Gas filters for acidic contaminants
10639588 ยท 2020-05-05
Assignee
Inventors
- Chaoyi Ba (Urbana, IL, US)
- Weihua Zheng (Savoy, IL, US)
- Erich Diesel (Champaign, IL, US)
- James Langer (Urbana, IL, US)
- James Economy (Urbana, IL)
- Bita Vaezian (Champaign, IL, US)
- Xinyu He (Urbana, IL, US)
Cpc classification
B32B2535/00
PERFORMING OPERATIONS; TRANSPORTING
B32B27/18
PERFORMING OPERATIONS; TRANSPORTING
B32B27/06
PERFORMING OPERATIONS; TRANSPORTING
B01D2257/306
PERFORMING OPERATIONS; TRANSPORTING
B32B2255/02
PERFORMING OPERATIONS; TRANSPORTING
C09D181/00
CHEMISTRY; METALLURGY
B32B27/20
PERFORMING OPERATIONS; TRANSPORTING
B32B2255/00
PERFORMING OPERATIONS; TRANSPORTING
International classification
C09D181/00
CHEMISTRY; METALLURGY
B32B27/20
PERFORMING OPERATIONS; TRANSPORTING
B32B27/18
PERFORMING OPERATIONS; TRANSPORTING
Abstract
An example article includes a substrate and a coating applied to the substrate. The coating may include a basic reactant and a humectant. The coating may further include a preservative or a water-soluble polymer. A coating configured to be applied to an acidic gas filter substrate may include K.sub.2CO.sub.3, potassium succinate, dehydroacetic acid, and poly(2-acrylamido-2-methyl-1-propanesulfonic acid (PAMPS). An example system includes an acidic gas filter including a coating, and a sensor configured to sense an optical change in the coating.
Claims
1. An article comprising an acidic gas heating, ventilation, and air conditioning (HVAC) filter configured to filter acidic components from a gas, the acidic gas HVAC filter comprising: a substrate; a coating applied to the substrate, wherein the coating comprises a basic reactant and a humectant, wherein the basic reactant comprises at least one of K.sub.2CO.sub.3, Na.sub.2CO.sub.3, KHCO.sub.3, NaHCO.sub.3, NaOH, and KOH; and a stabilizer, wherein the stabilizer comprises a water-soluble polymer, and wherein the water-soluble polymer comprises poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS).
2. The article of claim 1, wherein the humectant is present in a weight ratio of about 1:20 to about 1:1 with respect to the basic reactant.
3. The article of claim 1, wherein the humectant comprises at least one salt comprising a sodium, potassium, or cesium salt of formate, acetate, nitrite, citrate, succinate, fluoride, glycolate, ascorbate, malonate, tartarate, gluconate, fumarate, sorbate, lactate, iminodiacetate, or malate.
4. The article of claim 1, wherein the coating comprises potassium succinate.
5. The article of claim 4, wherein the coating further comprises a preservative.
6. The article of claim 5, wherein the preservative is present in a weight ratio of about 1:5000 to about 1:10 with respect to the basic reactant.
7. The article of claim 5, wherein the preservative comprises at least one of potassium iodide, potassium nitrite, polyols, parabens, dehydroacetic acid, dehydroacetate salts, and benzoates.
8. The article of claim 5, wherein the preservative comprises dehydroacetic acid.
9. The article of claim 1, wherein the water-soluble polymer is present in a concentration between about 0.2 and about 20% by weight with respect to the coating.
10. The article of claim 1, wherein the water-soluble polymer further comprises at least one of metal polyacrylates, polyvinyl alcohol (PVA), polyacrylamide (PAM), poly(ethylene glycol) (PEG), polydiallyldimethylammonium chloride (PDADMAC), polymaleic acid, polyethylenimine (PEI), ethoxylated polyethylenimine (EPEI), poly(N-hydroxyethyl acrylamide) (PNHEA), and copolymers thereof.
11. The article of claim 9, wherein the water-soluble polymer has a molecular weight between about 5 million and about 10 million.
12. The article of claim 1, wherein the coating further comprises a pH indicator.
13. The article of claim 12, wherein the pH indicator comprises at least one of neutral red, phenol red, nitrazine yellow, bromophenol red, cresolphenol red, and brilliant yellow.
