Attestation of Own Work.

This project is solely the work of Kieran Sexton unless otherwise indicated and is Submitted in partial fulfillment of the Degree of Bachelor of Engineering in Chemical and Biopharmaceutical Engineering

Signed -------------------------Date --------------------------

Acknowledgements I would like to thank Dave and Phil, the Lab technicians who were always there to help us during our research project. I would also like to thank Noel Duffy and Aisling OGorman who both gave me advice through out my project.

Table of Contents-Pilot Plant

1.0 2.0 3.0

Executive Summary Objectives Literature Review

3.1 Introduction to Nanofiltration 3.2 Organic Solvent Nanofiltration 3.3 Membrane Configuration 3.4 Membrane Parameters 3.5 Transport Model 3.6 Case Study 1- Nanofiltration of Highly Concentrated Salt solutions up to seawater salinity 3.7 Case Study 2 - Fine Chemical- Organic Solvent Nanofitration- a lower energy alternative

3.8 Case Study 3 Choosing appropriate solvent 4.0 Equipment 4.1 Setting Temperature and Pressure Switches 5.0 Operating Procedures 5.1 Pure Water Runs 5.2 Salt-Water Runs 5.3 Risk Assessment 6.0 Experimental Data 6.1 Experimental Formula 6.2 Pure Water Runs 6.3 NaCl Runs 7.0 Discussion 8.0 Conclusion 9.0 Recommendations 10.0 Bibliography and References

Table of Figures: Figure 1: Spiral Wound Membrane Figure 2: Plate Cross-Section Figure 3: Tubular Cross Figure 4:Nanofiltration Rejection vs. Flux of Nalco Figure 5: Organic Solvent Nanofitration Efficiency Figure 6: Toluene Rejection Figure 7: Flux vs. Tear Mass Fraction Figure 8: Organic Solvent Nanofiltration Pilot Plant Figure 9: Pressure and Temperature Switches Graph 1: Pure Water Flux vs. Time

Graph 2: Rejection vs. Time Graph 3: Permeate Flux vs. Time Executive Summary: The research project I was given was organic solvent nanofiltration. The aim of my research project is to commission the pilot plant for, 1) Pure water Runs 2) Salt-Water Runs Pure water runs The reason I did pure water runs was to firstly calculate the maximum permeate flux the of the nanofiltration membrane and secondly to verify, after already doing a visual (with the P&IDS) that there is no leaking or loose valves in the pilot plant.

I also chose an appropriate organic solvent on the basis of my literature review. The organic solvent that I think should be used in this system is Toluene and using TOABr as the solute. It is expected to get very close to 100% rejection. You will see from the literature data that Nanofiltration, especially Organic Solvent Nanofiltration is in a big growth spurt at the moment as there is a demand for purer products, which use less energy than other proposed methods of liquid solution separation, such as distillation.

Abstract: My research project is to investigate the parameters surrounding the organic solvent Nano filtration pilot plant. I am using a Koch membrane used for Nanofiltration. Firstly I will be investigating the results of a pure water solution varying the Pressure and the Pump speed. Comparing this to my literature review there should be an increase in permeates flux. This will indicate the maximum permeate flux of the membrane I am using. The second thing I will be investigating will be is the salt-water solution runs and the effects of altering their parameters will have on the pilot plant. I am using NaCl as the salt and varying the salt concentration from 1000PPM, 5000PPM and 10000PPM. Like the Pure water runs I will be also varying the Pressure and the Pump speed. This will give me a wider understanding of what individual affects the parameters have on the membrane and solution. Finally I will be getting the literature data on the organic solvent I believe the next operator should use in the system. This organic solvent will be the first organic solvent to be run in the system should they use my literature data. As you will see the parameters for this project have a direct influence on the membranes ability to be effective in either rejecting solute or allow permeate through. It is clear from all the data and the literature review that ideal situation

in a plant is to have high rejection and high permeate flux. So ideal goal of this pilot plant is to see how you can maximize those parameters. 1.0 Objectives: Since there was an issue with time, my initial objectives have changed slightly since I originally started.

1) Commission the organic solvent nanofiltration system for a Pure Water Runs 2) Commission the organic solvent nanofiltration system for a Salt-Water Solution

3) Identify an appropriate organic solvent to be run through the system for the next operator.

2.0 Literature Review 1.1 Introduction to Nanofiltration: Nanofiltration is a cross-flow filtration technology which ranges somewhere between ultrafiltration and reverse osmosis. The pore sizes of its membrane ranges from 1-5 nanometers (nm). Since the pressure drop across the membrane is much lower than that using reverse osmosis, the operating cost of running a nanofiltration system is a lot cheaper. This is one of the main reasons for the huge surge in recent years, by a lot of industries, to try and introduce nanofiltration into their process. Nanofiltration is a liquid phase separation process, which separates organic or inorganic substances from a solution of liquid. History of Nanofiltration: Nano filtration is the most recent method used by industries as a pressuredriven membrane-based separation process, whose characteristics fall between those of ultrafiltration and Reverse Osmosis. Nano filtration membranes were first introduced during the late 1970s for water filtrating and purification. Until recently, as in the last 20 years, Nano filtration had a very limited use in the world as it was only used as pre-treatment to desalinate the water before reverse osmosis was used for a higher rejection rate. With many advancements being developed in the Nano filtration systems, a growing popularity for the use of these has ensued. Much advancement has been made into; 1. The development of innovative materials 2. Creating advanced properties for the membranes

