Patent Grant
10106436
The present disclosure relates generally to apparatus, systems and methods related to drinking water purification.
The pollution of ground and drinking water by metalloids, especially arsenic, a wide range of toxic metals, such as but not limited to, lead, mercury, cadmium, chromium, nickel, iron, cupper, platinum, and palladium, as well as various organic chemicals, has attracted increasing attention in recent decades throughout the world. Particularly, the contamination of water by arsenic has been one of the most serious health hazards and its remediation to the Level of Concern (LOC) (10 ppb) has proven challenging.
The presence of arsenic in waterways is due to both natural and anthropogenic causes. For example, arsenic may be released into waterways due to volcanic activity and from erosion of natural deposits such as rocks and terrain that has been burned due to forest fire. Further, arsenic may be released into waterways due to agricultural runoff, industrial production waste runoff, etc. For example, some fertilizers contain arsenic and further, industrial practices such as copper smelting, mining, and coal burning also contribute to arsenic in the environment.
Consuming excessive amounts of arsenic from drinking water may contribute to a number of mild to severe health effects. For example, arsenic has been linked to thickening and discoloration of the skin, stomach pain, nausea, vomiting, diarrhea, numbness of the extremities, partial paralysis, and blindness. Further, arsenic has been credited as a carcinogen and linked to cancer of the bladder, lungs, skin, kidney, nasal passages, liver, and prostate, as well as a factor contributing to cardiovascular disease.
Since ground water sources and surface water sources are susceptible to arsenic contamination, it is imperative to purify water from these sources prior to human and animal consumption. The World Health Organization (WHO) and US Environmental Protection Agency (EPA) have set the arsenic standard for drinking water at 0.010 parts per million (10 ppb) to protect consumers served by public water systems from the effects of long-term, chronic exposure to arsenic. While the EPA standard applies to municipal water treatment facilities, it is desirable to remove arsenic from other water treatment systems as well. Indeed, in the United States, the National Resources Defense Council estimates that over 34 million Americans drink from water supplies with average arsenic concentrations that pose unacceptable cancer risks.
Arsenic removal technology can be applied to large scale water treatment systems, small scale water treatment systems, point-of-use water treatment systems, well water treatment systems, portable water treatment systems, and other systems.
Previous solutions for removing arsenic from drinking water involve processes/technology such as flocculation, modified coagulation/filtration, modified lime softening iron oxide adsorption, activated alumina, ion-exchange, reverse osmosis, electrodialysis, subterranean arsenic removal (SAR), and metal loaded polymers. Flocculation and iron oxide adsorption techniques generally use an iron-based coagulant to remove arsenic by co-precipitation and/or adsorption. However, the toxic arsenic sludge resulting from coagulation often clogs the system and the toxic arsenic sludge has to be disposed of by concrete stabilization. While this may be a sufficient short term solution, the toxic arsenic sludge may leach over time and thus be reintroduced into the environment.
Ion-exchange has traditionally been used as a water-softening process and has some ability to remove arsenic. However, arsenic exists in two oxidation states in water depending on the oxidation-reduction conditions and the pH of the water. As(III) is usually associated with groundwater under anaerobic conditions, while As(V) is associated with surface water under aerobic conditions. As(III) is found as the neutral species, arsenous acid (H3AsO3), below pH 9. As(V) occurs as the monovalent and the divalent arsenate species, H2AsO4− and HAsO42−, respectively, between pH 6 and 9. Ion-exchange is ineffective in removing non-charged arsenic(III) species. Further, the presence of sulfate and high total dissolved solids can significantly affect run length and maintaining an ion-exchange column is costly and requires a skilled technician.
Reverse osmosis and electrodialysis techniques can remove arsenic but result in high salinity waste water, which presents an issue in that it requires further waste water treatment. Further, both technologies are high cost. SAR technology utilizes an oxidation zone to trap iron and arsenic underground. The technology relies upon soil dwelling microorganisms to metabolize iron and arsenic and break these substances down to other molecular species. Such a technology is extremely expensive to develop and operate. In addition, this technique is not simple and requires well simulated (calculated) and balanced aquifer oxidation. Otherwise, the oxidation procedure will just lead to arsenic and iron co-precipitation rather than adsorption, resulting in the subsequent release of arsenic. Metal-loaded polymers and granular metal, especially Fe(III) are interesting due to the possibility to remove both As(III) and As(V), however, the arsenic binding is pH dependent and there remains the possibility of releasing the impregnated metal in solution and adversely affecting the quality of drinking water
Embodiments for water purification systems are provided. In one embodiment, a system comprises a purification chamber comprising a selective adsorbent activated carbon fiber fabric including one or more selective functional groups that bind arsenic. The selective adsorbent fabrics may be differently functionalized and may include an arsenic-selective functional group configured to adsorb one or more ionic structures of arsenic.
One approach to overcome at least some of the issues presented above is to use a selective adsorbent fabric to selectively remove one or more arsenic species from contaminated water. In some embodiments, the selective adsorbent fabric may include an arsenic-selective functional group that binds at least one arsenic ionic species via adsorption. For example, the arsenic-selective functional group may sequester As(V) and/or As(III) species from water in which such ionic species are present. The selective adsorbent fabric may at least reduce the need for downstream waste water treatment since the selective adsorbent fabric does not produce a toxic arsenic sludge like previous methods. Further, such a selective adsorbent fabric may be easily manufactured and cost effective for use in any water treatment system.
It will be appreciated that the selective adsorbent fabric may be of any suitable size and geometric shape to accommodate virtually any type of waste water treatment system. For example, the selective adsorbent fabric may be configured for a large scale water treatment facility, a small scale water treatment facility, a point-of-use water treatment system, a well water treatment system, a portable water treatment system, and other systems.
The adsorbent fabrics may selectively adsorb arsenic, while precursors of the adsorbent fabrics may also adsorb various hazardous organic toxins such as, but not limited to, industrial effluent, pesticides, and various sources of Endocrine Disrupting Chemicals (EDCs) which have been gaining increasing concerns over their possible effects on human health. The pollution of ground and drinking water by the above mentioned organic chemicals has attracted increasing attention in recent decades all over the world.
The fabrics disclosed herein and treated physico-chemically also adsorb a wide range of toxic metals, such as, but not limited to, lead, mercury, cadmium, chromium, nickel, iron, cupper, platinum, and palladium.