14. The article of claim 12, wherein the pH indicator comprises one or both of phenol red or nitrazine yellow.
15. The article of claim 1, wherein the substrate comprises a fibrous substrate.
16. The article of claim 1, wherein the coating at least partly impregnates a surface of the substrate.
17. The article of claim 1, wherein the stabilizer further comprises an inorganic stabilizer.
18. The article of claim 17, wherein the inorganic stabilizer comprises one or more of clay, nanoclay, bentonite, montmorillonite, or colloidal silica.
19. An article comprising an acidic gas heating, ventilation, and air conditioning (HVAC) filter configured to filter acidic components from a gas, the acidic gas HVAC filter comprising: a fibrous substrate; and a coating applied to the fibrous substrate, wherein the coating comprises: a cross-linkable polymer and a cross-linker that form an ionic gel, poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS), and a basic reactant.
20. The article of claim 19, the coating further comprising at least one of potassium succinate and dehydroacetic acid.
21. The article of claim 19, the coating further comprising a color changing dye comprising one or more of neutral red, phenol red, nitrazine yellow, bromophenol red, cresolphenol red, and brilliant yellow.
22. The article of claim 19, wherein the cross-linkable polymer comprises alginate, and wherein the cross-linker comprises a calcium salt.
23. A system comprising: an acidic gas heating, ventilation, and air conditioning (HVAC) filter comprising: a coating on a substrate, wherein the coating comprises a basic reactant and a humectant, wherein the basic reactant comprises at least one of K.sub.2CO.sub.3, Na.sub.2CO.sub.3, KHCO.sub.3, NaHCO.sub.3, NaOH, and KOH, and a stabilizer, wherein the stabilizer comprises a water-soluble polymer, and wherein the water-soluble polymer comprises poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS); and a sensor configured to sense an optical change in the coating and generate a signal indicative of the optical change.
24. The system of claim 23, wherein the coating comprises a dye, and wherein the optical change is a change in a color of the dye.
25. The system of claim 24, wherein the dye comprises a pH indicator.
Description
BRIEF DESCRIPTION OF DRAWINGS
(1) The foregoing and other aspects of this invention are made more evident in the following Detailed Description, when read in conjunction with the attached Drawing Figures, wherein:
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(20) It should be understood that features of certain Figures of this disclosure may not necessarily be drawn to scale, and that the Figures present non-exclusive examples of the techniques disclosed herein.
DETAILED DESCRIPTION
(21) Acidic contaminants may be removed from a gas, for example, air or an enclosed atmosphere using air filtration systems that may be part of (heating, ventilation, and air conditioning (HVAC) systems. Systems for removing acidic contaminants from gases or air may include a chemical filter that includes strong base ion-exchange resins, activated carbon, or base-impregnated activated carbon, or their mixtures. However, known systems and techniques may not exhibit sufficient capacity, may not be stable over relatively longer time periods, and may be expensive, among other disadvantages.
(22) Example articles according to the present disclosure may provide advantages such as a higher capacity for removal of bases at low concentration ranges, maintaining baseline performance for a longer time (better breakthrough performance), better mass transfer within the working conditions provided by the efficiency of contact, lower costs, lower carbon or energy footprint, and an indication of remaining filter life or of filter failure.
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(24) The humectant may attract moisture from air and maintain a certain amount of water in the coating. The humectant may include at least one salt comprising formate, acetate, nitrite, citrate, succinate, fluoride, fluoride, glycolate, ascorbate, malonate, tartarate, gluconate, fumarate, sorbate, lactate, iminodiacetate, and malate. The salt may include a sodium, potassium, or cesium salt. For example, the humectant may include one or more of potassium formate, potassium acetate, potassium nitrite, potassium citrate, potassium succinate, potassium fluoride, cesium fluoride, potassium glycolate, potassium ascorbate, potassium malonate, potassium tartarate, potassium, gluconate, potassium fumarate, potassium sorbate, potassium lactate, potassium iminodiacetate, or potassium malate. Each humectant has a certain critical relative humidity (i.e., the humidity at which the substance will self-saturate with water). For removal of acid gas contaminants such as sulfur dioxide, potassium succinate may be preferred. Without being bound by theory, potassium succinate may improve the mass transport between gas/liquid and liquid/solid interfaces. For applications sensitive to volatile organic acids, salts whose conjugate acids are volatile, for example, potassium acetate, should be avoided as humectants, as the conjugate acid may have a tendency to volatilize once the pH drops to the neutral range.