3. Increasing the membranes life span (which accounts for a major cost of using Nano filtration as a technique) 4. Increasing the number of applications spanning many industrial sectors. (This led to the innovative method of using organic solvent membranes in the pharmaceutical sector as a purification technique) Global market: The global market research into the use of Nanofiltration as a process is predicted to increase exponentially in the next few years. According to a BCC research report, who have thirty-five years of reporting on top industries world wide, the global market for nanofiltration membranes are said to increase from $89.1million in 2006 to an estimated $310.5 million in 2012. Over 72% of these membranes are used in water treatment and with increasing technological advances in membrane materials and in new methods being used in industry, there is a continuous growth pattern predicted in this market. (http://www.google.com/url?sa=t&rct=j&q=&esrc=s&source=web&cd=1&sq i=2&ved=0CCkQFjAA&url=http%3A%2F%2Ffiles.bvs.br%2Fupload%2FS%2 F1519-8928%2F2009%2Fv34n1%2Fa243260.pdf&ei=UxLhTp3WFJO2hAfjvenxBA&usg=AFQjCNHO75Mb1hPoXWQPKKLKhy4Vg6z8A, pages 251,252) A lot of this current growth and predicted growth can be accounted for with the development into the solvent resistant nanofiltration membranes. This has exponentially increased the possible applications of this membrane within the fine chemicals industry in relation to the separation techniques used in removing organic solvents. 1.2 Organic Solvent naofiltration: During the 1990s the first large-scale application off Organic Solvent Nanofiltration was realized for solvent recycle in lube oil production. This method of solvent recycle is still practiced worldwide today in the refineries. Organic Solvent Nanofiltration membranes can separate molecules between the molecular weight ranges of 200-1000. The typical pore sizes associated with nanofiltration membranes are in the region of 0.1-05 nm, and only using pressures in the region of, typically, 5-30 bar. Comparing this pressure region to reverse osmosis, which is typically between 10-85 bars, it is clear to see that it has a needs a lot less pressure to work effectively. This method of separation is mainly used in the following processes; 1. Recycling catalysts and integration of reaction and separation in membrane reactors 2. Solvent operations such as solvent exchanges and fractionation 3. Structured chemical reactors 4. As a separation process in a continuous process alternative to traditionally used methods such as distillation and chromatography Organic Solvent Nanofiltration is being used as follows to increase their yields. A very demanding sector in industries is in the recovery of crystals in the

purification step. Using solvent resistant membranes in the purification process enhances crystallization of organic compounds. By introducing an anti-solvent to the cooling crystallization process more crystals are recovered giving higher yields. Benefits of Nanofiltration: Alternative separation technique Increases product Value Reduces Processing time It is environmentally friendly Operating costs drop immensely Especially if it is switching from a none pressure driven technique Uses low pressure compared to Reverse Osmosis

Using Membrane Extraction Technology (MET), Organic Solvent Nanofiltration process greater than 99% exchange of solvents at ambient temperature can be achieved using up to 80% less energy than distillation and without need for solution to go to dryness.

Applications of Organic Solvent Nanofiltration: As stated above Organic Solvent Nanofiltration is a relatively new method used by industries today. It is definitely going to grow in the amount of applications it will under take but currently the main applications of this system are as follows: 1. 2. 3. 4. 5. 6. Removal of polymeric impurities Product purification Monomer/Dimer Separation Solvent Exchange at room temperature Solvent recycling Catalyst recycling/reuse

The three most commonly practiced applications used today by industry are product purification, solvent exchange and catalyst recovery. (http://duramem.evonik.com/sites/dc/Downloadcenter/Evonik/Product/Dura Mem-PuraMem/brochures/flyer-duramem-and-puramem.pdf.)

Membrane: Membranes used in Nanofilration are either composed of natural polymers such as cellulose polymers or synthetic polymers, which are made of plastic materials or inorganic ceramic materials.

1.3 Membrane Configuration:

Spiral Wound Membranes: The spiral wound membrane was originally made for the purpose of desalination of water, but the compact design and its low cost of production has made it very appealing to other districts in the industry. Flowing under pressure the feed solution enters the membrane and spirals towards its core only to exit as permeate.

Figure 1: Spiral Wound Membrane The great thing about using spiral wound membranes in industry means that a process can be constantly kept running for weeks with a constant flux of 20L/m^2hr. This is done in the full-scale drinking water plant in Norway. Advantages: 1. Its a compact membrane 2. Since the change of pressure across the membrane is low it uses a minimal amount of energy. 3. Its operating cost and capital cost is low Disadvantages: 1. 2. 3. 4. Not suitable to very viscous liquids It has a lot of dead space Very difficult to clean If there is a small fault in the membrane, like a tiny tear, the whole module must be replaced. 5. Intolerant to large pressure drops across the membrane (http://www.google.com/url?sa=t&rct=j&q=&esrc=s&source=web&cd=4 &ved=0CDoQFjAD&url=http%3A%2F%2Fwww.cdr.wisc.edu%2Fprogra ms%2Fdairyingredients%2Fpdf%2Fmembrane_config.pdf&ei=HQjhTtS7J cbPhAfcnNHvBA&usg=AFQjCNEVfPQqbOZR-L1pehC2MS8LCPE1Gw)

Plate and Frame Membranes: This is a membrane, which is sandwiched between membrane support plates, which are arranged in stacks.

Figure 2: Plate Cross-Section Plate and frame membranes used to be very popular in the dairy industry before the mid 90s but due to the high cost of design and lack of development in improving this type of membrane module, most of the dairy industry switched to the cheaper and continuously improving method, which uses a spiral, wound membrane. Plate and frame membranes are still used today and are seen in a lot of lab scale research into the properties of the membrane. Advantages: 1. 2. 3. 4. Low hold up volume Permeate from individual membrane element Membrane replacement is easily done Can deal with high pressure (exceeding 100bar)

Disadvantages: 1. 2. 3. 4. It is difficult to clean Susceptible to plugging It is expensive Operation involves labor and operation

Hollow Fiber Membrane: Hollow fiber membranes are tightly packed membrane fibers, which are usually 2mm thick, and are packed into a similar design as the tubular module.