The disclosure is illustrated by way of example and not by way of limitation in the figures of the accompanying drawings, in which the like references indicate similar elements and in which:
Exemplary purification systems for use in water treatment systems are illustrated herein. The purification system may optionally include one or more reservoirs such as an untreated reservoir and a treated reservoir. Further, the purification system may include a purification chamber, including one or more purification cartridges, also referred to herein as filtration modules. Briefly, by directing the untreated water through the filtration module, refreshed or treated water, also referred to herein as purified water, may be generated and used as clean water. Untreated water may include toxins such as arsenic from natural and/or anthropogenic sources, and such toxins may not be desirable in drinking water for human and animal consumption, for example.
Briefly,
As shown in
It should be appreciated that although the reservoir (water tank) and purification chamber are shown as separate devices linked through couplers, such as a tubing system 3, one or more the chambers and/or reservoirs may be integrated together. Typically, the purification chamber is disposed intermediate the untreated reservoir and the treated reservoir, however other configurations may be possible. For example,
It should be appreciated that a tubing system may include fluid inflow and fluid outflow. Further, the tubing system may be a conduit connecting a fluid source (such as a ground water source) to the purification chamber. The tubing system may be continuous, and may connect various components, such as one or more reservoirs and the purification chamber. Various pumps, flow meters, pressure gauges, and toxin detectors may be provided to enable flow into and out of the purification chamber and reservoir(s).
Fluid, such as untreated water, may flow (or be pumped) into an untreated reservoir in the direction of the arrow. Untreated water may be stored in the untreated water reservoir, and when needed, may flow downstream.
The untreated water temporarily stored in the untreated water reservoir may flow (or be pumped) into the purification chamber in the direction of the arrow. The purification chamber may remove toxins from the untreated water using one or more toxin traps. For example, in some embodiments, the purification chamber may include a filtration module with fibers as described in more detail below. These fibers may be capable of trapping or retaining arsenic and/or other toxins. Once the toxins are removed, the water may be considered to be purified such that it is refreshed water. In some embodiments, the purification chamber may include, in addition to the toxin trap, one or more semi-permeable membranes to separate small particles which may be contained in the water such as ground water. In other embodiments, the purification chamber may be configured without a semi-permeable membrane or the like.
For example, the filtration module may include a selective adsorbent fabric that selectively removes toxins. The selective adsorbent fabric may adsorb arsenic from the untreated water flowing through purification chamber in an example. As described in more detail below, the selective adsorbent fabric may reduce the concentration of arsenic in the untreated water such that water exiting purification chamber includes minimal arsenic, and hence, may be referred to as purified water in this respect. The fabrics disclosed herein and treated physico-chemically may also adsorb a wide range of toxic metals, such as, but not limited to, lead, mercury, cadmium, chromium, nickel, iron, cupper, platinum, and palladium.
As described in more detail below, the fabric may be disposed within the filtration module to maximize water flow contact. In some examples, the filtration module may be a flat module configuration or a spiral wrapped configuration. Although these two modules are described in detail below, it should be appreciated that different configurations of the fabric within the cartridge are possible and are within the scope of the disclosure.
Treated water may flow (or be pumped) from the purification chamber to a treated water reservoir or other clean water outlet. It will be appreciated that treated water may flow downstream to an additional water treatment process and/or to a municipal end point (e.g. a faucet), for example. In some examples, highly contaminated water may be redirected back through the system until the toxins are sufficiently removed.
It will be appreciated that the directionality of the water flow is provided by way of example and as such is not meant to be limiting. The tubing system may be configured in any suitable form to transport water in any suitable direction. For example, one or more sections of tubing system may redirect the water flow in another direction than those illustrated in
In some embodiments, the size requirements may be so reduced as to enable the purification system to be portable. By reducing the size of the purification system, a user may purify water in remote environments, for example, backpackers and travelers may use such a portable purification system. Further, pitchers and other systems may utilize the filtration module described herein.
It will be appreciated that various sensors may be used to monitor water quality, as shown in
It should be noted that in the disclosed system water is pumped through the purification chamber using one or more pumps. In some embodiments, the pumps may be roller pumps, while in alternative embodiments, the pumps may include air pumps, electrical pumps, manual pumps, or any combination thereof. In some embodiments, the pumps may be capable of adjusting the flow rate of the respective fluid that the respective pump is pumping.
In some embodiments, the purification chamber (or filtration module) may be manually detached from the tubing system, sensors, and other water treatment components and discarded and replaced with a new purification chamber. Thus, the filtration module may be considered a replaceable cartridge. As another alternative, the removed purification chamber may be dismantled to replace one or more disposable components housed within the purification chamber, such as an arsenic-selective fabric or a support screen. Once the disposable purification chamber component is replaced with a new component, the purification chamber housing may be closed and the purification chamber may be reattached to its original location in the water treatment system.
As a non-limiting example, an inlet may be disposed in a cartridge top. The cartridge top may be configured to fit or couple to a cartridge or chamber housing. Coupled with or contained in the cartridge top and cartridge housing may be sealing devices, such as one or more O-rings and/or gaskets, such as a bottom gasket. Such sealing devices may be configured to maintain the system as a closed system and prevent leakage of water from the housing.
Further contained within the filtration module may be a selective adsorbent fabric 38. This selective adsorbent fabric may remove toxins from the water while substantially maintaining the appropriate levels of minerals which influence the taste of the water as well as promote desired body salt balance. The fabric may be formed of a sufficient tortuosity and thickness to ensure good contact with the water flow. Further, the fabric may be wrapped, wound, or otherwise positioned to increase the surface area of the fabric to the water flow.
As described above, untreated water (toxin-laden water) may be introduced into the filtration module through an inlet. The untreated water may encounter the selective adsorbent fabric. The toxins may be captured by the fabric and retained such that refreshed water exits through an outlet. In some embodiments, the toxins may be retained within the fabric or along the screen. In other embodiments, a second outlet, such as elimination port, may be provided to remove the trapped toxins. Toxins may be released through the elimination port such that the toxins are not retained in either the purification chamber or circulated back to a reservoir.
Turning now to
Regardless of the configuration, the toxin-laden water is directed into the filtration module (such as the module in either
It should be appreciated that any suitable fiber may be used. In some embodiments, the fabric may be composed of carbon fibers or other suitable fiber-like materials, including plastics, polymers, resins, silicone, cotton, etc. Further, in some embodiments, as an alternative, particles, aggregates, weaves, rings, tubes, such as grapheme, carbon nanotubes, etc., may be used in place of fibers. In some embodiments, the fibers may be acid-treated or oxidized, while in other embodiments, the fibers may not be acid-treated or oxidized.