(25) In examples, coating 120 may further include a preservative. The preservative may protect the filter from attack by bacteria, fungi or other microorganisms, and thus promote the lifetime of the filter. In examples, the preservative may include potassium iodide, potassium nitrite, polyols, parabens, benzoates, dehydroacetic acid, or combinations thereof. It is believed potassium iodide may be slowly oxidized into triiodide, which is a safe and effective bactericidal material. Preferably, the preservative may include dehydroacetic acid. Nitrite may also be effective, but has the drawback that its conjugate acid nitrous acid is volatile. In examples, the preservative may include nitrite salts. In examples, the preservative may be present in a weight ratio of from about 1:5000 to about 1:10 with respect to the basic reactant.
(26) In examples, coating 120 may further include a water-soluble polymer. Since the coating contains a certain amount of water, which may promote reaction between acids to be removed and the basic reactant, the coating may not be stable due to the flowing and drifting of the liquid solution. A water-soluble polymer may be used to increase the viscosity of the liquid phase to stabilize the coating on the fiber, and possibly to contribute to neutralizing acidic components from the gas. For example, increasing the viscosity may reduce flow or drifting of coating 120. A chemically stable water-soluble polymer is preferred. In examples, the water-soluble polymer may include polyelectrolytes. The water-soluble polymer may include one or more of group 1 metal polyacrylates, PAA-potassium, polyvinyl alcohol (PVA), polyacrylamide (PAM), poly(ethylene glycol) (PEG), polydiallyldimethylammonium chloride (PDADMAC), poly(3-acrylamidopropyltrimethylammonium chloride) (PAPTMAC), polymaleic acid, polyethylenimine (PEI), ethoxylated polyethylenimine (EPEI), poly(vinyl amine) (PVAm, Lupamine 9095), poly(2-acrylamido-2-methyl-1-propanesulfonic acid (PAMPS), poly(sulfonic acids), poly(phosphonic acids), poly(N-hydroxyethyl acrylamide) (PNHEA), polymers of NHEA, a polymer comprising carboxylic acid monomers, or copolymers comprising monomers of any of the aforementioned polymers. In some examples, the polymer may include repeat units including carboxylic acids or carboxylate, for example, poly(acrylic acid), carboxymethylcellulose, or alginic acid. In some examples, the water-soluble polymer includes PAMPS. PAMPS may be synthesized with a good control of molecular weight in a range of 0.8-15 million. A high molecular weight is desired to stabilize the coating. However, too high molecular weight may lead to very high viscosity of the coating solution and poor processability. A molecular weight between about 5 and about 10 million is preferred. In some examples, a molecular weight of less than 5 million, for example, about 1 million, or less than about 1 million, may be used.
(27) In examples, the water-soluble polymer is present in a concentration between about 0.2 and about 20% by weight with respect to the coating. Cross-linkable polymers may be used so that once cross-linked by thermal, chemical or photo methods, the coating materials may be fixed and thus stabilized onto the substrate. By this approach, drifting of the coating materials at high relative humidity environments over time can be prevented. Cross-linkable polymers may include poly(N-hydroxylmethylacrylamide) (PNHMA), poly(N-hydroxylmethylacrylamide-co-2-acrylamido-2-methyl-1-propanesulfonic acid) (PNHMA/PAMPS), poly(N-hydroxylmethylacrylamide-co-3-acrylamidopropyltrimethylammonium chloride) (PNHMA/PAPTMAC), poly(diacetone acrylamide) (PDAAM), poly(diacetone acrylamide-co-2-acrylamido-2-methyl-1-propanesulfonic acid) (PDAAM/PAMPS), and poly(diacetone acrylamide-co-diallyldimethylammonium chloride) (PDAAM/PDADMAC). The copolymers may contain 5 to 30 wt % of cross-linkable component, e.g. PNHMA or PDAAM. PNHMA can be cross-linked at high temperature. PDAAM can form a cross-linked hydrogel with adipic acid dihydrazide (ADH). PNHMA and PDAAM/PAMPS may form stable cross-linked structure at elevated temperatures. Biopolymers may also be used to form a cross-linking structure by thermal, chemical, ionical and photo methods. Such biopolymers may include one or more of alginate, humic acid, modified celluloses, starches, modified starches, xanthan gum, chitosan and chitin. Multivalent cations, for example, calcium, magnesium, zinc, aluminum, copper, barium, ferric, ferrous, cobalt, and nickel, may be included to act as ionic cross-linkers to form a strong gel. For example, alginate can immediately form gel in the presence of calcium chloride. In order to stabilize the gel particles, some antiscalants such as amino trimethylene phosphonic acid (ATMP) and 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) may be added. Solution viscosity may need to be adjusted by high molecular weight polymers such as xanthan gum, hydroxypropyl cellulose (HPC), carboxymethyl cellulose (CMC), and polyvinyl alcohol.
