Apparatus, systems, and methods for fluid filtration
10071927 ยท 2018-09-11
Assignee
Inventors
Cpc classification
C02F2101/22
CHEMISTRY; METALLURGY
B01D2311/04
PERFORMING OPERATIONS; TRANSPORTING
B01D2311/04
PERFORMING OPERATIONS; TRANSPORTING
B01D65/08
PERFORMING OPERATIONS; TRANSPORTING
C02F9/00
CHEMISTRY; METALLURGY
B01D63/066
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01D65/08
PERFORMING OPERATIONS; TRANSPORTING
C02F9/00
CHEMISTRY; METALLURGY
Abstract
The present disclosure relates, according to some embodiments, to apparatus, systems, and methods for reduction and/or removal of one or more contaminants (e.g., heavy metals, chromium, phosphorous, phosphorous compounds, nitrogen, nitrogen compounds) from a feed composition (e.g., a fluid). Apparatus, systems, and methods, in some embodiments, may be operable to decontaminate a fluid with comparatively little or no contaminant containing waste fluid.
Claims
1. A decontamination system for removing a contaminant from an intake fluid comprising the contaminant, the system comprising: (a) a fluid reactor configured (i) to receive the intake fluid, (ii) to permit the contaminant to bind an adsorbent to form a contaminant-adsorbent material, and (iii) to form a fluid reactor output stream comprising the contaminant-adsorbent material; (b) a catalyst recovery unit (CRU) (i) comprising a CRU porous membrane defining a CRU retentate portion and a CRU permeate portion of the catalyst recovery unit, (ii) configured to receive the fluid reactor output stream in the CRU retentate portion of the CRU porous membrane and fractionate the fluid reactor output stream into a CRU retentate comprising the contaminant-adsorbent material in the CRU retentate portion of the catalyst recovery unit and a CRU permeate substantially free of the contaminant in the CRU permeate portion of the catalyst recovery unit, wherein the CRU retentate portion is in fluid communication with an intake stream and a CRU filtrate forms a first discharge stream; (c) a contaminant-concentrating module (DeWRS) (i) in fluid communication with the CRU retentate portion of the catalyst recovery unit, (ii) comprising a DeWRS porous membrane, oriented in a vertical position, defining a DeWRS retentate portion and a DeWRS permeate portion of the contaminant- concentrating module, (iii) configured to receive at least a portion of the CRU retentate in the DeWRS retentate portion of the contaminant-concentrating module and fractionate the CRU retentate into a DeWRS retentate comprising the contaminant-adsorbent material in the DeWRS retentate portion of the contaminant-concentrating module and a DeWRS permeate substantially free of the contaminant in the DeWRS permeate portion of the contaminant-concentrating module, wherein a DeWRS filtrate forms a second discharge stream, and (iv) configured to permit the contaminant-adsorbent material in the DeWRS retentate to settle into a contaminant trap positioned below the DeWRS porous membrane, and form a contaminant trap slug; (d) a contaminant-adsorbent desorption unit, wherein the contaminant-adsorbent desorption unit: (i) is in fluid communication with the DeWRS retentate portion of the contaminant-concentrating module and in fluid communication with a first storage tank so as to receive an acidic composition or a basic composition of the first storage tank, (ii) comprises a heating unit, a desorbed adsorbent separation device comprising a contaminant-adsorbent desorption unit porous membrane defining a contaminant-adsorbent desorption unit retentate portion, the first storage tank configured to contain the acidic composition having a pH below about 7 or the basic composition having a pH above about 7, and a contaminant-adsorbent desorption unit permeate portion of the the contaminant-adsorbent desorption unit, (iii) is configured to receive at least a portion of the DeWRS retentate in the contaminant-adsorbent desorption unit retentate portion of the a contaminant-adsorbent desorption unit and fractionate the received DeWRS retentate into a contaminant-adsorbent desorption unit retentate comprising the contaminant-adsorbent material in the contaminant-adsorbent desorption unit retentate portion of the contaminant-adsorbent desorption unit and a contaminant-adsorbent desorption unit permeate substantially free of the contaminant in the contaminant-adsorbent desorption unit permeate portion of the contaminant-adsorbent desorption unit, wherein the contaminant-adsorbent desorption unit filtrate forms a third discharge stream; receive from the first storage tank into the contaminant-adsorbent desorption unit retentate portion of the contaminant-adsorbent desorption unit an amount of the acid composition, desorb the contaminant from the adsorbent by mixing the contents of the contaminant-adsorbent desorption unit retentate portion of the contaminant-adsorbent desorption unit to permit desorption of the contaminant from the adsorbent to form a desorbed contaminant stream, a desorbed adsorbent stream, and, optionally, a residual contaminant-adsorbent material, wherein the heating unit is configured to heat the contents of the contaminant-adsorbent desorption unit retentate portion of the contaminant-adsorbent desorption unit to promote desorption of the contaminant from the adsorbent, and convey the optional residual contaminant-adsorbent material, if present, to the first storage tank; (e) a clean adsorbent storage tank in fluid communication with the desorbed adsorbent stream and the intake stream; (f) a second storage tank configured to contain a second storage tank fluid comprising (i) a base if the first storage tank contains the acidic composition, or (ii) an acid if the first storage tank contains the basic composition; (g) a rinse tank in fluid communication with the desorbed contaminant stream, in fluid communication with the second storage tank and configured to receive and mix the received desorbed contaminant stream with the received second storage tank fluid to permit formation of a contaminant precipitate and a rinse tank supernatant, wherein the rinse tank supernatant forms a fourth discharge stream.