Additionally, the fibers may be activated fibers or non-activated fibers. Further, the fibers may be nanofibers. For example, in one embodiment, the fibers may be activated carbon fibers. Activated carbon fibers may be made by the carbonization and activation of precursor fibers (e.g. polyacrylonitrile, phenol resin, pitch, rayon, cotton, etc.) at high temperature and in the flow of air containing oxygen, or in the flow of inert gas such as nitrogen or argon.
For example, activated carbon may be made by burning hardwood, nutshells, coconut husks, cottons, animal bones, pitch, carbon-containing polymers (such as rayon, polyacrylonitrile, etc.), and other carbonaceous materials. The charcoal becomes “activated” by heating it with steam, carbon dioxide, or carbon monoxide to high temperatures in the absence of oxygen. This heating removes any residual non-carbon elements and produces a porous internal microstructure with an extremely high surface area.
Further, activated carbon fibers may be subject to washing treatments and/or further heat treatment to increase consistency of batch-to-batch samples. As one example, activated carbon fibers may be heated at 325° C. for 8 hours. As another example, activated carbon fibers may be heated at 300° C. for 24 hours. These additional heat treatments may increase the surface area, pore size stability, meso pores, crystalline structures, C—O and C═O (if under the air), and decrease in hydrogen content. Therefore, it will be appreciated that activated carbon fibers may be subject to any pre-treatment including washing and heating, and further, that duration, frequency, temperature, etc., of washing/or heating may be a suitable value.
In one embodiment of the present disclosure, the selective adsorbent fabric may include one or more arsenic-selective functional groups, or another arsenic- or toxin-selective functional group. Alternative embodiments may include traps selective for other waste products to be purified including, but not limited to, mercury, lead, cadmium, copper, and other heavy metals, ammonia, and other organic and inorganic contaminants.
Any suitable fabric may be used as a selective adsorbent fabric. The arsenic-selective fibers may be disposed in any orientation, for example, the fibers may be in an overlapping, bi-parallel orientation. It should be appreciated that the fibers may be oriented in a variety of patterns, including a chaotic arrangement. Fibers may be uniform or variable sizes within fabric. Although not illustrated in
Fibers may be produced using a furnace in house and/or be commercially available activated fibers (AF). In some embodiments, activated carbon fibers (ACF) and fabrics are used. One exemplary fiber for use in the purification system described herein may be a basket weaved fiber with a specific surface area of 600/m2/g to 2,000 m2/g. Another exemplary fiber for use in the purification system described herein may be felt type, which may have a similar specific surface area. Although an exemplary fiber is provided, other fabrics and fibers may be used with wide ranges of density, specific surface area, pore structures, and pore size distributions without departing from the scope of the disclosure. For example, other commercially-available economical fibers or prepared fibers/fabric may be used because the economy of the water purification system is one of the most critical factors.
It should be noted that the fibers may have a three-dimensional configuration. Within the three dimensional configuration, the fibers may be disposed such as to form macropores, mesopores, micropores, and nanopores, or structures that may contain select functional groups. Such structures may be configured to trap or retain select ions and organic toxins. For example, the pores may be charged to selectively trap oppositely-charged ions. In one example, the pores may be positively charged, thus configured to attract and trap negatively-charged ions, such as arsenic(V) and chemicals rich with functional groups with partially negatively charged and/or high electron density and/or rich in π electrons.
Once a fabric is selected, the fabric fibers may be prepared for use as the selective adsorbent fabric. In some embodiments, the fiber surface may be modified to increase the concentration of oxygen-containing functional groups. The modification to the surface may be such that the surface of the fiber is oxidized. For example, the surface may be modified by treating the selective adsorbent fabric with nitric acid (HNO3) and sulfuric acid (H2SO4) to achieve the addition of carboxylic acid groups and hydroxyl groups to the selective adsorbent fabric. In some examples, fibers will be functionalized to create functionalized activated carbon fibers, such as ACF-SO3H, ACF-PO3H and ACF-NH2; ACF functionalized with amino groups (several surface modification methods are available); ACF-SBX; ACF functionalized with strongly-basic anion-exchange groups as shown in the figures, etc.
Further, the fabric fibers may be additionally prepared for use as the selective adsorbent fabric. In some embodiments, the fiber surface may be modified to increase the concentration of sulfur-containing functional groups, and/or other non-metal-containing functional groups. The modification to the surface may be such that the surface of the fiber is sulfided. For example, the modification to the surface may be such that the surface of the fiber contains a methyl sulfide (SH), also referred to as a thiol or a mercaptan. For example, the surface may be modified by treating an oxidized selective adsorbent fabric with thiourea (CH4N2S), hydrogen bromide (HBr), and/or sodium hydroxide (NaOH) to achieve the addition of a methyl sulfide to the selective adsorbent fabric.
Any suitable method may be used to modify the surface, including, but not limited to, heat treatments, peroxide treatments, acid treatments, etc. Modification of the surface of the fiber to include high oxygen concentration and higher relative concentration of carboxylic and hydroxyl groups may provide the functional groups for sulfur binding and enable further modification of the fiber. It should be appreciated that surface, as used herein, may be any portion of the fiber that may be exposed or exposable to the water flow.
Additional examples of the filtration modules and the configuration of the fabric and water flow path are further illustrated in
Returning to
ACF-SBX, ACF-H, ACF-OH and ACF-NH2 are all reasonably good adsorbents for various organic toxins. Particularly, ACF-SBX and ACF-H are very good adsorbents for various organic toxins, as shown in Table 1 below.
♦0.5
♦Estimated time to achieve designated toxin removal (min). All experiments were performed in Standard Synthetic Test Water (STW) which was prepared by dissolving 31.90 mg Na2SiO3•5H2O, 252.06 mg NaHCO3, 61.60 mg MgSO4•7H2O, 50.85 mg MgCl2•6H2O, and 147.20 mg CaCl2•2H2O in 1 L ultra-pure DI water. The pH is adjusted to 6.9~7.0.
†DEHP; bis(2-ethylhexyl)phthalate, deca-BDE; decabromodiphenyl ether, 2,4-D; 2,4-dichlorophenoxy acetic acid.