(28) In examples, coating 120 may include a pH indicator. pH indicators may help indicate breakthrough of the article 100a because coating 120 may exhibit a pH change as it progressively captures acidic gas components such as SO.sub.2. Preferably, a pH indicator should have a stable and bright color during storage and a sharp and apparent color change at a predetermined change in pH that may correspond to parameters such as, for example, remaining capacity of the article 100a or concentration of acid breaking through the filter. The pH indicator should preferably not negatively impact the filter performance. In examples, the pH indicator may be uniformly dispersed through coating 120. In examples, the pH indicator is disposed within a predetermined volume or region of coating 120. For example, the pH indicator may be disposed within a volume of the coating having a square, circular, oval, rectangular, or any other suitable surface area boundary. In examples, the pH indicator comprises at least one of thymol blue, bromothymol blue, nitrazine yellow, lacmoid, 2,6-dichlorophenol indophenol, bromophenol blue, bromocresol green, bromocresol purple, chlorophenol red, bromophenol red, brilliant yellow, cresol red, curcumin, phenol red, alizarin, alizarin red S, congo red, neutral red, methyl orange, methyl red, meta-cresol purple, and 2-(4-dimethylaminophenylazo)pyridine. Chlorophenol red, phenol red, brilliant yellow, cresol red are preferred due to their relatively high stability, proper pH change range, bright colors and sharp color change at breakthrough.
(29) Substrate 140 may include a woven, nonwoven, foam, porous, solid, or any other suitable substrate. In examples, substrate 140 may include one or more of fibers, granules, beads, monoliths (for example, carbon monoliths, or inorganic monoliths such as clay monoliths), or powders. As shown in
(30) In the example shown in
(31) In examples, coating 120 may include a basic reactant, a cross-linkable polymer, a cross-linker, a stabilizer, a preservative, and a color-changing dye. In examples, the stabilizer may include water-soluble polymers described with reference to
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(34) In some examples, source 275 may include one or more of sunlight, incandescent, halogen, fluorescent, light-emitting diode, organic light-emitting diode, laser, or a combustion source. In some examples, one or both of sensor 270 and source 275 may be powered by a power source, for example, AC or DC power source, batteries, photovoltaics, piezoelectric devices, fuel cells, capacitors, turbine-driven generators, radio- or microwave-frequency energy harvesters, thermoelectrics, or a combination thereof. In some examples, system 250 may not include source 275, and sensor 270 may sense ambient light interacting with region 210 of acidic gas filter 200.
(35) In some examples, system 250 may include a computing device 290. Computing device 290 may receive signals generated by sensor 270 by sensing region 210 that may be indicative of a status of acidic gas filter 200. Sensor 270 may send signals to computing device 290 may a wired or wireless connection, for example, through a wire, cable, fiber optic, or other communication medium, or by a wireless communication protocol, for example, WiFi, Bluetooth, or other suitable wireless communication. In some examples, system 250 may not include a separate computing device, and instead, computing device 290 may be integrated in sensor 270. Computing device 290 may include one or more processors, including one or more microprocessors, digital signal processors (DSPs), application specific integrated circuits (ASICs), field programmable gate arrays (FPGAs), or any other equivalent integrated or discrete logic circuitry, as well as any combinations of such components. The term processor or processing circuitry may generally refer to any of the foregoing logic circuitry, alone or in combination with other logic circuitry, or any other equivalent circuitry. In some examples, computing device 290 may be remote from acidic gas filter 200 and sensor 270. In some examples, computing device 290 may execute modules to analyze signals received from sensor 270 to determine the status of acidic gas filter 200. In some examples, computing device 290 may output a signal indicative of a status of acidic gas filter 200. In some examples, sensor 270 may analyze the sensed signals, and output a signal indicative of a status of acidic gas filter 200. The signal indicative of the status may include one or more of a visible or audible alert, for example, a light, an icon, an alert tone, an alert message, or a digital communication encoding the status.
