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Advances in Filtration Technology Argonide Corporation, Sanford, Florida Argonide Corporation DTRA.

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1 Advances in Filtration Technology Argonide Corporation, Sanford, Florida Argonide Corporation DTRA

2 Introduction to Filtration: The Basics Filtration Comfort Zone Distillation Ion Exchange Carbon Adsorption Microporous Filtration (MF) Ultraporous Filtration (UF) Reverse Osmosis (RO) Backwashable vs. Disposable Cartridge Filters vs. Bag Filters Cartridge Filters Bag Filters

3 Filtration Comfort Zone Most veteran filtration professionals are comfortable with filtration that works through mechanically sieving particles that are equal to or larger than the poresize of the filter media Most veteran filtration professionals are comfortable with filtration that works through mechanically sieving particles that are equal to or larger than the poresize of the filter media A filter with a poresize of 2 μm will retain particles to 2 μm with great efficiency, but will pass particles that are finer in size. A filter with a poresize of 2 μm will retain particles to 2 μm with great efficiency, but will pass particles that are finer in size. A surface filter (i.e. membrane) will retain particulate on its surface that faces the influent stream A surface filter (i.e. membrane) will retain particulate on its surface that faces the influent stream Standard fibrous depth filters have an advantage as they capture dirt throughout their filtration matrix, thereby increasing the dirt holding capacity Standard fibrous depth filters have an advantage as they capture dirt throughout their filtration matrix, thereby increasing the dirt holding capacity These standard fibrous depth filters are still limited in their efficiency at capturing smaller particulate by their poresize even with an increased efficiency through filter cake build-up These standard fibrous depth filters are still limited in their efficiency at capturing smaller particulate by their poresize even with an increased efficiency through filter cake build-up

4 Distillation Distillation is probably the oldest method of water purification. Water is first heated to boiling. The water vapor rises to a condenser where cooling water lowers the temperature so the vapor is condensed, collected and stored. Most contaminants remain behind in the liquid phase vessel. However, there can sometimes be what is called carry-overs in the water that is distilled. Organics such as herbicides and pesticides, with boiling points lower than 100°C cannot be removed efficiently and can actually become concentrated in the product water. Another disadvantage is cost. Distillation requires large amounts of energy and water. Distilled water can also be very acidic, having a low pH, thus should be contained in glass. It lacks oxygen and minerals and has a flat taste, which is why it is mostly used in industrial processes.

5 Ion Exchange The ion exchange process percolates water through bead-like spherical resin materials (ion-exchange resins). Ions in the water are exchanged for other ions fixed to the beads. The two most common ion-exchange methods are softening and deionization. Deionization can be an important component of a total water purification system when used in combination with other methods discussed in this primer such as RO, filtration and carbon adsorption. DI systems effectively remove ions, but they do not effectively remove most organics or microorganisms. Microorganisms can attach to the resins, providing a culture media for rapid bacterial growth and subsequent pyrogen generation. Softening is used primarily as a pretreatment method to reduce water hardness prior to reverse osmosis (RO) processing. The softeners contain beads that exchange two sodium ions for every calcium or magnesium ion removed from the "softened" water.

6 Carbon Adsorption Activated carbon effectively removes many chemicals and gases, and in some cases it can be effective against microorganisms. However, generally it will not affect total dissolved solids, hardness, or heavy metals. The rate of adsorption is a function of the molecular weight and size of the organics. Carbon also removes free chlorine and protects other purification media in the system that may be sensitive to an oxidant such as chlorine. Carbon is usually used in combination with other treatment processes. The placement of carbon in relation to other components is an important consideration in the design of a water purification system. Activated carbon is created from a variety of carbon-based materials in a high- temperature process that creates a matrix of millions of microscopic pores and crevices. The carbon adsorption process is controlled by the diameter of the pores in the carbon filter and by the diffusion rate of organic molecules through the pores.

7 Microporous Basic Filtration There are three types of microporous filtration: depth, screen and surface. Depth filters are matted fibers or materials compressed to form a matrix that retains particles by random adsorption or entrapment. Screen filters are inherently uniform structures which, like a sieve, retain all particles larger than the precisely controlled pore size on their surface. Surface filters are made from multiple layers of media. When fluid passes through the filter, particles larger than the spaces within the filter matrix are retained, accumulating primarily on the surface of the filter. In many respects, surface filters can often be constructed from multiple layers of Screen Filters.