‡Logarithm of measured partition coefficient,
▪HBD; hydrogen bond donors, HBA; hydrogen bond acceptors.
ACF-SBX was the best sorbent for rapidly removing a wide spectrum of organic chemicals. ACF-H was found to be a fairly good adsorbent as well although it was not a good adsorbent for anthracene, DEHP, and some other tested chemicals. ACF-SBX also appears to be a good sorbent for chemicals rich in hydrogen bond acceptors. Although the levels of all of these toxic chemicals in ground water are generally quite low (ppb level), initial adsorption studies were performed at much higher concentrations (ppm level) to readily screen them with minimal errors. One liter of water contaminated with total 100 ppb range (high contamination level) of typical organic toxin mixtures will be rapidly (seconds level) removed by 0.1 g ACF-SBX. The loading capacity of ACF-SBX and ACF-H for most of toxins in Table I is the range of 150 mg˜300 mg/g. Assuming a total organic contamination of 500 ppb (one of the highest cases in the drinking water/well water), 14 liters of drinking water per day (standard for four member family), the cartridge containing 100 gram of ACF-SBX filter would clear organic toxins through one year. Thus, ACF-SBX will be very powerful water purifier and suitable for use as water faucet attached purification device. The strength of ACF-SBX is that it is able to adsorb As(V) in addition to various toxic organic chemicals.
It should be appreciated that there is diversity of coordination schemes of arsenic with functional groups in proximity in a ACF-SH (III) matrix as shown in
The strength of the ACF material is the ability to vary pore dimensions and customize pockets with multiple ligands to attract and sequester arsenic. N and O heteroatoms can be positioned within and upon the ACF material to take advantage of favorable non-bonding donor-acceptor interactions with arsenic. The ACF material can be functionalized with ligands to attract and tightly sequester arsenic through multiple bonding interactions. The proximal location of different functional groups with complimentary bonding modes can enhance binding of arsenic. Optimum binding of arsenic is dependent on the location and proximity of ligands as well as the dimensions of the layers and pockets within the ACF material.
The degree of the proximity (distance) and number of coordination between arsenic and functional groups will be controlled by the preparation methods of ACF-SH (III) from the ACF-H including the oxidation of ACF-H as well as the heat treatment condition of ACF to prepare the ACF-H. And, the apparent maximal adsorption capacity of ACF-SH (III) varies, for example in a range of 5 mg/g to 30 mg/g, for both As(III) and As(V) in the STW environment. ACF-SH (III) is also an effective adsorbent for lead and mercury in the STW environment with adsorption capacity of more than 60 mg/g for both toxic metals.
The following case studies are provided as examples of the functionality of various arsenic-selective functional groups incorporated into activated carbon fibers.
Case study #1: Preparation of chloromethyl ACF (ACF-CH2Cl)
ACF-CH2Cl is a key intermediate in the production of a subset of the arsenic-selective fabric fibers and also for ACF-SBX production, presented below. ACF-CH2Cl was prepared through two different routes. The first method used the reaction of the ACF with paraformaldehyde and acetamide in the presence of sulfuric acid under a nitrogen atmosphere. This method has been readily utilized for the chloromethylation of aromatic compounds. Briefly, the ACF were heated in the sulfuric acid containing paraformaldehyde (1 equivalent) at 55° C. for 5 hours. Acetamide (3 eq.) was added to the reaction medium in portions and maintained the reaction mixture at 55° C. for 8 hours. ACF was extensively washed with water, toluene and finally ether before drying in vacuo. The ACF was placed in xylene containing phosphorus oxychloride (2 eq.) and dimethylformamide (1 eq.), and subsequently the mixture was heated to reflux for eight hours under a nitrogen atmosphere. The ACF-CH2—Cl was washed with water and ether to remove any unreacted materials and contaminants. The ACF-CH2—Cl was then dried in vacuo, and stored under nitrogen until use.
In the alternative method, ACF was reacted with chloromethylmehtyl ether (1. equivalent) and zinc chloride (0.1 eq) in dichloromethane at 50° C. for 8 hours under a nitrogen atmosphere. The ACF was extensively washed with methanol, and subsequently with water before drying in vacuo. ACF-CH2Cl was stored under nitrogen until use. The ACF-CH2—Cl may be used to prepare ACF-SH (II), ACF-NH—SH (I), ACF-NH—SH (II), and ACF-SNX, presented below.
Case Study #2: ACF-SH (II)
ACF-SH (II) was prepared by reaction of ACF-CH2—Cl with sodium hydrosulfide. Methods for the preparation of aromatic and aliphatic: thiols have been extensively reported in the literature. Briefly, the ACF-CH2—Cl was placed in water containing sodium sulfide (1 eq.) and the mixture heated to reflux for 8 hours under a nitrogen atmosphere. The reaction was terminated by soaking the ACF in hydrochloric acid. The ACF-SH was washed extensively with water and dried in vacua. The prepared ACF-SH (II) was stored under nitrogen until use.
Case Study #3: ACF-NH—SH (I)
The ACF-NH—SH (I) was prepared through the reaction of the ACF-CH2—Cl with 2-aminoethanethiol (1 eq.) in water at 60° C. for 8 hours. The reaction was carried out under a nitrogen atmosphere. The ACF-NH—SH (I) then was extensively washed with water before drying in vacua. The prepared ACF-NH—SH (I) was stored under nitrogen until use.
Case Study #4: ACF-NH—SH (II)
The ACF with multiple thiol groups (ACF-NH—SH (II) was prepared by reacting ACF-CH2—Cl with 3-amino-1,2-propandiol (1 eq.) in water at 60° C. for 7 hours under a nitrogen atmosphere. The ACF was washed with water, and subsequently refluxed with thiourea (1 eq.) and hydrobromic acid (1 eq.) in water for 16 hours under a nitrogen atmosphere. The reaction was cooled to medium to room temperature and sodium hydroxide was added (2 eq.), and then the reaction was refluxed medium again for 16 hours under a nitrogen atmosphere. The functionalized ACF was extensively washed with water until the solution reached to a neutral pH. The ACF-NH—SH (II) was dried in vacua and stored under nitrogen until use.