Advantages: 1. It has an extremely high packing density 2. Back-flushing may be possible 3. It has a lower energy/operation cost Disadvantages: 1. It cant handle large pressure changes 2. Only works efficiently at low feed velocities and pressure 3. It is easily plugged Tubular Membranes: Tubular membranes have a simple tube in shell design.

Figure 3: Tubular Cross They are popularly used in academic projects, as it is relatively easy to calculate the Reynolds number and mass transfer coefficient from its results. Unfortunately it has a lot of disadvantages as you will see below which dont make it ideal to be used in most industry processes. Advantages 1. 2. 3. 4. It can deal with large particles in the feed. It can handle high viscosity products/solutions The feed stream can be easily controlled Cleaning this membrane module is a lot easier than all the other membrane configurations

Disadvantages: 1. Its membrane area to volume ratio is the lowest of all the membrane modules 2. It has high hold up volumes

3. It uses the most amount of energy compared to the other membrane modules due to its substantial pressure drops 4. It requires a large amount of space. As you can see from the advantages verses the disadvantages of using a tubular membrane it is clear to see why it isnt cost effective to use in industry.

1.4 Membrane Parameters for Nanofiltration: 1. Pressure: Nanofiltration is a pressure driven separation system, so it goes without saying that pressure plays a vital role in the performance level of the pilot plant. As you will see in my literature review pressure has a direct relationship with the permeate flux. An increase in pressure increases the permeate flux, which is what industries want to do 2. Temperature: With an increase of temperature in the system you increase the membrane flux due to the fact that the solution becomes less viscous as the temperature increases. Temperature has little to no effect on the rejection of the membrane while it does increase the permeate flux. 3. Driving Force (Pump Speed) By increasing the pumps speed in the pilot plant, you increase the cross flow rate of the solution. This, like the pressure will increase the permeate flux when it is increased. Advantages of running the nanofiltration system at a higher flow rate is that it reduces the risk of membrane fouling, but it does run the risk of tearing the membrane if it set too high. 4. pH The pH of an organic solvent nanofiltration membrane is generally slightly negative. PH can affect the separation performance within a nanofiltration system to a great extent. For this main reason the pH must be always monitored in the system. The solubility of ions can be controlled with pH 5. Salinity: Desalinating water is a major industry in the world and unfortunately the higher the salt concentration is in the solution the lower the rejection percentage is on the membrane. As the ions increase in the solution less

binding occurs on the membrane and therefore increase in salt concentration decreases the rejection rate.

Membrane Fouling: Membrane fouling is going o occur in a system where it has organic or salt solutions passing through it. Mainly there is going to be a build up of cake, along the membrane wall, which will lower the efficiency of the nanofiltration system. There are a few methods to decrease and even eliminate all fouling in the membrane. You can physically clean the system, which uses mechanical forces to remove the fouling from the membrane. Examples of this are, a. Air Sparge b. CO2 back permeation c. Scrubbing The main method of cleaning the system is with chemical cleaning agents The idea behind using chemical agents is to break the chemical bonds of the fouling factor and let it be cleared. Examples of these are d. e. f. g. Hydrolysis Dispersion Peptization Saponification

1.5 Transport models: Speigler-Kedem: A very popular transport model for Nanofiltration is using the Speigler-Kedum model. This method is based on irreversible thermodynamic and shows the direct relationship between the permeate flux (solvent solution flux) and the rejection of the membrane. The transport mechanism of ions through the nanofiltration membrane is described when using the speigler-kedem method to calculate the retention of ions in a single and mixed electrolyte solution. This equation ignores the charge of the solution.

Where, R= observed rejection J= Permeate flux = Reflection coefficient Ps= solute permeability coefficient

Calculating the real rejection: The actual rejection can be calculated using the following formula, R = 1 Cp/Cr, Where, R= rejection Cp= Concentration of permeate Cr= Concentration of retentate

Solution Diffusion Model: A commonly used transport model for nanofiltration is the solution diffusion model. It is a homogenous model and is based on the permeants dissolving into the membrane material and then diffuse through the membrane and down to the concentration gradient. The separation between the permeants is based on which of them diffuses through the membrane quicker and which one dissolves into the membrane quicker. So it is clear that the solution diffusion model transports on the basis of pressure differences across the membrane and the concentrations of the permeants. From that we get the following formulas to calculate the Solute Flux and the Water Flux: 1)

Where,

Js= Solute Flux A=Permeability of Solute Cs = Concentration Difference across the membrane

2)

Where, Jw=Water Flux B=Permeability of Solvent p= Pressure difference across the membrane = Osmotic Pressure difference across the membrane

1.6 Case Studies: Nanofiltration of Highly Concentrated Salt solutions up to seawater salinity: In this case study the author investigates the efficiency of using nanofiltratin as a pre-treatment to desalinate the water. Using three commercially used nanofiltration membranes, (NF90, NF270, N30F), he shows the effects that pore size, and pressure and salt concentration can have on the system. The salt in question that he wanted to get rejected is NaCl. The salt concentration in which he is comparing ranges from 5000-25000PPM. Taking the salt concentration at 5000PPM and a pressure of 9bar as the standard, the following results were recorded in this article. 1. The rejection of NaCl level respectively of NF90, NF270 and N30F membranes was 95%, 11-29% and 3-6%. 2. Once he maximized the salt concentration to 25000PPM the NF 90 membranes rejection went from 95% to 41%. 3. For pure water flux through the system the NF270 membrane had the highest flux under all the studied membranes under all pressures while N30F had the lowest flux. 4. The rejection level of all the membranes increased with increasing pressure. While NF90 membranes rejection at 25000PPM and at 9bar is

41%, when we change the pressure to 2bar the rejection level decreases to 3.1%. This shows the drastic effect pressure can have on the systems effectiveness to desalinate the solution. 5. With the increase of pressure comes an increase in permeate flux. 6. Using the spiegrel-kedem tansport model it was found that with at low salt concentration we get high flux and high rejection from the system while at high salt concentration he found that he got low flux and low rejection results.