(36) While in the example of
(37) In some examples, region 210 may be static or dynamic. For example, one or both of source 275 or sensor 270 may move or reposition, for example, by a motor or other displacement mechanism to sense different regions of acidic gas filter 200. In some examples, region 210 may include a portion of a surface of acidic gas filter 200. In some examples, region 210 may include substantially an entire surface of acidic gas filter 200.
(38) In some examples, the optical property may be indicative of filter status, for example, one or more of saturation, breakthrough, contamination, capacity, presence or absence of one or more predetermined chemical species in acidic filter 200 that may have been absorbed from air, or amount of a chemical or contaminant removed by acidic gas filter 200.
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(41) Thus, example articles and techniques according to the present disclosure provide filtration of acidic gas components from air.
(42) The present disclosure will be illustrated by the following non-limiting examples
EXAMPLES
Example 1
(43) SO.sub.2 removal from air was carried out by a media developed by coating a composition including reactants on a fiber substrate. The effect of coating compositions on SO.sub.2 removal performance was studied in the present example. Two performance of compositions including K.sub.2CO.sub.3 was compared with that of compositions including KHCO.sub.3. Each sample had a weight composition of PAMPS-K (MW 5 million M):potassium iodide:potassium succinate:base in a weight ratio of 0.2:0.1:0.5:3 respectively. K.sub.2CO.sub.3 is more basic and may have a higher potential capacity than KHCO.sub.3. Therefore it may be advantageous to use K.sub.2CO.sub.3 as the base or reactant. However, K.sub.2CO.sub.3 can gradually absorb CO.sub.2 from the air and convert to KHCO.sub.3.
Example 2
(44) Polymers including polyacrylic acid (PAA), polymethacrylic acid (PMAA), poly(acrylic acid-co-maleic acid) (PAAMA), polyacrylamide (PAM), and poly(2-acrylamido-2-methylpropane sulfonic acid) (PAMPS) were evaluated for their effect on acid gas component removal. The PAA or PAAMA polymers were used to prepared fiber filters with the formula of PAAK (or PAAMAK)/IDAK/KHCO3 (0.2:1:4) wt % (K referring to potassium in this notation). The breakthrough pH and capacity of each sample are plotted in
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Example 3
(46) The effect of the molecular weight of PAMPS on SO.sub.2 removal was evaluated.
Example 4
(47) While PAA and PAMPS are preferred, the presence of polymer may affect viscosity and surface tension of the coating solutions. For large scale fiber manufacturing, high concentration coating solutions may be used to save energy for drying. The concentration of the polymer needs to be controlled so that the coating solutions have moderate viscosity and low surface tension. Therefore, the fiber substrate can get wet evenly and quickly. Solution viscosity surface tension was measured by Cannon-Fenske viscometer and a custom capillary surface tension apparatus. The test results are shown in
Example 5
(48) The effect of humectant on acid gas component removal was evaluated. Several humectant substances were used in both the carbonate and bicarbonate systems, including acetic acid, formic acid, iminodiacetic acid (IDA), citric acid, lactic acid, malic acid, and succinic acid. The physical properties of these chemicals are summarized in Table 1. Among them, acetic acid was the best humectant so far because of its favorable pKa value, miscibility with water, and high diffusion rate in water. The acetic acid/acetate buffer may serve as a high efficient vehicle to continuously and effectively carry the proton from the gas/liquid interphase to the liquid/solid interface until the carbonate/bicarbonate was completely converted. With potassium acetate as the humectant, the conversion degree could possibly reach 100%. However, acetic acid is volatile. So it cannot be used in this application because acetic acid may be released from the sample once breaking through at low pH. The formic acid has the same problem. From this point of view, only the organic acids with very low vapor pressure were selected as the humectant additives. Other organic acids listed in Table 1 have various solubility and pKa values. Their effects on sample performance were tested and results are shown in
(49) TABLE-US-00001 TABLE 1 Melting Vapor Miscibility Point Pressure (/100 mL Acid ( C.) (Pa) water) pKa Acetic 16 15.8 miscible 4.76 Formic 8.4 40 miscible 3.77 Iminodiacetic 243 2.43 g 2.98, 9.89 Lactic 16.8 0.0813 miscible 3.86 Malic 130 0.0009 55.8 g 3.40, 5, 20 Citric 156 .sup.10.sup.7 147.76 g 3.13, 4.76, 6.4 Succinic 184 .sup.10.sup.5 5.8 g 4.2, 5.6
Example 6
(50) The effect of preservative on the acid gas component removal capacity after aging was evaluated. Potassium iodide (KI) was used as a preservative.