Case Study #5: ACF-SBX
The ACF-SBX which is ACF functionalized with strongly-basic anion-exchange groups was prepared by reacting ACF-CH2—Cl with trialkylamines. This method is commonly used to functionalize polystryrene resins with strongly basic anion exchange groups. The resulting ACF-SBX was washed with ether and water, and then washed the salt form with water until the pH reached neutral. ACF-SBX was stored in water until use. Briefly, the ACF-SBX was prepared by reacting the ACF-CH2—Cl with trimethylamine (1 eq.) in water at 55° C. for 5 hours under a nitrogen atmosphere. The ACF was washed with water, dilute sodium hydroxide and water. The ACF-SBX was converted to the chloride form by treating it with 0.1 M hydrochloric acid. The fabric was washed extensively in water before drying in vacuo.
The Case Study #7: ACF-SH
ACF-SH may be prepared without utilizing the ACF-CH2—Cl. The ACF-SH was first prepared via synthesis of the intermediate, choloromethyl ACF (ACF-CH2—Cl) and was designated ACF-SH (II). We also attempted to prepare ACF-SH, designated as ACF-SH (I), through a more direct reaction of ACF with thiourea. This was to pursue the more economic route of the preparation of ACF-SH. Specifically, ACF was reacted with thiourea (1 eq.) and hydrobromic acid (1 e.q) in water at 100° C. for 16 hours under a nitrogen atmosphere, The reaction was cooled to medium to room temperature and added sodium hydroxide (2 eq.) and then the medium was refluxed for 16 hours at 100° C. under a nitrogen atmosphere. The modified ACF was extensively washed with water until the solution reached to a neutral pH before drying in vacuo. The prepared ACF-SH (I) was stored under nitrogen until use.
Case Study #8: ACF-SH (III)
We proposed that the increase in —OH groups of ACF would increase the subsequent formation of —SH groups on the ACF with thiourea, described previously. Therefore, we attempted to increase the density of —OH through rigorous oxidation of ACF according to the method developed in house as described below. ACF-SH (III) may be prepared without utilizing the ACF-CH2—Cl intermediate. First the acid treated ACF (ACF-OH) was prepared by reacting ACF with a 50/50 (v/v) mixture of nitric and sulfuric acids. The acid treated ACF was extensively washed with water until the solution reached to a neutral pH before drying in vacuo. The acid treated ACF was stored under nitrogen until use. Next, the ACF-SH was prepared using acid treated ACF which is rich in —OH groups. Specifically, the acid treated ACF was reacted with thiourea (1 eq.) and hydrobromic acid (1 eq.) in water at 100° C. for 16 hours under a nitrogen atmosphere. The reaction was cooled to medium to room temperature and sodium hydroxide (2 eq.) was added and then the medium refluxed for 16 hours at 100° C. under a nitrogen atmosphere. The modified ACF was extensively washed with water until the solution reached to a pH above 6.0 before drying in vacuo. The prepared ACF-SH (III) was stored under nitrogen until use.
Case Study #9: Measurement of Arsenic Adsorption by the Functionalized Carbon Fibers
Adsorption tests were used to measure the interaction of the functionalized carbon fibers. At first, we performed the study with arsenate (As(V)) in the absence of competing ions to evaluate the adsorption kinetics and reproducibility of the preparation of fibers. Next, we perform the kinetic studies under the various pH to see whether functionalized ACF can catch arsenate under the changing pH. Next, the interaction of the functionalized ACFs with As(V) was measured in the presence of synthetic ground water to see the competitive effects of common anions and cations on the arsenic adsorption of selected functionalized ACF. As there was a large number of samples to be analyzed in the adsorption experiments and general analysis of fibers such as titration, elemental analysis, surface analysis, limited amounts of fiber and a simple shaking method were used instead of a flow through method, although it is known that adsorption/absorption capacities are much higher when the arsenic solution is flowed through a column or module packed with the ACF.
The adsorption of arsenic, As(V) by functionalized ACF was measured as follows. One hundred mg of each functionalized ACF (dry wt.) was placed in 20 ml, of a test solution in an EDTA washed container at pH 7.0 (unless otherwise noted). The samples were shaken for a designated time period and the aliquots were removed for the determination of remaining arsenic. The adsorption (loading) was expressed as the mg of arsenic adsorbed divided by the mass of fabric used. The determined total arsenic concentration in all test solutions was made mainly by graphite furnace atomic absorption spectrometry (GFAA; EPA Method 200.9) in house and occasionally inductively coupled plasma mass spectroscopy (ICP-MS; EPA Method 200.8) for determination of As below 10 ppb.
Although there were some preliminary results in the adsorption kinetic studies using ACF-SH (II) with fixed concentration of arsenics, it was decided to use the same fabric amount (100 mg), with varying concentrations of arsenic (200 ppb instead of 1 ppm) for all the adsorption tests except isothermal binding experiments. Therefore, first the adsorption (binding) kinetic study using ACF-SH (II) to assess the approximate equilibrium time points of the adsorption, as shown in
As shown in
The first extensive screening of the functionalized ACF was performed using various pH with a fixed relatively low concentration of arsenic (200 ppb) and a fixed amount (100 mg) of ACF in 20 mL of deionized water (DI water). Each reaction medium was shaken at 180 rpm using an orbital shaker. After one hour, an aliquot was collected to measure the remaining arsenic by GFAA to determine the adsorbed amount of arsenic. Initial and final concentrations of the metalloids in the test solutions were measured by the analytical methods described above. Data were used to calculate theadsorbed amount of As(V) to the functionalized ACF.
In the results all the functionalized ACF preparations showed much higher absorption (loading) capacity than that of native ACF for arsenic. In addition, ACF-NH—SH (I), ACF-SH (III) and ACF-NH—SH (II) indicated higher adsorption (loading) capacity of arsenic than that of ACF-SH (II) and ACF-OH. ACF-SBX had relatively high adsorption capacity at pH 6.0. However, the adsorption capacity of ACF-SBX decreased rapidly in the pH higher than 7.0. Although ACF-SH (II) did not show higher adsorption capacity compared with ACF-NH—SH (I), ACF-SH (III) and ACF-NH—SH (III), the reproducibility of the preparation of ACF-SH (II) was one of the best among tested functionalized ACF. Therefore, we included this for the remainder of the study. On the other hand, the reproducibility of the preparation of ACF-SH (I) was the lowest among all the preparations. The preparation also did not have significant adsorption capacity of arsenic. It, along with ACF-Ph-SH and ACF-OH, ACF-SH (I) were excluded from further studies of arsenic adsorption properties.