Figure 4:Nanofiltration Rejection vs. Flux of Nalco

Using a lot of this data as the foundation of my own experiment I went to see if my results correspond to his results under the same parameters. I concluded that with this case study and my own results that with increase salt concentration result in decrease in rejection of the membrane. I also concluded that increasing the pressure would increase the solvent flux and the rejection percentage. So ideally when running a system we can see that we want to run at higher pressures and lower salinity to maximize the efficiency of our nanofiltration process. (Science Direct - Desalination: Nanofiltration of highly concentrated salt solutions up to seawater salinity. Available at: http://0www.sciencedirect.com.acpmil04web.ancheim.ie/science/article/pii/S0011916 40500576X)

1.7 Case Study 2: Fine Chemical- Organic Solvent Nanofitration- a lower energy alternative Organic Solvent Nanofiltration is a new and rapidly growing separation technique used in the chemical and pharmaceutical industries. This type of separation technique is that of the distillation columns and solvent extraction methods to carry out the purification and separation processes. The reasons for this sudden change in industry policies and methods are due to; 1. Tighter legislation control, which strongly encourages companies to use more environmentally friendly methods in their industries. 2. To save a lot of money on operation costs 3. To increase the recovery rate/yield of important products or catalysts. This is becoming increasingly important as the recovery of these solvents/catalysts saves a lot of money. Polymeric and ceramic Organic Solvent Nanofiltration membranes have only been in production in the last fifteen years. The reason why nanofiltration is only growing now so much across the different districts of industry is because when non-organic solvent nanofiltration membranes interacts with organic solvents the membranes lose stability and/or provide poor flux and rejection. As you can imagine this does not have a wide range of uses in the fine chemical district in industry. Using Membrane Extraction Technology (MET), Organic Solvent Nanofiltration process greater than 99% exchange of solvents at ambient Temperature can be achieved using up to 80% less energy than distillation and without the need for solution to go to dryness. Organic Solvent Nanofiltration used as an alternative method of solvent recovery:

Figure 5: Organic Solvent Nanofitration Efficiency As you can see above it is clear that organic solvent nanofiltration is a cost effective liquid-separation technique. Comparing the system to the commonly used distillation column we can see that it can have more than 99% exchange of solvents with using only 20% of the energy required by the distillation column. It is also a quicker process, as it doesnt require the solution to go to dryness. (Boam, A. & Nozari, A., 2006. Fine chemical: OSN a lower energy alternative. Filtration & Separation, 43(3), pp.46-48.) 1.8 Case Study 3: Identifying chemical components for organic solvent nanofiltration: The solute I have chosen Tetraoctylammonium bromide, (msds, http://www.google.com/url?sa=t&rct=j&q=&esrc=s&source=web&cd=19 &ved=0CFUQFjAIOAo&url=http%3A%2F%2Fdatasheets.scbt.com%2Fsc251208.pdf&ei=je7hTqS2KMPLhAeE0PCBAg&usg=AFQjCNGqW2IBBw6bi ZJX6h-iCa0u_fp7Bw) as it is soluble in water and has no real hazards. It is also applicable to my solvent, which is toluene. Membrane Name Nominal MWCO: 220Dalton^3 Manufacturer Max Pressure/Temperature Identity Starmem 122 220Dalton^3 Davison Membranes (supplied by Membrane Extraction Technology) 60bar and 50C Tetraoctylammonium bromide (TOABr)

Solute

MW Concentration (range) Solvent Identity Type MW Concentration (range) Flash point Spiral wound Cross-flow cell Solute flux Solute rejection Concentration polarisation Fouling Compaction Swelling Operating pressure (range) Solution diffusion Speigel-Kedem Solution diffusion + liquid film

546.81 (0-20wt%) and from (00.35M) Toluene non-polar. Aprotic 92.14 (0-0.04mole fraction) 4C

Apparatus Parameters

Transport model

30-50bar Predicts the permeate flux and solute rejection High polarization becomes significant according to the literature data at high concentrations

Analytical method

Free text commentary

The concentrations of TOABr were determined using a PerkinElmer Gas Chromatograph with a flame ionisation detector and an HP1 methyl siloxane column 30 m long 0.35 mm i.d. The temperature programmed ran from 80 to 300 C at a rate of 25 C min1, and the column temperature was held at 80 and 300 C for 3 min at the start and finish of the temperature programmed, respectively. The coefficient of variation was 2% for three independent measurements. TOABr and Toluene seem to be the ideal solute and solvent to be used to test the organic solvent nanofiltration membrane. One of the main reasons for this is that there are many relevant references to check up on to see if youre following the right path as

well as it being one of the safest methods to use, at these recommended concentrations. Link to Science Silva, P., Peeva, L.G. & Livingston, Direct or other A.G., 2010. Organic solvent source nanofiltration (OSN) with spiralwound membrane elements Highly rejected solute system. Journal of Membrane Science, 349(1-2), pp.167-174. Nunes, S.P. & Peinemann, K.-V., 2007. Membrane Technology: In the Chemical Industry, John Wiley & Sons.

From this literature data it is expected that the rejection should be very close to 100% due to the fact that the permeability of TOABr is very low.