8 Microporous Basic Filtration (cont.) The distinction between filters is important because the three serve very different functions. Depth filters are usually used as prefilters because they are an economical way to remove 98% of suspended solids and protect elements downstream from fouling or clogging. last possible point in a system to remove the last remaining traces of resin fragments, carbon fines, colloidal particles and microorganisms. Surface filters can remove 99.99% of suspended solids and may be used as either prefilters or clarifying filters. Microporous membrane (screen) filters are placed at the

9 Ultrafiltration A microporous membrane filter removes particles according to pore size. Taking it a step further, an ultrafiltration (UF) membrane does much the same, but with smaller pore structure providing a finer filtration level. Ultrafiltration membranes could be used to separate very fine suspended or un- dissolved contaminants from water. Over time, ultrafilters have also gained some acceptance relative to the separation of oil from water in oily emulsions. It is important to note that selection of the correct ultrafilter membrane is critical to the successful removal of targeted contaminants from water. Selection of the wrong membrane can result in ineffective removal of contaminants or irreversible fouling, which may result in an expensive membrane replacement.

10 Reverse Osmosis (R.O.) The pore structure of RO membranes is much tighter than UF membranes. RO membranes are capable of rejecting practically all particles, bacteria and organics >300 daltons molecular weight (including pyrogens). In fact, reverse osmosis technology is used by most leading water bottling plants. Because RO membranes are very restrictive, they yield slow flow rates. Storage tanks are required to produce an adequate volume in a reasonable amount of time. Reverse osmosis is highly effective in removing several impurities from water such as total dissolved solids (TDS), turbidity, asbestos, lead and other toxic heavy metals, radium, and many dissolved organics. The process will also remove chlorinated pesticides and most heavier-weight VOCs. RO is the most economical and efficient method for purifying tap water if the system is properly designed for the feed water conditions and the intended use of the product water. RO is also the optimum pretreatment for reagent-grade water polishing systems.

11 Backwashable vs. Disposable As an example: 1. Multi-media beds; 2. Sediment filters; 3. Micro or Ultraporous Membrane 4. R.O. Membrane Most applications will benefit from some form of gradient filtration. Stepping from coarse to fine to polishing modes extends the active life of each level of filtration, often improving the economics. At coarser levels of filtration, inexpensive filter elements (sometimes backwashable) are fairly common. When you move into the sub-micron filtration range, membranes become the only real viable alternative for backwashable filtration, but at a high cost.

12 Cartridge Filters vs. Bag Filters In many filtering applications, a choice between the use of a cartridge filter or a bag filter has to be made. Both are sediment filters, but there are some differences between these two filter systems: In general, cartridge filters are preferable for systems with contaminations lower than 100 ppm, that is to say with contamination levels lower than 0.01% in weight. Conversely, bag filters are preferable for systems with higher contamination loads. Conditions that can affect this choice include flow rates and the nature of the contaminants being filtered from the process stream.

13 Cartridge Filters Conventional cartridge filters can be surface or depth-type filters. The choice of which type of cartridge filter depends on the application: 1.Surface filters (that are usually made of thin materials like papers, woven wire, cloths) function by blocking particles on the surface of the filter. Surface filters are best if you are filtering sediment of similar-sized particles. If all particles are i.e. five micron, a pleated 5-micron filter works best because it has more surface area than other filters. 2.Depth-type filters capture particles and contaminants through the total thickness of the medium. Compared with pleated surface filters, depth filters have a limited surface area, but they have the advantage of depth. It can be generally stated that if the size of filter surface is increased, higher flows are possible, the filter lasts longer, and the dirt-holding capacity increases. Cartridge filters are typically designed as disposable.

14 Bag Filters In general, bag filters are frequently used for dust removal in industrial applications. Bag filters are mostly surface-type filters. The flow can be from the outside to the inside of the filter (that means, the separation of particles happens on the external surface of the filter) or the other way around, depending on the application. The particles are normally captured on the internal surface of the bag filter. The later is most common when filtering fluids. Bag filters are generally designed for replacement when they are clogged, but some bag filters for gaseous applications like dust removal can be cleaned, for example by mechanical shaking or by backwashing with compressed air (so called reverse-flow bag filters). Bag filters are generally designed for replacement when they are clogged, but some bag filters for gaseous applications like dust removal can be cleaned, for example by mechanical shaking or by backwashing with compressed air (so called reverse-flow bag filters). A rule of thumb is that for concentrations higher than 5 mg/m 3 a surface filter is favored, while for concentrations lower than 0.5 mg/m 3 a depth-type filter is preferred. In general, surface filters can by backwashed and cleaned more easily, while depth-type filters normally have to be disposed when clogged.