Next, review of the pH dependence of arsenic adsorption to selected functionalized ACF (ACF-NH—SH (I), ACF-SH (III), ACF-NH—SH (III), and ACF-SH (II)) was studied in detail between pH 2.0 and pH 10.0.
Although ACF-NH—SH (I) showed reasonable adsorption capacity for arsenic, it was not easily reproduced, and was difficult to obtain consistent arsenic adsorption profiles. ACF-SH (III) and ACF-NH—SH (II) were both promising as excellent arsenic adsorbents under the wide range of pH. Therefore, through pH dependence studies of arsenic adsorption to functionalized ACF, we determined that the best functionalized ACFs for further studies were ACF-SH (III) and ACF-NH—SH (II). However, ACF-SH (II) was used in many of the studies as it is easily and economically prepared while still showing reasonable arsenic adsorption capability. In addition, the improvement of the synthetic route of ACF-SH (II) to increase the adsorption capacity could be feasible.
The elemental analyses of selected functionalized ACFs were performed to determine elemental composition at normal resolution for each sample, illustrated in Table 2 below. The fabric samples showed that different degrees of sulfur, oxygen, and nitrogen atom contents that are consistent with methods of the treatments of ACF. The method employed in the preparation of ACF-SH (III) was the most efficient method for increasing the total sulfur content in the fabric.
The next isothermal binding studies were performed using the following three functionalized ACF: ACF-SH (III), ACF-NH—SH (II), and ACF-SH (H). The isothermal binding (adsorption) curve was complicated for ACF-NH—SH (II), having multiple adsorption phases and a lack of consistency (data not shown). The adsorption of arsenic to both ACF-SH (HI) and ACF-SH (II) showed good isothermal curves. In review, the arsenic binding to ACF-SH (III) was far higher than arsenic binding to ACF-SH (Th. Therefore, we focused on ACF-SH (III) to characterize its arsenic removal capacity.
Next, the adsorption experiments was performed using a standard synthetic test water (STW) solution (Table 3), containing most of the common ions found in drinking/groundwater. Briefly, the functionalized ACF (ACF-SH (III)) was placed in test bottles containing either STW solution or DI water which were subject to shaking (200 rpm) in a temperature-controlled water bath. After one hour, an aliquot was collected to measure the remaining arsenic by GFAA. It is encouraging that ACF-SH (III) maintained at least 70% (at >1 ppm arsenic) and 85% (at below 0.5 ppm) of its arsenic binding (adsorption) capacity in SWT.
Case study #11: Evaluation of functionalized ACF for removal of bound arsenic Selected fibers were evaluated, especially, ACF-SH (III) and ACF-NH—SH (II), and to some extent, ACF-SH (II) for the development of modules composed of arsenic-selective ligand-anchored ACF.
The first criterion for the evaluation is the optimal combination of adsorption capacity and regeneration efficiency. Those functionalized ACF, especially ACF-SH (III), show distinct notability in terms of adsorption capacity of arsenic over a wide range of pH and easily reproduced preparation through simple synthetic routes. The ACF-SH (III) was superior to any other functionalized ACF tested here in arsenic adsorption capacity in the presence of Standard Test Water (STW). In terms of regeneration, it was found that adsorbed (absorbed) arsenic bound to the ACF-SH (III) matrix and was not easily dissociated. Regeneration of other functionalized ACF including ACF-SH (I) was accomplished by changing the ionic concentration or the pH of the system.
Options to regenerate ACF-SH (III) by means of changing the ionic strength of the system and exposure to the arsenic-ACF-SH (III) complex to the low and high pH using 1-10 bed volumes of regeneration solution are considered. Neither trial proved an effective method of dissociating bound arsenics from ACF-SH (III). The above mentioned phenomenon is reasonable because ACF-SH (III) shows high arsenic adsorption capacity in wide range of pH and in the presence of salt solution.
The extremely tight binding of arsenic to ACF-SH (III) is not negative to the intended use. However, consideration is made to methods of disposing the recovered arsenic as a stabilized complex with ACF-SH (III). This ACF is light weight and easily forms complexes with stabilizing compounds to mask the ACF-SH (III) matrix.
A major factor in regulating the total cost of any remediation technology is the reusability of the adsorbent through regeneration, and the cost of regeneration of the adsorbent. In sonic cases, the cost of regeneration far outweighs the cost of replacement and produces the vast amount of solvent contaminated with arsenic. Therefore, if a simple and cost effective regeneration technique is not readily available, disposal of recovered arsenic as a stable complex is another option in drinking water remediation.
The reproducibility in preparing the fibers was the second important evaluation criteria for this functionalized ACF-based arsenic removal technology. In sonic systems, it was found ACF-SH (III) was superior to all the other functionalized ACF tested in terms of high binding capacity in the wide range of pH and in the STW, reproducibility in the preparation and adsorption assays. As such, in one example, ACF-SH (III) may remove greater than 95% Arsenic (V) from test solutions containing 0.05-1.0 mg/L Arsenic (V), and a maximal loading capacity (estimated by isothermal studies) of 5˜30 mg of Arsenic (V) per gram of functionalized ACF when incorporated into the tightly packed module. However, the operational capacity which does not release or remain more than 10 ppb arsenic will be much less and estimated to be around 100 μg/g. The operational loading capacities of ACF-PO4, ACF-SO4, ACF-OH and ACF-SH for removing lead, mercury, cupper (II), iron (II), platinum, nickel and palladium are generally much higher to be around 20˜80 mg/g fiber.