Figure 6: Toluene Rejection Experimental and calculated TOABr observed rejection for toluene/TOABr mixtures at 30 bar, 30 C and feed flow rate 550 L h1. As you can see above the actual rejection observed was 100%, or very close to it, which is consistent with the theoretical data.

Figure 7: Flux vs. Tear Mass Fraction => Experimental and calculated flux of toluene/TOABr mixtures at pressures, 30 C and feed flow rate 550 L h1. several

2.0 Equipment: The pilot plant being used in this process is an organic solvent nanofiltration plant.

Figure 8: Organic Solvent Nanofiltration Pilot Plant This is a Koch pilot plant, which is capable of separation of aqueous and solventbased solutions. This rig can operate up to 60 bar and with temperatures as high as 50C. The tank is a 50litre tank with an integrated jacket. Using this plant you would generally only do runs with volumes of up to 30L. The control panel holds the data logger, a computer program that allows you to record your results onto a computer while you are doing your runs on the plant. The system can be disassembled for cleaning purposes, with ease.

Using an ultrasonic bath you can then sterilize the component parts you have removed as to ensure no rusting occurs. By following the Site Acceptance Test (SAT) for this pilot plant I was able to calibrate the system and see if there were any real issues with the pilot plant. There didnt seem to be any issues with the pieces of equipment of the plant as they all worked properly. 2.1 Setting Temperature and Pressure Switches: The plant has a safety system set in place in its temperature and pressure switches. The idea is that if the nanofiltration system exceeds these parameters then the rig would automatically shut itself down as a safety feature. It is a must of the person doing the runs to set the parameters before starting with your runs. As seen in the figure below these switches are easily found. By opening the side cover of the switches you are able to set the parameters of your rig.

Figure 9: Pressure and Temperature Switches

5.0 Operating Procedure 5.1 Pure water Runs: 1. Make sure your wearing the proper protective gear for the labs 2. Before switching on the pump first do a visual inspection of the pilot plant. 3. Make sure the following are done before switching on the pilot plant a. Make sure there is oil in the pump b. Make sure that the pump dial and temperature dial is set at zero c. Ensure the pressure valve (PCV001) is fully opened before starting. (Turn the dial anti-clockwise to open it fully) d. Ensure that the valves V001 and V008 are fully opened e. Make sure the valves V002, V003, V005 AND V007 are fully closed 4. Now fill the tank with 30L of dionised water. 5. Now turn on the power switch at the side 6. Start turning the pump dial switch slowly up to your desired pumps speed. (In this case 20Hz) 7. Now slowly adjust the pressure by turning the pressure gauge to your desired pressure. 8. Now let your system run for the desired length of time you have set aside for it. 9. While this is going on you must take readings, such as pressure difference across the system as well as the temperature change. You must also take readings for the permeate flow (from FIT002) as well as the retentate flow at FIT001. 10. Repeat this procedure with the different variables you have set aside for yourself. Another words if your repeating the same process with a different pressure start again from step one from this operating procedure. 11. During your procedure you will notice that your pressure will vary sometimes. You must reset your pressure, and continuously keep an eye on it. 12. When shutting down the system you must follow these simple steps a. Bring the pressure back down to roughly 0. b. Bring the pump dial down to zero which leaves the pump speed t approximately 5 Hz c. Now press the emergency stop button 13. Now turn off the power switch to the rig and start draining the solution out of the pilot plant. 5.2 Salt Water Runs: 1. Make sure your wearing the proper protective gear for the labs 2. Before switching on the pump first do a visual inspection of the pilot plant. 3. Make sure the following are done before switching on the pilot plant a. Make sure there is oil in the pump

b. Make sure that the pump dial and temperature dial is set at zero c. Ensure the pressure valve (PCV001) is fully opened before starting. (Turn the dial anti-clockwise to open it fully) d. Ensure that the valves V001 and V008 are fully opened e. Make sure the valves V002, V003, V005 AND V007 are fully closed 4. Now fill the tank with 30L of dionised water. 5. Next add and stir in your desired concentration of salt you need. 6. Now turn on the power switch 7. Start turning the pump dial switch slowly up to your desired pumps speed. (In this case 20Hz) 8. Now slowly adjust the pressure by turning the pressure gauge to your desired pressure. 9. Now let your system run for the desired length of time you have set aside for it. 10. While this is going on you must take readings, such as pressure difference across the system as well as the temperature change every 10-15minutes. You must also take readings for the permeate flow (from FIT002) as well as the retentate flow at FIT001. 11. Every 10-15 minutes take a sample of your feed, permeate and retentate and test its conductivity and TDS as well as its pH. This will tell you your salt concentrations in each of the streams.

12. Repeat this procedure with the different variables you have set aside for yourself. Another words if your repeating the same process with a different pressure start again from step one from this operating procedure. 13. During your procedure you will notice that your pressure will vary sometimes. You must reset your pressure to its desired value, and continuously keep an eye on it. 14. When shutting down the system you must follow these simple steps a. Bring the pressure back down to roughly 0. b. Bring the pump dial down to zero which leaves the pump speed t approximately 5 Hz c. Now press the emergency stop button 15. Now turn off the power switch to the rig and start draining the solution out of the pilot plant. 16. When dumping the solution from this tank make sure the pH is that close to deionized water otherwise you will need to dump it in the special disposal bins for acidic and basic solutions.

5.3 Risk Assessment:

A risk assessment report is very important to do before starting with the pilot plant as to assess the hazards and risks in your work environment. The table above shows a list of potential risks that I found around my work environment. These were mainly the entire mainly note worthy ones, that can be improved to ensure the safety of the operator. Other risks worth noting is the potential build up of static in the pilot plant, but the pilot plant is earthed so I dont think there is any further improvements to be made on the system in relation to static build up. The main one above that I think is simple to fix is providing a non-stick mat beside the nanofiltration system. There are a lot of little spillages emptying the system as its drained at the bottom side.