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16 NanoCeram ® – Next Generation Filtration General Background – Nano Alumina (NanoCeram) Filters How Does It Work? Nano Alumina Filter Characteristics Electron Microscopic Image Filtering Dirt Particles Comparison of Flow Capacity Adsorption Curves for Different Size of Latex Spheres Prefilters for Reverse Osmosis (RO) Membranes Metals Reduction Iron Removal Iron Regeneration Studies The Value of Iron Removal

17 General Background - NanoCeram Filters 1. Dirt holding capacity of NA filters exceeds typical UP membranes by ~ 100 times 2. Flowrates of NA filters are two orders of magnitude greater than UP membranes 3. NA filters have higher particle retention efficiency than MP and UP membranes Nano alumina (NC for nano ceramic or NanoCeram) fibers are combined into a non-woven filter, and retain particles by electrostatic forces Data are presented on dirt holding capacity, flowrate and filtration efficiency, focusing on sub-micron particles, showing:

18 How Does It Work? 1. Average poresize of 2µ yields an absolute rating of 0.2µ 2. Flowrates of NA filters are many times greater than 0.2µ MP membranes with similar 0.2µ particle retention efficiency 3. NA filters have higher particle retention efficiency than MP and UP membranes Nano alumina fibers with an average diameter of 2nm are infused throughout the entire structure of the filter medias matrix. Literally trillions of highly electropositive nano alumina fibers per ft 2 of media provide a high degree of freedom in designing filtration solutions: This freedom in designing filtration solutions can be extended into other arenas including air filtration. By adjusting the porosity of the filter media, reduced pressure drop can be achieved, often with efficiencies far beyond other existing technologies.

19 Nano alumina fibers are combined with microglass fibers to produce a non-woven filter media with a pore size of ~2 microns; Nano alumina fibers are combined with microglass fibers to produce a non-woven filter media with a pore size of ~2 microns; These nano alumina fibers are highly electropositive and retain particles by electroadhesion; These nano alumina fibers are highly electropositive and retain particles by electroadhesion; The media is ~0.8 mm thick; The media is ~0.8 mm thick; It can retain silica, activated carbon, natural organic matter, metals, cysts, bacteria, DNA/RNA and virus; It can retain silica, activated carbon, natural organic matter, metals, cysts, bacteria, DNA/RNA and virus; The media can be pleated or rolled to form cartridges; formed into a bag; or used as flat stock in filter presses and other filtration devices. The media can be pleated or rolled to form cartridges; formed into a bag; or used as flat stock in filter presses and other filtration devices. Nano alumina fibers are combined with microglass fibers to produce a non-woven filter media with a pore size of ~2 microns; Nano alumina fibers are combined with microglass fibers to produce a non-woven filter media with a pore size of ~2 microns; These nano alumina fibers are highly electropositive and retain particles by electroadhesion; These nano alumina fibers are highly electropositive and retain particles by electroadhesion; The media is ~0.8 mm thick; The media is ~0.8 mm thick; It can retain silica, activated carbon, natural organic matter, metals, cysts, bacteria, DNA/RNA and virus; It can retain silica, activated carbon, natural organic matter, metals, cysts, bacteria, DNA/RNA and virus; The media can be pleated or rolled to form cartridges; formed into a bag; or used as flat stock in filter presses and other filtration devices. The media can be pleated or rolled to form cartridges; formed into a bag; or used as flat stock in filter presses and other filtration devices. Nano Alumina Filter Characteristics

20 Electron Microscopic Image NanoCeram ® Fibers The active ingredient of the filter media is a nano alumina (AlOOH) fiber, only 2 nanometers in diameter. The nano fibers are highly electropositive. The filter media is manufactured through paper making tech- nology. In a multi-step process, the nano fibers (right) are dispersed and adhere to glass fibers. The nano alumina is seen as a fuzz on the microglass fiber (left). Because the nano alumina is fully dispersed, particles have easy access to the charged surface.

21 Capacity of NanoCeram media when tested with A2 fine test dust (~1-4 µm) vs data presented by C. Shields for other media. Its dirt holding capacity of 574 mg/in 2 is almost twenty times greater than microglass filter media when compared at a pore size rating of 1 µm; and far greater than that if compared at the smaller pore size ratings. Filtering Dirt Particles

22 Comparison of Flow Capacity Pore size rating The NanoCeram filters flow rate is superimposed over Shields data [1] for clean water. Its flow rate is about four times that of 1 µm microglass media and even greater when compared to 0.2 or 0.5 µm pore size filters. The flow rate through meltblown and membrane media are even much less. 1 - C. Shields, High Performance Microfiltration Media, Presented at American Filtration Meeting, Marriott, Baltimore/Washington Airport, Nov , 2004

23 Adsorption Curves for Different Size Latex Beads Adsorption Curves for Different Size Latex Beads A single layer 25 mm diameter NanoCeram filter disk was 3 cm/min by a continuous stream of latex beads. The filter eventually clogs without exhibiting a breakthrough curve, except for the smallest (0.03 µm) beads. Bacteria size particles (0.2 to 4.5 µm) are intercepted with high efficiency.