Next, competitive adsorption studies were performed using both As(V) and As(III). The adsorption of As(III) in the absence of STW is very similar to that of As(V). ACF-SH (III) maintained at least 85˜92% of its binding (adsorption) capacity for As(III) in SWT, which is somewhat better than that of As(V) (70˜85%). As(III) bound very tightly to ACF-SH (III) over a wide range of pH (2-10), which is similar to the case of As(V) binding to ACF-SH (III) (data not shown). It has been determined that 2 hours treatment times with 100 ppb for both arsenic species will provide comparable binding data (data not shown). There were no significant effects of tested well known competitive ions (Fe(II), Fe(III), Cu(II), Mn(II), Mn(IV), nitrate and phosphate) at five times mass equivalent of As(V) and As(III) on the adsorption of both arsenic species to ACF-SH (III), under the experimental conditions employed here. Also, >20 ppm oxygen had no effect on either As(V) or As(III) adsorption onto ACF-SH (III). As expected from the previous studies, STW inhibited the binding of both As(V) and As(III) to ACF-SH (III) at 8% and 13%, respectively. The adsorption capacity of ACF-SH (III) for As(III) and As(V) in the presence of increasing concentrations of Fe(III) (up to a 50-fold equivalent of As(V) and As(III)) were studied. At 50-fold mass equivalents, Fe(III) did not have any significant effect on the removal of As(V) or As(III) by ACF-SH (III), Data not shown
Referring back to
The following in regards to
The ion-selective barrier may include fatty acid chain extensions with carbon chains of C4-C25. The carbon chains may extend away from the body of the fabric to form a physical barrier to cations, such as K+, Na+, Mg2+, and Ca2+. It should be noted that such cations may be of an increased size due to hydration. Thus, although the fiber may be charged such that various ions are attracted to the fiber, some large molecules (such as the highly hydrated cations) may be prohibited from entering into the fiber by the fatty acid chain extensions. Thus, the chains may operate as an ion-selective barrier, allowing small molecules to pass through into the fiber, (thus trapping the less hydrated molecules within the fiber), while physically preventing the larger molecules (such as the hydrated cations) from passing through to the trap.
The hydrophobic nature of the ion-selective barrier must be balanced with the accessibility of aresenic to the selective functional groups that bind arsenic. Thus, the barrier must be sufficiently hydrophobic to repel the substantial cations (minerals), but be not so hydrophobic as to significantly decrease the rate of diffusion of As(V) which is negatively charged as well as relatively hydrophilic organic toxins. Most of organic toxins are less hydrophilic or rather hydrophobic as shown by the log p values in Table 1. Therefore, those organic toxins will be well adsorbed by ACFs and even some organic toxins with extended carbon chains (which are generally difficult to be removed) could be trapped by the ion-selective barrier.
For example, essential minerals, such as K+, Na+, Mg2+, and Ca2+may be substantially unable to penetrate the physical barrier presented by the carbon chains. The essential cations may be considered to be repelled from the ion selective hydrophobic barrier. Thus, the essential cations are retained in the treated water, thereby maintaining ionic homeostasis and mineral balance which are important for body health and bone remodeling as well as taste in the water.
However, toxins may be able to penetrate the barrier and thus may be readily adsorbed by the fiber. The toxins become trapped within the barrier. The chains may also be configured to allow arsenic or other toxins to pass through and be trapped by the barrier. It should be appreciated that in some embodiments the carbon chains may be of different sizes along the length of the fiber or the fabric. In other embodiments, the carbon chains may be of the same length along the fiber or fabric. The position of the chains may be dependent on the effectiveness of the barrier. Moreover, in some embodiments, where shorter length chains are utilized, the shorter length chains may be positioned in relatively close proximity, while, in other embodiments, longer length chains may be more separated. Such spacing may be effective as the longer chains may cover more area and provide an appropriate physical barrier without being as closely positioned as shorter length chains. Further, although shown as extended carbon chains, in some embodiments, the chains may include one or more rings, or other configurations, such that the carbon chains are considered a carbon barrier. It should be noted that the addition of the ion-selective barrier to this water purification system will be optional and depends upon the needs of people and quality of drinking water.
Although other suitable ion barriers may be prepared on the fiber, the following method of constructing an ion barrier on the activated fiber is provided for illustrative purposes. Specifically, in one embodiment, a surface-modified activated fiber, such as an acid-treated activated fiber, may be further modified to create an ion barrier by addition of a fatty acid. The fatty acid may be as short as C4 or may extend to C25. In some embodiments, fatty acids with chain lengths of C14 to C17 may be used. It is noted that the carbon of the carboxyl group of the fatty acid is counted when discussing the number of carbons in the fatty acids. In other examples, the ion barrier may not be employed.
In an exemplary embodiment, an ion-barrier may be constructed on the activated fiber by reacting a surface-treated activated fiber, such as an acid-treated activated fiber, with palmitoyl chloride in the presence of an acid scavenger, such as pyridine, triethylamine, 4-(dimethylamino)pyridine, Proton-Sponge®, and several polystyrene-divinylbenzene (PSDVB)-supported acid scavengers including several PSDVB-supported piperidine compounds. The reaction may result in addition of palmitoyl groups (C16) attached to the activated fiber. It should be appreciated that any other suitable carbon chain or carbon barrier may be attached to the activated fiber, in addition to, and/or alternatively to, the palmitoyl groups.
Further the fibers may be modified to include both an ion barrier and immobilized enzyme or microbial biofilm. The immobilized enzyme may be configured to decompose arsenic into smaller molecular ions. The ions may be trapped by the fabric. For example, positively-charged ions may be attracted to a negatively-charged fabric. As another example, negatively-charged ions may be attracted to a positively-charged fabric. It will be appreciated that the fabric may be negatively-charged or positively-charged. As another example, the fabric may include negatively-charged zones and positively-charged zones for attracting positively-charged ions and negatively-charged ions respectively.
Any suitable method may be used to immobilize the selected enzyme. In some embodiments, it may be selected to covalently attach arsenate reductase, or other suitable enzyme, to the fiber. Any suitable biochemical methods may be used to attach or otherwise immobilize the select enzyme or enzymes. For example, coupling agents, and/or covalent linkers, as well as other biochemical methods, may be used to immobilize arsenate reductase, or an alternative ion-selective compound, onto the fiber.
As described above, in one exemplary embodiment, the synthesized selective adsorbent fabric may include one or more fibers with one or more of the following: a hydrophobic layer adjacent to attached lipid chains, an ion-selective barrier formed by the lipid chains, immobilized arsenic reductase capable of catalyzing the hydrolysis of arsenate to arsenite ions, for example, and other chemical reaction intermediaries, and hydrophilic pores capable of trapping other toxins and/or ions from the hydrolysis of arsenic.