6.1 Experimental Data: Formulas: 1. Permeate Flux Flux Rate (L/m^2.hr)= Permeate Rate (L/hr.)/Total membrane Area (m^2)

2. Using Kochs formula for the recommended corrected flux for the system the following equation s given:

Where, C is the correction factor based on temperature (Temperature Correction. Available at: http://www.watertreatmentguide.com/temperature_correction.htm) Mainly using these two formulas the following results were gotten. 6.2 Pure Water Runs: The reason we calculate the pure water flux of the membrane is to calculate the maximum flux for that particular membrane. These results can then be compared to a non-pure water flux. By testing regularly your pure water fluxes I between processes you can determine the degradation of the membrane. This could save a lot of money in industries as they wont be losing product or time due to unexpected surprise of a degrading membrane in their system.

1. The first pure water sample I ran was running the system at 9 bar and at 20Hz. The following table is a summary of my results: Perm Flow rate (L/min)

Time Temp (Minutes) (Feed)

Ret Flow Rate (L/min)

Flux RATE Corrected Flux (L/m^2hr) (L/m^2hr.bar)

0 10 20 30

17.5 17.9 18.4 18.7

0.1032 0.0721 0.0445 0.0377

6.8271 7.1024 7.3213 7.5323

4.4229 3.0900 1.9071 1.6157

323.6727 124.3725 66.7500 41.9565

40 50 60 70 80

19.1 19.6 20.4 21.5 22.4

0.0312 0.0271 0.0219 0.0189 0.0122

7.7231 7.9132 8.1023 8.4231 8.7424

1.3371 1.1614 0.9386 0.8100 0.5229

71.7600 37.3980 26.9839 29.6386 22.1526

2. The second run I did was run at 20 bars and the pump flow was still set at 20 Hz. The following table is a summary of my results: Perm Flow rate (L/min)

Time Temp (Minutes) (Feed)

Ret Flow Rate (L/min)

Flux RATE Corrected Flux (L/m^2hr) (L/m^2hr.bar)

0 10 20 30 40 50 60 70 80

17.5 17.7 18.4 19.1 19.8 20.4 21.3 22.4 22.8

0.112 0.1072 0.0973 0.0843 0.06123 0.0423 0.0398 0.0201 0.0153

11.5213 11.7152 11.8923 11.9231 12.0123 12.02384 12.8421 12.9123 13.4239

4.8000 4.5943 4.1700 3.6129 2.6241 1.8129 1.7057 0.8614 0.6557

351.2727 336.2182 372.9833 290.8350 234.7150 208.4786 152.5667 86.6812 27.7816

3. The third run I did was run the system at 9 bar again but changed the pump speed from 20Hz to 25 Hz. The following table is a summary of my results:

Time Temp (Minutes) (Feed)

Perm Flow rate (L/min)

Ret Flow Rate (L/min)

Flux RATE Corrected Flux (L/m^2hr) (L/m^2hr.bar)

0 10 20 30 40 50 60 70 80

17.9 18.2 18.7 19.5 20 20.7 21.3 22 22.8

0.1123 0.0834 0.0634 0.0321 0.02832 0.0221 0.0132 0.0102 0.0066

9.1434 9.2426 9.3132 9.3912 9.4995 9.5843 9.6932 9.9123 10.0123

4.8129 3.5743 2.7171 1.3757 1.2137 0.9471 0.5657 0.4371 0.2829

387.4350 359.6625 273.4125 138.4313 88.8218 76.2450 56.9250 29.3250 28.4625

Finally here is a graph that illustrates the data shown in these summary tables.

Pure Water Flux vs Time

500.0000 450.0000 400.0000 350.0000 300.0000 Water Flux 250.0000 (L/m^2hr.bar) 200.0000 150.0000 100.0000 50.0000 0.0000 0 50 Time (Minutes) 100

"Pure Water Flux at 9 bar and 20Hz" Pure Water Flux at 20bar and at 20Hz Pure water flux at 9 bar and at 25 Hz

Graph 1: Pure Water Flux vs. Time The graph above illustrates the affects pressure and the pumps flow rate has on the water flux of the system. When we raise the pressure from 9 bar to 20 bar we can se the largest influence on the permeate flux. Its end point after 80 minutes of running goes from 22.2(L/m^2.bar.hr) to 27.8(L/m^2.bar.hr). The end point after 80 minutes of the run that ran at 25Hz at 9 bar finished at 28.5(L/m^2.bar.hr). Each of these statistics is to be expected and correspond within my literature data. We received an increase in permeate flux when we raised the pressure and the pump speed. Were I to test for the pure water flux again I would hopefully use more time to see it reach completion. So in conclusion it was found that with increasing pressure and in increasing the pump speed the permeate flux increases. With that said I found that for this membrane the maximum end permeate flux it should reach is 28.5(L/m^2.bar.hr) under all the conditions I used. Experimental Data:

6.3 Table of results: NaCl runs: 1. Salt and water solution was made up using 1000PPM of NaCl at 10bar and I set the pump speed to 20Hz. The following table is a summary of my results TDS TDS Time Perm Ret (Minutes) (mg/L) (mg/L) 0 0.67 0.78 10 0.68 0.79 20 1.67 1.93 30 1.62 1.95 40 1.61 1.94 50 1.63 1.95 60 1.64 1.95 70 1.64 1.97 80 1.66 1.96 Perm Flow rate Flux RATE Corrected Flux Rejection (L/min) (L/m^2hr) (L/m^2hr.bar) (%) 0.0521 2.23 17.97 14.10 0.0504 2.16 17.39 13.92 0.04712 2.02 16.26 13.47 0.04134 1.77 14.26 16.92 0.04344 1.86 14.99 17.01 0.03964 1.70 13.68 16.41 0.0345 1.48 11.90 15.90 0.0344 1.47 11.87 16.75 0.0341 1.46 11.76 15.31