2. A decontamination system according to claim 1, wherein the fluid reactor is configured to permit the change of oxidation state of at least a portion of the contaminant to form a reduced contaminant or an oxidized contaminant.
3. A decontamination system according to claim 1, wherein the fluid reactor comprises a photocatalytic reactor operable to photo reduce the contaminant.
4. A decontamination system according to claim 1, wherein the contaminant is chromium.
5. A decontamination system according to claim 1, wherein the contaminant is hexavalent chromium.
6. A decontamination system according to claim 2, wherein the reduced contaminant is trivalent chromium.
7. A decontamination system according to claim 1, wherein the adsorbent comprises titanium.
8. A decontamination system according to claim 1, wherein the adsorbent comprises titanium oxide.
9. A decontamination system according to claim 1, wherein the CRU porous membrane comprises a ceramic membrane.
10. A decontamination system according to claim 9, wherein the CRU porous membrane is configured to operate as a crossflow membrane.
11. A decontamination system according to claim 1, wherein the concentration of the contaminant-adsorbent material in the CRU retentate is from about 10 times to about 20 times higher than the concentration of the contaminant-adsorbent material in a reduction reactor output stream.
12. A decontamination system according to claim 1, wherein the DeWRS porous membrane comprises a ceramic membrane.
13. A decontamination system according to claim 12, wherein the DeWRS porous membrane is configured to operate as a dead-end membrane.
14. A decontamination system according to claim 1, wherein the concentration of the contaminant-adsorbent material in the contaminant trap slug is from about 10 times to about 20 times higher than the concentration of the contaminant-adsorbent material in the CRU retentate.
15. A decontamination system according to claim 1, wherein the contaminant-concentrating module is further configured to pulse the DeWRS porous membrane with a fluid shock.
16. A decontamination system according to claim 1, wherein the contaminant-adsorbent desorption unit is further configured to receive the at least a portion of the DeWRS retentate in the contaminant-adsorbent desorption unit retentate portion of the contaminant-adsorbent desorption unit under pressure.
17. A decontamination system according to claim 1, wherein the contaminant-adsorbent desorption unit is further configured to mix the contents of the contaminant-adsorbent desorption unit retentate portion of the contaminant-adsorbent desorption unit to form a contaminant-adsorbent desorption unit mixture by bubbling a gas through the contents of the contaminant-adsorbent desorption unit retentate portion of the contaminant-adsorbent desorption unit.
18. A decontamination system according to claim 1, wherein the contaminant-adsorbent desorption unit is further configured to receive the amount of the acid composition at a temperature of about 40 ? C. to about 60 ? C., at a concentration of up to about 5 wt. %, and at a pH of less than about 1.
19. A decontamination system according to claim 1, wherein the first storage tank is in fluid communication with a make-up tank configured to contain a volume of a make-up acid composition or a volume of a make-up base composition.
20. A decontamination system according to claim 1, wherein the first storage tank acid composition comprises sulfuric acid.
21. A decontamination system according to claim 1, wherein the contaminant comprises chromium.
22. A decontamination system according to claim 1, wherein the contaminant comprises phosphorous or a phosphorous compound.
23. A decontamination system according to claim 1, wherein the contaminant comprises nitrogen or a nitrogen compound.
24. A decontamination system according to claim 1, wherein the first discharge stream, the second discharge stream, the third discharge stream, and the fourth discharge stream each comprises less than about 20 ppb of the contaminant.
25. A decontamination system according to claim 1, wherein the first discharge stream, the second discharge stream, the third discharge stream, and the fourth discharge stream each comprises less than about 1 ppb of the contaminant.
26. A decontamination system according to claim 25, wherein the first discharge stream, the second discharge stream, the third discharge stream, and the fourth discharge stream together form a composite discharge stream.
27. A decontamination system according to claim 26, wherein the composite discharge stream comprises less than about 20 ppb of the contaminant.
28. A decontamination system according to claim 26, wherein the composite discharge stream comprises less than about 1 ppb contaminant.