Example 7
(51) The effect of different substrates on acid gas component removal was evaluated. Different substrates were also used for SO.sub.2 removal filters.
Example 8
(52) The effect of water, moisture, or humidity on performance of acid gas component removal coatings was evaluated. While water may enhance adsorption, it may cause drifting of the coating materials, resulting in handling and storage problems and decrease in absorption performance. In order to improve the drifting stability of the coating materials at high humidity, several strategies may be considered to modify the properties of the coating layer, including 1) increasing the concentration and/or the molecular weight of the polymer, 2) the use of less soluble base materials such as Na.sub.2CO.sub.3, 3) the use of multivalent cations to induce ionic cross-linking, 4) and the use of cross-linkable polymers. The effect of each method was evaluated by measuring the weight loss after putting the samples in a desiccator with predetermined relative humidity. A saturated sodium chloride solution and pure water were used to get relative humidity of 75% and 100%, respectively. The drifting tests were performed at room temperature for 48 hours. A certain amount of the coating materials drifted out of the samples. Then the samples were dried at 80 C. for 30 min and weight loss was calculated. The target was to minimize the weight loss at high humidity while maintaining high absorption performance. Table 2 shows the drifting results of each modifying method.
(53) Sample SX-0 was the original sample with the coating composition of PAWS (MW: 10 million)/potassium iodide/potassium succinate/K.sub.2CO.sub.3 (0.4:0.1:0.7:3). It exhibited weight losses of 30.8% and 47.4% at 75% and 100% relative humidity respectively. The absorption capacity was tested at 50% relative humidity, 20 ppm SO.sub.2 concentration, and 2.6 L/min flow rate. Based on coating weight, the SX-0 had a capacity of 0.33 g S02/g. From SX-1 to SX-3, increasing concentration of PAMPS or higher molecular weight was used. The weight losses slightly decreased; indicating that higher viscosity of the coating solution could alleviate the coating drifting. However, the polymer could not completely stop the drifting because of its high solubility in water. The partial replacement of K.sub.2CO.sub.3 by Na.sub.2CO.sub.3 (SX-4) could also help to alleviate the drifting because Na.sub.2CO.sub.3 has a much higher critical relative humidity (92%) than K.sub.2CO.sub.3 (43%). Due to the poor absorption capacity, this approach could not be accepted. Divalent cations such as Ca.sup.2+, Ba.sup.2+, Mg.sup.2+, and Zn.sup.2+ have shown a high capability to stop drifting (SX-5-SX-9). They almost completely stopped drifting at 75% RH. This may be because of the formation of ionic cross-linking between polymer chains and the formation of small carbonate particles. These particles could form relatively stable suspension in the solution. Upon drying, these particles may coalesce and form reinforced composite. In particular, MgCl.sub.2 and ZnCl.sub.2 performed well at 100% RH. ZnCl.sub.2 was able to form stable suspension in the solution when adding ZnCl.sub.2 dilute solution in the rest of mixture solution. Colloidal silica (LUDOX AM) can be used as well due to the same mechanism.