2. Salt and water solution was made up using 5000PPM NaCl at 9 bars and I set the pump speed to 20Hz. The following table is a summary of my results: Perm TDS TDS Flow Perm Ret rate Flux RATE Corrected Flux Rejection (mg/L) (mg/L) (L/min) (L/m^2hr) (L/m^2hr.bar) (%) 4.14 4.29 0.0488 2.09 120.26 3.50 4.19 4.35 0.0488 2.09 168.36 3.68 4.11 4.27 0.0282 1.21 64.86 3.75 4.23 4.39 0.0135 0.58 33.27 3.64 4.23 4.4 0.0068 0.29 29.33 3.86 4.28 4.46 0.008 0.34 30.67 4.04 4.29 4.49 0.0028 0.12 12.08 4.45 4.21 4.42 0.003 0.13 12.94 4.75 4.19 4.39 0.0024 0.10 9.20 4.56 3. Salt and water solution was made up using 10000PPM NaCl at 9 bar and I set the pump speed to 20Hz. The following table is a summary of my results:

Time (Minutes) 0 15 30 45 60 75 90 105 120

Time (Minutes) 0 15 30 45 60 75 90 105 120

TDS Perm (mg/L) 8 7.88 7.81 8.24 7.84 7.75 7.72 7.81 7.7

Perm TDS Ret Flow rate Flux RATE Corrected Flux Rejection (mg/L) (L/min) (L/m^2hr) (L/m^2hr.bar) (%) 8.15 0.0142 0.61 44.54 1.84 8.01 0.0106 0.45 36.57 1.62 7.9 0.0064 0.27 31.54 1.14 8.32 0.008 0.34 25.09 0.96 7.92 0.0035 0.15 13.42 1.01 7.83 0.0021 0.09 8.05 1.02 7.79 0.0042 0.18 14.49 0.90 7.88 0.0039 0.17 13.46 0.89 7.76 0.0035 0.15 10.98 0.77

4. Salt and water run was made up using 5000PPM NaCl at 2bar and I set the pump speed to 20Hz. The following table is a summary of my results: Perm TDS TDS Flow Perm Ret rate Flux RATE Corrected Flux Rejection (mg/L) (mg/L) (L/min) (L/m^2hr) (L/m^2hr.bar) (%) 4.19 4.33 0.022 0.94 84.33 3.23 4.27 4.42 0.02012 0.86 77.13 3.39 4.16 4.32 0.0108 0.46 46.58 3.70 3.94 4.12 0.0072 0.31 31.05 4.37 4.09 4.29 0.0064 0.27 27.60 4.66 4.06 4.27 0.0051 0.22 19.55 4.92 3.95 4.16 0.0016 0.07 7.89 5.05 3.8 4.01 0.0008 0.03 3.94 5.24 3.82 4.07 0.0006 0.03 2.30 6.14

Time (Minutes) 0 15 30 45 60 75 90 105 120

5. Salt and water run was made up using 5000PPM NaCl at 9 bar and I set the speed of the pump to 25Hz. The following table is a summary of my results: TDS Perm (mg/L) 4.09 4.19 4.05 4.06 3.93 4.13 4.13 4.11 4.19 TDS Ret (mg/L) 4.23 4.35 4.21 4.23 4.11 4.33 4.34 4.33 4.42 Perm Flow rate Flux RATE Corrected Flux Rejection (L/min) (L/m^2hr) (L/m^2hr.bar) (%) 0.05818 2.49 200.72 3.31 0.05818 2.49 167.27 3.68 0.05381 2.31 154.70 3.80 0.0365 1.56 96.87 4.02 0.0268 1.15 84.05 4.38 0.0158 0.68 77.87 4.62 0.0106 0.45 30.47 4.84 0.0084 0.36 28.98 5.08 0.0075 0.32 19.90 5.20

Time (Minutes) 0 15 30 45 60 75 90 105 120

These results can be more easily compared by the following graph, which shows theyre corresponding, permeate flux and rejection rates.

Rejection Percentage vs. Time:

Rejection vs Time @ 20Hz

18.00 16.00 14.00 12.00 10.00 Rejection (%) 8.00 6.00 4.00 2.00 0.00 10000PPM of NaCl @ 9bar 5000 PPM OF NaCl @ 9 bar (@25HZ) 5000PPM of NaCl @ 2bar 1000PPM of NaCl @ 10bar 5000PPM of NaCl @ 9bar

Time (Minutes)

Graph 2: Rejection vs. Time As you can see from the following graph it is clear to see that the salt concentration directly affects the effectiveness of the nanofiltration membrane and its ability to reject. This corresponds to Case Study 2, where it stated that at higher salt concentration the rejection value would be lower. As you can also see from this graph it is clear that the change in pressure has little or no effect on the membranes ability to reject the solute.

Permeate Flux vs. time

Permeate Flux vs Time at 20Hz

250.00

200.00

1000PPM of NaCl @ 10bar 150.00 permeate Flux (L/m^2.hr.bar) 100.00 5000PPM of NaCl @ 9 bar ( @ 25Hz) 5000PPM OF NaCl@ 2bar 50.00 5000PPM NaCl @ 9 bar 10000PPM of NaCl @ 9 bar

0.00 0 50 100 Time(Minutes) 150

Graph 3: Permeate Flux vs. Time It is clear to see from the following graph that two variables effect the permeate flux directly. As you can see the two variables that stand out is the pressure and the pump speed. Firstly by increasing the pump speed from 20Hz to 25Hz there was directly an increase in the permeate flux which can be clearly seen in the graph. This change also had a direct influence on the pressure as I had to readjust for a while to get the pressure to stay at 9bar. The second, and more noteworthy variable that influences the permeate flux is the pressure. As you can see from when comparing the results from the systems running at 9bar to the system running at 2bar, it is clear that there is a big decrease in permeate flux. This data also corresponds to the literature data.