24 Prefilters for Reverse Osmosis (RO) Membranes RO filters are expensive to replace and are highly sensitive to fouling by sub-micron particles. Ultraporous (UP) membranes are often used as RO prefilters. They too are subject to fouling, and are used in a cross- filtration mode to minimize fouling. Cross flow results in a waste stream, often 3-10 times greater than the stream being purified. NanoCeram filters can sustain high flow in a dead-end mode and generate no waste stream. Results include significant increase of flux through an RO membrane by significantly reducing the quantity of sub- micron particulate (silt) challenging the membrane during operation.

25 Metals Reduction Independent laboratory testing has shown that this electropositive filter media is effective in adsorbing a variety of metals in both ionic and particulate form. These include: Iron Iron Aluminum Aluminum Copper Copper Tin Tin Lead Lead Chromium III Chromium III Filtered Volume through 8.2 cm 2 NanoCeram Filter

26 Iron Removal Testing performed at TMMK for iron reduction in chill water determined that although quite effective at iron removal, a typical 4.5 x 20 filter cartridge would plug after filtering only 2,400 gallons of chill water with a 3 ppm iron concentration. Considering that the levels of iron would decline as filtration continued over time, this scenario would require a total of 4,000 filter cartridges to bring the iron levels down to near zero. The combination of iron and iron bacteria in that system leads to corrosive conditions requiring continuous maintenance and repair of chiller tubes; and eventually the many linear miles of iron piping comprising this closed loop system. These filter cartridges are not inexpensive and the project was not feasible considering that each cartridge is considered a dead end filter. Prior experience with these filters has shown that it is nearly impossible to remove adsorbed contaminants from the filters after they have been adsorbed. Recharging the filters has been an ongoing subject for several years.

27 Iron Regeneration Studies In part, due to this testing performed at TMMK for iron reduction, Argonide embarked on a program that has shown that NanoCeram filters can be recharged when used in an iron reduction mode. Laboratory testing using a simple process has yielded a recovery rate of approximately 90% for a standard NanoCeram filter cartridge for iron. This testing has shown that the iron capacity of a standard NanoCeram filter is approximately 4 times improved over the initial results achieved at TMMK. This process can be utilized on-site with minimal interruption of service. In the scenario previously mentioned, total filter usage is much more reasonable and brings the project closer to an acceptable ROI.

28 The Value of Iron Reduction In addition to chill water systems at TMMK and other plants, additional areas of interest include: Steam Condensate Recovery – a pilot project is underway at TMMI to recover approximately 40 gpm of steam condensate that is currently being sent to waste. This waste water is at 90°C contains approximately 0.15 ppm of Iron. Recovery of this water will save Toyota both in terms of water waste and energy consumption. Robotic Welders – although not currently under study, reducing the iron fouling in the cooling lines may significantly extend the lifetime of those lines providing savings in materials and labor.

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30 The Future of Activated Carbon Filtration Advancement in Organics Reduction SEM of PAC in Nano Alumina / Microglass Dynamic Iodine Adsorption by NanoCeram-PAC Dynamic Chlorine Adsorption by NanoCeram-PAC Filtration of Sub-Micron Organic Particles (TOC)

31 NanoCeram technology excels as a particle adsorber. NanoCeram technology excels as a particle adsorber. Use this attribute to capture and retain other functionalized adsorbent materials in particle form... in the smallest size particle available. Use this attribute to capture and retain other functionalized adsorbent materials in particle form... in the smallest size particle available. NanoCeram-PAC contains approximately 32% (by weight) of powder activated carbon with an average particle size of 25 microns. NanoCeram-PAC contains approximately 32% (by weight) of powder activated carbon with an average particle size of 25 microns. This provides enormous activated carbon surface area which is not partially occluded by adhesives or glues, nor is the carbon capacity compromised by the organics in such adhesives. This provides enormous activated carbon surface area which is not partially occluded by adhesives or glues, nor is the carbon capacity compromised by the organics in such adhesives. Advancement in Organics Reduction

32 Competitive media was sectioned from commercial cartridges and tested as 25 mm discs. Microscopic exam shows 2 of the 3 competitive medias tested use granular activated carbon. Competitive media was sectioned from commercial cartridges and tested as 25 mm discs. Microscopic exam shows 2 of the 3 competitive medias tested use granular activated carbon. There is a remarkable retention of I 2 (iodine) by one layer of PAC-NC to a low cut-off (0.5 ppm, the level at which Iodine is detectable by taste and odor); There is a remarkable retention of I 2 (iodine) by one layer of PAC-NC to a low cut-off (0.5 ppm, the level at which Iodine is detectable by taste and odor); Approximately 180 times longer than competitive activated carbon media at comparable basis weight; Approximately 180 times longer than competitive activated carbon media at comparable basis weight; The dynamic adsorption by immobilized ultra fine PAC is believed to be responsible. The dynamic adsorption by immobilized ultra fine PAC is believed to be responsible. Advancement in Organics Reduction (cont.)

