.014 0.023 0.008 0.02 0.011 S = saturated reading

3.2.2 The pure water permeation and sea water sample fluxes desalination’s feed and permeate for sea water sample. From Table 4 and Figure 1 shown the results obtained for pure water From Table 5 and Figure 2, shown that Polyamide RO AK permeation of RO water and sea water sample fluxes for Pulau membrane gives the highest salt rejection of 72.9% and Polyamide Besar’s sample. Based on membrane type performance, the highest RO AD membrane gives 36.10 % at maximum operating pressure of yield of pure water permeation of RO water and sea water sample 20 bar. The graph show tendency by the fact that the salt rejection is fluxes is Polyamide RO AK membrane and the lowest is Polyamide directly proportional to the net operating pressure Thus, water flows RO AD membrane. The description of RO (darken color graph) and in the reverse direction to the natural flow across the membrane, SAMPLE (lighten color graph) for each membrane type represent leaving the dissolved salts behind with an increase in salt RO water permeation and the sea water sample flux. The flux of the concentration. From this graph, by using equation of trend line, the membrane increases almost linearly. It can be explained by the fact net operating pressure in order to achieve target of 1000 mg/l TDS that the permeate flux is directly proportional to the net operating is obtained for each membrane type. Since the graph R square value pressure, whereas the solute diffusion across the membrane on the for each membrane is > 0.9, this data acceptable to be use as a other hand is not affected by the applied pressure, so an increase in standard graph for Salt rejection RS versus operating pressure of water flux with applied pressure will result in a low salt Pulau Besar’s sample. concentration in the permeate and thereby an increase in salt rejection. For the fouling properties, mainly refers to the deposition 3.2.4 Optimum sea water flux and salt rejection RS of RO of foulants on top of the membrane surface or within the membrane membrane systems pore and can be generally categorized into inorganic fouling, The optimum membrane performance for each type of membrane is colloidal fouling, organic fouling and biofouling. It must be pointed determined based on major aspect in desalination which are sea out that fouling portrays the prominent constraint in seawater water sample flux and salt rejection. The evaluation is done desalination process. It deteriorates membrane performance and accordingly by defined the operating pressure for each type of shortens its lifespan, leading to increased operation cost. For these membrane at the point of target TDS. The flux for each sea water reasons, membrane fouling control is highly recommended as an sample also been defined at the point of operating pressure which imperative way to control the economics of seawater reverse achieved target TDS. osmosis (SWRO) desalination process.

3.2.3 Salt rejection RS of RO membrane systems For the Salt rejection RS of each RO membrane systems, the sea water sample is tested accordingly to the net operating pressure. Hence below as in Table 5 and Figure 2 is the results obtained. For the results show in table, symbolic F and P is represent of

4 Published by FAZ Publishing http://www.fazpublishing.com/fmc Fuel, Mixture Formation and Combustion Process Vol. 1 No. 2 (2019) p. 1-8 Table 4 : Flux of RO water and sea water sample Pulau Besar

Flux (L/m²h) of RO water and Pulau Besar’s sea water Membrane AD AG AK Pressure AD RO AD SAMPLE AG RO AG SAMPLE AK RO AK SAMPLE 5 3.8336 0.2309 18.6123 0.7985 23.1049 1.0834 10 5.2936 0.3008 29.4524 1.2111 39.5660 2.8148 15 6.8607 0.4681 40.4222 1.8512 52.4628 6.1034 20 10.6209 0.7126 59.5593 2.5901 66.3550 9.3400

Flux of RO Water and Pulau Besar's Seawater Sample for each membrane 80 10 AD RO 70 9 8 60 AG RO 7 50 6 40 5 AK RO 30 4

3 AD SAMPLE Flux (L/m²h) RO Flux(L/m²h)

20 Sample (L/m²h) Flux 2 10 1 AG SAMPLE 0 0 0 5 10 15 20 25 AK SAMPLE Operating Pressure (bar) Figure 1 : Flux of RO water and sea water sample Pulau Besar versus operating pressure.