7.0 Discussion: The main objectives I undertook in this project were to calibrate the pilot plant for pure water system and salt water run. Firstly calibrating the pure water runs was standard operating procedure as seen above in 3.0. By measuring the permeate flux I was able to calculate the maximum permeate flux this membrane was going to allow me to receive. This was important as I could compare my NaCl solution permeate flux to my pure water ones. The results showed me that the permeate flux for salt-water runs were around half that of the pure water runs. I was originally meant to do organic solvent runs, but due to time management issues it didnt come about that I would be able to get the material needed to do all the runs. Instead I did a case study (case study 3) on the organic solvent I would use. Toluene is a very common solvent used in industries today and the fact that the organic solvent nanofiltration plant should give high rejections; any operators would easily see it why it is the ideal solvent. The other reason I chose toluene is that there is plenty of referenced case studies using it, as an organic solvent so there is plenty of results to compare to. Deciding on a salt, I chose NaCl. There are other salt solutions, which give a higher rejection, such as MgSO4, but with NaCl already being in the lab in bulk, and the fact that I found some literature review on it I thought it would do just as well. I believe the results were very satisfactory as they followed the trend that I was expecting comparing it to the literature data. Although if I were to repeat the salt runs again I would run them at a higher pressure and at a lower salinity value as it would give me more ideal results. During my runs I was meant to have the data logger program recording my results as I was taking down the ones I saw visually. Unfortunately the computer did not recognize the data logger and even though I had done all the preparations for it to work, it just wouldnt take any readings. After asking the lab with the lab technicians and asking the lecturers who were in the lab, it was plain to see no one knew how to program this data logger properly so that it would take readings. This was very unfortunate, as I cannot compare my results to the ones t was meant to take. Seemingly when it was run 2 years ago there was an issue with the flow meters readings. During the course of my lab work I ordered eight waste disposal bins for organic solvents and solution wastes that cant go down the drain. This was done because there was a huge shortage of them in the lab and if there was a use for them there wouldnt be enough to be continuously dumping organic solvent wastes into them. These waste disposal bins only came in last week and took over six weeks to arrive. This means that if I had the organic material for the organic runs

I would have been very limited on the number of runs as I would be disposing 30L which every run.

8.0 Conclusion: My results are split into three categories. Two experimental, which are my Pure water runs and my Salt-water runs, and then there is my literature data on using an organic solvent in the pilot plant. Firstly as we can see the Pure-water runs and the salt-water runs both followed the same trend in that if you increased the pressure or the pump speed of the nanofiltration system it will result in an increase in permeate flux. With this boundary I found that the maximum permeate flux of this membrane was 28.5 (L/m^2.bar.hr). This compared to the salt-runs maximum permeate flux which was 19.90 (L/m^2.bar.hr) told me that the pump speed had the biggest influence on the permeate flux as well as pressure. There has to be caution when increasing the pump speed as if you go too high permanent damage is to be expected on the membrane. In conclusion, as you can see from my results or literature data, we can have some relative control over the way we want the pilot plant to work. Firstly we can control the amount of permeate flux by increasing pressure and/or increasing the pumps speed. Both of these parameters increase the permeate flow. Monitoring the concentration of salt in the solution can control the rejection percentage of the solute. As you can see in my literature data, as well as my results the salinity of the solution has a huge effect on the rejection value. By decreasing the salinity of your solution you get an increase in the rejection. From my literature data you will see that I have chosen Toluene as the ideal organic solvent to be used in this pilot plant. As you can see in Case Study -3 a rejection of nearly 100% is to be expected. Since youre only using 0.04M concentration of the solvent there isnt any concern over safety. The solute I have chosen is Tetraoctylammonium bromide. I have supplied two references, which gives results and background pertaining to the toluene-TOABr mixed solution and both are very detailed and easy to follow.

9.0 Recommendations: Some of these recommendations didnt affect me, due to the fact that I didnt do an organic solvent run, but in my opinion they need to be dealt with before anyone can do one. The first recommendation I would like to make is that the operator doing this project should only do an organic solvent run or a salt run. There isnt enough time to calibrate for all three scenarios of; 1) Pure water runs

-This one needs to be done as to determine the maximum permeate flux of the membrane as well as making sure everything works without any major difficulty 2) Salt-Water Runs - This one I dont see the importance of doing with an organic solvent nanofiltration plant. I would recommend dropping this calibration 3) Organic Solvent Run - I didnt get an opportunity to do an organic solvent run this semester due to time management problems. I believe the organic solvent and the solute should be ordered in the first week of college for the next operator as doing these runs take a lot of time and waiting for the components to come in could take up to 8 weeks, like the waste disposal bins I ordered. Secondly I recommend that waste disposals also be ordered in the first two weeks of the semester. The waste disposal bins for the solutions are only 25L big, meaning you will use a full one for each run. With at least 6 organic runs needed to be done that means you would want to make sure your able to dispose of your solution before starting. I would recommend having someone able to use the delogger program. I know that there is a manual, which is easy to follow, but the reason I couldnt get it working wasnt because I couldnt run it, but because it wouldnt connect to the computer. Since no one knew how to fix this problem no results were gotten from the delogger program. So in conclusion I recommend having someone able to connect and run the program successfully near the lab to get more accurate results. If someone is to do salt runs again I would probably recommend that they use MgSO4 as there salt solution. This solution should give higher, and more acceptable rejection values.

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