33 SEM of PAC in Nano Alumina/Microglass Note: fine fraction of PAC particles incorporated into structure.

34 Dynamic Iodine Adsorption by NanoCeram-PAC Test Method: 20 ppm Iodine thru single layer, 25 mm 50 ml/min. Two ml aliquots collected into a cuvette and measured at 290 nm using UV/VIS spectrophotometer. The detection limit is ~ 0.3 ppm.

35 Dynamic Chlorine Adsorption by NanoCeram-PAC Modeling also indicates that a standard 2.5 x 10 filter cartridge manufactured with NanoCeram-PAC media will reduce free chlorine from 2ppm to < 1ppm for over 2,000 2 gpm flow rates.

36 The filter is excellent for adsorbing turbidity. Filters (25 mm diameter) were challenged with humic acid, an organic particle small enough to pass through Absolute 0.2 µ filters. Breakthrough was detected by both optical turbidity and spectrophotometric methods. Note the high filtration efficiency until the filter is exhausted at about 0.4 L of fluid/cm 2 of filter area. Filtration of Sub-Micron Organic Particles (TOC) Filtration of Sub-Micron Organic Particles (TOC)

37 Other Applications Reduction of chlorine and other organics through the use of NanoCeram-PAC technology Reduction of chlorine and other organics through the use of NanoCeram-PAC technology Recycling industrial water thereby increasing water re-use rates Recycling industrial water thereby increasing water re-use rates Polishing filtration downstream of UP, MP and even RO systems. Polishing filtration downstream of UP, MP and even RO systems. Prefiltration prior to ultraviolet or ozone treatment to minimize the burden on such sterilization devices Prefiltration prior to ultraviolet or ozone treatment to minimize the burden on such sterilization devices Prefiltration prior to ion exchange beds extending their useful life and reducing the frequency of cleaning cycles Prefiltration prior to ion exchange beds extending their useful life and reducing the frequency of cleaning cycles Develop adsorption data for endocrine disruptors, antibiotics and dioxin from industrial waste streams using PAC (Initial data are promising) Develop adsorption data for endocrine disruptors, antibiotics and dioxin from industrial waste streams using PAC (Initial data are promising)

38 Specialty Filters PACB & PB Series: Hybrid Cartridges DP Series: Dual Layer NC & PAC Cartridges LR-19 Series: Lenticular Replacement Cartridges Gravity Flow Water Purifier

39 PACB & PB Series: Hybrid Cartridges Hybrid designs which incorporate a carbon block as the centercore with a pleated layer wrapped around the block. 2.5 and 4.5 diameter cartridges fit in standard housings.

40 DP Series: Dual Layer NC & PAC Cartridges Dual pleated layer 2.5 and 5 diameter cartridges fit in standard housings.

41 LR Series: Lenticular Filter Replacement Filter Cartridges The dual pleated layer NC (or NC-PAC) cartridge on the left is a drop in replacement for the lenticular filter (right). Lenticular filters are also known as Disc Filters.

42 Gravity Flow Water Purifier This purifier operates where there is no source of running water nor electricity. Eureka Forbes designed the device using NanoCeram-PAC filter technology and, with Argonides help, manufactures the filter cartridges.

43 NanoCeram - Worldwide Active Distribution Direct Sales Latin American Territories and Costs

44 Active Distribution NanoCeram Distributors United States Canada South Korea (Exclusive) Japan Italy Sweden Poland France Greece South Africa Turkey United Kingdom Ireland Kuwait Azerbaijan

45 Direct Sales NanoCeram Sales United States Canada Italy Norway France United Kingdom Ireland United Arab Emirates (UAE) Slovenia Brazil Thailand Japan Russia Norway

46 Latin America: Exclusive Territories & Costs Colombia:$46,000 USD Venezuela:$46,000 USD Peru:$44,000 USD Argentina:$66,000 USD Ecuador:$35,000 USD Mexico:$80,000 USD NanoCeram Sales

47 THANK YOU Henry Frank ( x103)


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