Table 5 : Salt rejection RS of Pulau Besar’s sample

Total Dissolved Solids (g/l) of Pulau Besar's sample Membrane AD AG AK Pressure F P Rs F P Rs F P Rs 5 24.4537 23.3909 4.35% 24.5342 20.0334 18.35% 24.8965 16.7162 32.86% 10 24.4537 21.3619 12.64% 24.4537 18.6747 23.63% 25.0173 15.6655 37.38% 15 24.5745 18.4593 24.88% 24.4134 12.2355 49.88% 25.0576 12.0342 51.97% 20 24.1316 15.4199 36.10% 24.4537 7.3321 70.02% 25.1381 6.8128 72.90%

RO Membrane Performance for Pulau Besar's Seawater 80% Sample AD 70% 60% AG R² = 0.9471 50% AK 40% R² = 0.9302 Linear 30% (AD) Linear

Salt RejectionRs 20% R² = 0.9942 (AG) 10% Linear 0% (AK) 0 5 10 15 20 25 Operating Pressure (bar)

Figure 2 : Salt rejection RS versus operating pressure of Pulau Besar’s sample.

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From the Table 6 and Figure 3, the evaluation is done and 4.0 Conclusion based on the ratio of sea water flux to operating pressure. The ratio The seawater desalination process is successfully done by using for Polyamide RO AG and Polyamide RO AK is 0.12 compare to polyamide RO membranes. Based on the seawater’s parameters had 0.49. In terms of economical analysis, raw cost for both membranes shown that Pulau Besar’s seawater sample got TDS of 24.12 -25.14 is same, but due to different ratio flux to operating pressure, the g/l. Based on representative VPSEM images of the cross-section of highest ratio is chosen. As the TDS goal is 1000 mg/l (fresh water), the membrane for before (blank) and after (sample Pulau Besar) this Polyamide RO AK membrane is the best membrane permeation. The pores size and interconnectivity is determined, and performance accordingly to its highest flux ratio and salt rejection is use to justify and predict the membrane performance interms of rate to the net operating pressure. salts rejection and flux rate. The permeate flux and salt rejection is directly proportional to the net operating pressure, whereas the 3.2.5 RO membrane characterization through Variable solute diffusion across the membrane on the other hand is not Pressure Scanning Electron Microscope (VPSEM) affected by the applied pressure, so an increase in water flux with Variable Pressure Scanning Electron Microscope (VPSEM) LEO applied pressure will result in a low salt concentration in the 1450 is used and magnifying up to 1000 times to characterize the permeate and thereby an increase in salt rejection. From this membrane cross sectional area and shown as in Table 7. experiment, as the TDS goal is 1000 mg/l (fresh water), we can conclude that the Polyamide RO AK membrane is the best membrane performance accordingly to its highest flux ratio and salt rejection rate to the net operating pressure

Table 6 : Salt rejection RS and Flux of Pulau Besar’s sample

Target of 1 g/l TDS for Permeate RO Membrane AD AG AK Salt Rejection (%) 95.90% 95.91% 96.00% Operating Pressure (bar) 49.1439 27.9756 31.1171 Flux (L/m²h) 1.5976 3.4661 15.2777

Polyamide RO AK Membrane Performance for Pulau Besar's Seawater Sample 80% 10

60%

40% 5

20% Flux(L/m²h)

Salt Rejection Rs Salt Rejection 0% 0 0 5 10 15 20 25 Operating Pressure (bar) SALT REJECTION FLUX (L/m²h)

Figure 3 Salt rejection RS and flux versus operating pressure of Pulau Besar’s sample.

Table 7 : VPSEM characterization for Pulau Besar’s sea water sample operation of each membrane

Before Desalination After Desalination Polyamide RO AD

Representative VPSEM images of the cross-section of the polyamide RO AD membrane for before (blank) and after (sample Pulau Besar) permeation. The pores size and interconnectivity is quit no so good because not fully or clearly formed. That’s why rejection is low. Beside that that the pores are fulfill with solute. This lead to increase fouling rate.

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Polyamide RO AG

Representative VPSEM images of the cross-section of the Polyamide RO AG membrane for before (blank) and after (sample Pulau Besar) permeation. The pores size and interconnectivity is not clear formed. Shown that the pores is most fulfill with solute. This lead to increase fouling rate.

Polyamide RO AK

Representative VPSEM images of the cross-section of the Polyamide RO AK membrane for before (blank) and after (sample Pulau Besar) permeation. The pores size and interconnectivity is good and clear formed, straightly lead to good salt rejection. Shown that the pores is almost fulfilling with solute. This lead to less of increase fouling rate compare to others type of membrane.

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