(54) TABLE-US-00002 TABLE 2 75% RH 100% RH Capacity Weight Weight (g SO.sub.2/g loss loss coating Sample Method (%) (%) material) SX-0 30.8% 47.4% 0.33 SX-1 1.5x PAMPS 22.8% 40.6% 0.31 (MW: 10 million) SX-2 2x PAMPS 24.7% 38.2% (MW: 10 million) SX-3 1x PAMPS 21.3% 31.5% (MW: 20 million) SX-4 KNaCO3 10.2% 31.2% 0.07 SX-5 Ca(OH).sub.2 (6% of coating) 0.00% 19.2% 0.09 SX-6 CaCl.sub.2 (13% of coating) 6.45% 29.3% 0.25 SX-7 Ba(OH).sub.2 0.00% 27.3% 0.27 (17% of coating) SX-8 MgCl.sub.2 (17% of coating) 2.70% 7.89% SX-9 ZnCl.sub.2 (17% of coating) 2.78% 7.58% SX-10 SiO.sub.2 (17% of coating) 2.22% 10.5% SX-11 CG39/PAA 0.90% 1.08% SX-12 S1/PAA 5.56% 29.7% SX-13 PDAAM-co-PAMPS cross- 2.08% 4.17% linked by ADH
Example 9
(55) The effect of cross-linkable polymers on drifting was evaluated. Cross-linkable polymers may significantly reduce or prevent drifting. Polyacrylic acid (PAA) was mixed with glycerol and NaH.sub.2PO.sub.4 in water to form a coating solution (PAA:glycerol:NaH.sub.2PO.sub.4=1:0.1:0.3 weight ratio), which was coated onto fiber substrates like glass fiber and S1. The coating layer became cross-linked upon heating at 170 C. for 10 min. This cross-linked PAA can form stable hydrogel after absorbing water. Therefore, the coating materials were not able to flow out of the hydrogel layer. No drifting was observed even at 100% RH (SX-11). However, since PAA cross-linking happens at high temperature, this method did not work well for polymer substrate S1. The S1 substrate became soft and generated a strong plastic odor.
(56) Ideally, the coating solution should be stable and storable for a fairly long time. During or after coating onto the substrate, the cross-linking may be triggered by mild conditions including pH adjustment (acid or base), drying, relatively low temperature and UV. The polymers may include functional groups like epoxy, amines, vinyl, ketone, aldehyde etc. A reaction between diacetone acrylamide (DAAM) and adipic dihydrazide (ADH) to form Schiff base may be used. Both chemicals are non-toxic and the reaction only has water as by-product. In addition, the cross-linking reaction may be activated during drying. Since poly(diacetone acrylamide) is not water soluble, a copolymer of diacetone acrylamide and 2-acrylamido-2-methylpropane sulfonic acid (PDAAM/PAMPS) with 1:1 molar ratio was synthesized. This copolymer was used to replace PAMPS and it worked together with ADH to form hydrogel during the manufacturing of the base media. It was observed that the coating solution maintained homogeneous. After coating and drying, due to the high temperature and concentration, the polymer became cross-linked and effectively stopped drifting even at 100% RH.
(57) The copolymer PDAAM/PAMPS may form stable cross-linking structure with PNHMA at elevated temperature. Depending on the cross-linking degree, the formed hydrogel had different stability and water uptake. It was observed that with a cross-linking degree of 33%, the samples prepared with K.sub.2CO.sub.3 or KHCO.sub.3 showed very good stability of coating materials at both 75% and 100% relative humidity. Almost no weight loss was observed for a week. However, sample capacity was decreased somewhat, likely due to the enhanced difficulty for the gas molecule to diffuse into the gel.
Example 10
(58) The use of pH indicators for indicating the state of the acid gas removal coating was evaluated. Because of the significant change in pH during SO.sub.2 absorption, it is possible to use a pH indicator to determine the breakthrough of the fiber. A desired pH indicator may have a stable and bright color during storing and a sharp and apparent color change at breakthrough. In addition, the indicator should preferably have no negative effect on filter performance. The pH indicators used in this study included bromothymol blue, neutral red, phenol red, and bromocresol purple. They were selected because they can change color at about neutral pH. The samples were prepared by adding about 0.3% of indicator to the coating mixture. The fiber was then exposed to HCl vapor to initiate the pH and color change.
Example 11
(59) For applications at high relative humidity of >90%, drifting of the coating materials may pose a serious problem due to several reasons. Firstly, polyester substrate is hydrophobic. The coating materials cannot spread very well on the surface of the fibers. Secondly, potassium carbonate (K.sub.2CO.sub.3) is a strong humectant and has a low critical relative humidity of 43%. It tends to draw water from moisture air at relative humidity of >43%. Thirdly, K.sub.2CO.sub.3 has a relatively low solubility (112 g/100 mL at 20 C.). When converted to KHCO.sub.3 by absorbing CO.sub.2, the solubility is even lower (33.7 g/100 mL at 20 C.). Therefore, when drying the solution, K.sub.2CO.sub.3 may precipitate out from the polymer solution. When water-soluble polymer stabilizer was used, K.sub.2CO.sub.3 phase always formed separately. At humid conditions, the K.sub.2CO.sub.3 phase would dissolve and drift.