Turning to
A solution (2.0 ml) containing 2 ppm each of atrazine, p-dichlorobenzene (p-DCB), diuron, 2,4-dichlorophenoxyacetic acid (2,4 D), N-nitrosodiethylamine (NDEA), bisphenol A (BPA), and diethyl phthalate (DEP) in pH 6.9 STW was applied each time. The applications were repeated at least 300 times without any elution of above chemicals except NDEA (after 200 times) which is known concerned toxic chemicals difficult to remove from drinking water. Since HPLC profile on the eluted through ACF-SBX was just flat. The eluted fraction (at 200 times) was subjected to more sensitive LC/MS after SPE extraction—concentration of eluted solution. There were some background peaks (very minimal) were observed, but, no chemicals equivalent to the masses of applied seven chemicals was found. Therefore, it is very likely that all the chemicals repeatedly applied were adsorbed and also no leaching out
From the above experimental results, the maximal operational capacity (95% to 100%) of 7 toxins was assessed by repeatedly applying the chemicals (about 2.0 ppm each). The resulting toxin concentration of 14 ppm total toxins is about 100˜200 times higher than the total toxic organic chemical concentration at most sites of ground/drinking water contamination (other than industrial waste water sites). The results indicate that if there is no strong competitive materials in ground/well water, an ACF-SBX module containing 100 grams of ACF will filter up to 5-10 grams (5-10% of fiber weight) without leaching. Assuming a total organic contamination of 500 ppb (one of the highest cases in the drinking water/well water), 14 liters of drinking water per day (standard for a four-member family), the filter would need to clear 7 mg/day and 2.56 grams organic toxins/year. Therefore, unless extreme environments exist, such as very high concentrations of organic toxins or natural organic matter (NOM), residents will not have to change the filter for at least a year. Thus, the combination of ACF-SBX and ACF-SH (III) will create the powerful tool for water purification contaminated with both arsenic, toxic metals, and toxic organic chemicals.
Thus, the systems described above provide for a system capable of removing toxins from water for water purification. In an embodiment, the system comprises a purification chamber comprising a selective adsorbent activated carbon fiber fabric including one or more selective functional groups that bind arsenic.
The fabric may be disposed to create a water flow channel in the purification chamber. In one example, the fabric is in a spiral configuration. In another example, the fabric is in a flat layered configuration. The system may further comprising a pump to move water along the flow channel. The one or more selective functional groups may be included on a surface of the activated carbon fiber. The one or more selective functional groups may include one or more of a sulfur-containing group, a hydroxyl, a carboxylic acid, a carbonyl, an ester, a nitrogen-containing group, and strongly-basic anion-exchange group. In an example, the selective adsorbent fabric includes a bound arsenic reductase enzyme.
The system may further comprise one or more functional groups to adsorb toxic metals or toxic organic chemicals, where the toxic metals comprise one or more of lead, mercury, cadmium, chromium, nickel, iron copper, platinum, and palladium. The functional groups to adsorb toxic metals or toxic organic chemicals may be included within or on a surface of the activated carbon fiber.
The purification chamber may include an ion-selective barrier, for example coupled to the activated carbon fibers. The system may be portable, or the system may be stationary, for example for use in treating a municipal water source. The system may include an inlet from one of well or ground water.
In an embodiment, a water purification system comprises an inlet to admit untreated water; a purification chamber comprising a selective adsorbent activated carbon fiber fabric having a surface including one or more selective groups that bind arsenic; and an outlet to discharge treated water.
The one or more selective groups that bind arsenic may comprise one or more of a thiol selective group and a strongly basic anion exchange group. The fabric may be disposed in the purification chamber to create a water flow channel fluidically coupling the inlet to the outlet. In an example, the fabric is disposed in a spiral configuration.
Turning now to
The purification chamber may be a suitable chamber housing a selective adsorbent fabric adapted to trap arsenic and/or other toxins, such as the purification chamber described above with respect to
Thus, as indicated at 204, after the untreated water is directed to the purification chamber, it is passed over the selective adsorbent activated carbon fiber fabric in the chamber to create treated water. The treated water is then directed to an end location at 206. The end location may be a treated water reservoir separate from or integrated with the purification chamber. In other examples, the end location may be a facet, municipal water tank, storage or drinking vessel, or other suitable location.
Thus, in an example, method 200 described above provides for a method for purifying water, comprising directing untreated water to a purification chamber; and passing the untreated water over a selective adsorbent activated carbon fiber fabric in the purification chamber to create treated water, the fabric including one or more selective functional groups that bind arsenic.
Directing untreated water to the purification chamber may include directing well or ground water to the purification chamber via a pump. In an example, passing the untreated water over the selective adsorbent activated carbon fiber fabric may include passing the untreated water over a selective adsorbent activated carbon fiber fabric including a sulfur-containing group. In an example, passing the untreated water over the selective adsorbent activated carbon fiber fabric may include passing the untreated water over a selective adsorbent activated carbon fiber fabric including a bound arsenic reductase enzyme.
It should be appreciated that although the purification chamber and associated fabric is described for use in a water treatment system, the purification chamber and associated fabric may be used in any purification system. As such, the purification chamber and associated fabric may be used in other systems that require removal of toxins from a fluid. For example, the purification chamber may be used to remove toxins from fish hatcheries, and other aquaculture based industries.
Further, it will be appreciated that the above toxin trap may be used to trap other types of toxins, including pathogens, viruses, bacteria, etc. In these systems, the traps may include an alternative adsorbent, specific to trap the select toxin. For example, such a system may be applied to reduce or minimize the presence of toxins, including pathogens, viruses, bacteria, etc. that may contaminate waterways and contribute to waterborne diseases.
Although the present disclosure includes specific embodiments, specific embodiments are not to be considered in a limiting sense, because numerous variations are possible. The subject matter of the present disclosure includes all novel and nonobvious combinations and sub-combinations of the various elements, features, functions, and/or properties disclosed herein. The following claims particularly point out certain combinations and sub-combinations regarded as novel and nonobvious. These claims may refer to “an” element or “a first” element or the equivalent thereof. Such claims should be understood to include incorporation of one or more such elements, neither requiring, nor excluding two or more such elements. Other combinations and sub-combinations of features, functions, elements, and/or properties may be claimed through amendment of the present claims or through presentation of new claims in this or a related application. Such claims, whether broader, narrower, equal, or different in scope to the original claims, also are regarded as included within the subject matter of the present disclosure.
This is a continuation of U.S. patent application Ser. No. 14/214,196, filed on Mar. 14, 2014, which in turn claims the benefit of U.S. Provisional Application No. 61/802,514, filed Mar. 16, 2013. Applicant's prior applications are incorporated herein by reference in their entirety.
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| Number | Date | Country | |
|---|---|---|---|
| 20170334741 A1 | Nov 2017 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61802514 | Mar 2013 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 14214196 | Mar 2014 | US |
| Child | 15669577 | US |