(60) To solve this problem, a strong gel may be used to stabilize the coating layer. Potassium alginate is soluble in water. It can form a water insoluble strong gel with multivalent cations such as calcium chloride because of the carboxylic groups. The effect of different cross-linking methods is shown in Table 3. The formula of SX-14 was PAM:PAMPS 2:1/alginate/CaCl.sub.2/HEDP-K.sub.3/K.sub.2CO.sub.3 (0.6:0.2:0.2:0.4:2.6). PAM-PAMPS 2:1 was used to increase viscosity of the solution and stabilize the suspension. HEDP was neutralized by KOH and used as antiscalant to decrease the particle size. Both the polymer and antiscalant worked together to make a coating suspension which could be stable for several days to several weeks. K.sub.2CO.sub.3 was used as the base to absorb acid gases. Different ratios of alginate and CaCl.sub.2 and ZnCl.sub.2 were studied. As shown in Table 3, all samples showed very low drifting at 100% humidity (<5%). Sample SX-16 had double amounts of alginate and CaCl.sub.2 than SX-14. It had the lower weight loss than SX-14. The sample had visually even coating after putting in a 100% relative humidity chamber for 3 days. Therefore, this formulation was effective for drifting prevention. ZnCl.sub.2 was also tested. It was found to not be as effective as CaCl.sub.2.
(61) TABLE-US-00003 TABLE 3 Weight loss at Sample Cross-linking method 100% RH SX-14 Alginate/CaCl.sub.2 (1:1) 4.69% SX-15 Alginate/CaCl.sub.2 (1:2) 4.29% SX-16 Alginate/CaCl.sub.2 (2:2) 1.07% SX-17 Alginate/CaCl.sub.2 (2:1) 4.95% SX-18 Alginate/ZnCl.sub.2 (2:2) 4.01% SX-19 Alginate/ZnCl.sub.2 (2:1) 4.44%
(62) Instead of forming a suspension solution, the cross-linker can also be sprayed onto an alginate containing media. Two samples were prepared using the formulation of SX-16. As shown in
(63) TABLE-US-00004 TABLE 4 Capacity Sample Preparation method (mg/g) SX-16-1 Adding CaCl.sub.2 to the coating 132 solution to form a suspension SX-16-2 Spraying CaCl.sub.2 to the alginate- 59 containing media Test conditions: 50% relative humidity; 2.6 L/min; 30 ppm SO.sub.2
(64) Based on the same cross-linking method as SX-16, different amounts of potassium carbonate were added to the solution. The effect of K.sub.2CO.sub.3 concentration on SO.sub.2 absorption performance is shown in Table 5 and
(65) TABLE-US-00005 TABLE 5 Sample % K.sub.2CO.sub.3 Capacity (mg/g) SX-16-3 72% 153 SX-16-4 65% 132 SX-16-5 60% 97 Test conditions: 50% relative humidity; 2.6 L/min; 30 ppm SO.sub.2
Example 12
(66) The use of inorganic particles as stabilizer for the coating solutions was evaluated. Sodium or calcium bentonite powder was added to the coating solution. The weight content of the inorganic particles in the solid coating materials was controlled to be between 5 and 20%. The coating solution was prepared by first mixing PAMPS-K:potassium succinate:K.sub.2CO.sub.3:phenol red in a weight ratio of 0.5:0.7:3:0.008 with water to make a 15% solution. Various amounts of sodium or calcium bentonite were added to form a stable suspension. After coating onto a nonwoven polyester substrate, the samples were placed in a 100% relative humidity chamber. Only slight drifting was observed with 5% of bentonites added. The sample with 20% bentonites showed little drifting although the samples were still wet. When KHCO.sub.3 was used instead of K.sub.2CO.sub.3, the sample with 20% bentonites became even more stable because KHCO.sub.3 absorbs less moisture than K.sub.2CO.sub.3. The samples showed no drifting, and very little material adhered to a probe when the probe contacted the media. Without being bound by theory, this may be because the bentonites formed strong gel within the coating and significantly increased the viscosity. The result indicated the effectiveness of bentonites to stabilize the coating materials.
(67) Various examples of the invention have been described. These and other examples are within the scope of the following claims.