29. A method for separating an intake fluid comprising a contaminant into a contaminant solid fraction and a discharge fluid fraction substantially free of the contaminant, the method comprising: (a) reducing the contaminant in a reduction reactor to form a reduced contaminant or oxidizing the contaminant in an oxidizing reactor to form an oxidized contaminant; (b) adsorbing the reduced contaminant or the oxidized contaminant to an adsorbent to form a contaminant-adsorbent material; (c) forming a fluid reactor output stream comprising the contaminant-adsorbent material; (d) optionally combining a portion of the fluid reactor output stream into the intake fluid; (e) fractionating up to all of the fluid reactor output stream in a catalyst recovery unit (CRU) comprising a CRU porous membrane into a CRU retentate comprising the contaminant-adsorbent material and a CRU permeate substantially free of the contaminant, wherein the CRU permeate forms a first discharge stream; (f) fractionating the CRU retentate in a contaminant-concentrating module (DeWRS) comprising a DeWRS porous membrane oriented in a vertical position, into a DeWRS retentate comprising the contaminant-adsorbent material and a DeWRS permeate substantially free of the contaminant, wherein the DeWRS permeate forms a second discharge stream; (g) gathering the contaminant-adsorbent material in the DeWRS retentate into a contaminant slug; (h) fractionating the contaminant slug in a contaminant-concentrating mixer tank (DeWMT) comprising a DeWMT porous membrane into a DeWMT retentate comprising the contaminant-adsorbent material and a DeWMT permeate substantially free of the contaminant, wherein the DeWMT permeate forms a third discharge stream; (i) adding acid from an acid storage tank to the DeWMT retentate comprising the contaminant-adsorbent material to form an acidified DeWMT retentate or adding acid or base from a storage tank to the DeWMT retentate comprising the contaminant-adsorbent material to form an acidified or basic DeWMT retentate; (j) mixing the acidified or basic DeWMT retentate to desorb the contaminant from the adsorbent and form a desorbed contaminant stream, a desorbed adsorbent stream, and, optionally, a residual contaminant-adsorbent material; (k) optionally combining up to an entirety of the desorbed absorbent stream into the intake fluid; (l) combining in a rinse tank the desorbed contaminant stream with sufficient base to form a contaminant precipitate and a rinse water tank supernatant, wherein the rinse water tank supernatant forms a fourth discharge stream; and (m) optionally conveying the residual contaminant-adsorbent material to the acid storage tank or the storage tank, wherein the contaminant precipitate forms the contaminant solid fraction and the first, second, third, and fourth discharge streams together form the discharge fluid fraction.
30. A method for separating an intake fluid according to claim 29, wherein reducing the contaminant in the reduction reactor to form the reduced contaminant further comprises photo reducing the contaminant.
31. A method for separating an intake fluid according to claim 29, wherein the contaminant is chromium.
32. A method for separating an intake fluid according to claim 29, wherein the contaminant is hexavalent chromium.
33. A method for separating an intake fluid according to claim 29, wherein the reduced contaminant is trivalent chromium.
34. A method for separating an intake fluid according to claim 29, wherein the contaminant comprises phosphorous or a phosphorous compound.
35. A method for separating an intake fluid according to claim 29, wherein the contaminant comprises nitrogen or a nitrogen compound.
36. A method for separating an intake fluid according to claim 29, wherein the adsorbent comprises titanium.
37. A method for separating an intake fluid according to claim 29, wherein the adsorbent comprises titanium oxide.
38. A method for separating an intake fluid according to claim 29, wherein the CRU porous membrane comprises a ceramic membrane.
39. A method for separating an intake fluid according to claim 29 further comprising operating the CRU porous membrane as a crossflow membrane.
40. A method for separating an intake fluid according to claim 29, wherein the concentration of the contaminant-adsorbent material in the CRU retentate is from about 10 times to about 20 times higher than the concentration of the contaminant-adsorbent material in the fluid reactor output stream.
41. A method for separating an intake fluid according to claim 29, wherein the DeWRS porous membrane comprises a ceramic membrane.
42. A method for separating an intake fluid according to claim 29 further comprising operating the DeWRS membrane as a dead-end membrane.
43. A method for separating an intake fluid according to claim 29, wherein the concentration of the contaminant-adsorbent material in the contaminant slug is from about 10 times to about 20 times higher than the concentration of the contaminant-adsorbent material in the CRU retentate.
44. A method for separating an intake fluid according to claim 29 further comprises pulsing the DeWRS porous membrane with a dynamic shock.
45. A method for separating an intake fluid according to claim 29 further comprising conveying the DeWRS retentate to the contaminant-concentrating mixer tank under pressure.
46. A method for separating an intake fluid according to claim 29, wherein the mixing the acidified or basic DeWMT retentate further comprises bubbling a gas through contents of the contaminant-concentrating mixer tank.
47. A method for separating an intake fluid according to claim 29, wherein the acid added to the DeWMT retentate is pre-heated to a temperature of about 40 ? C. to about 60 ? C. and has a concentration of up to about 5 wt. % and a pH of less than about 1.
48. A method for separating an intake fluid according to claim 29 further comprising conveying make-up acid from a make-up acid storage tank to the acid storage tank.
49. A method for separating an intake fluid according to claim 29, wherein the acid comprises sulfuric acid.
50. A method for separating an intake fluid according to claim 29, wherein the contaminant comprises chromium.
51. A method for separating an intake fluid according to claim 29, wherein the first discharge stream, the second discharge stream, the third discharge stream, and the fourth discharge stream each comprises less than about 20 ppb of the contaminant.
52. A method for separating an intake fluid according to claim 29, wherein the first discharge stream, the second discharge stream, the third discharge stream, and the fourth discharge stream each comprises less than about 1 ppb of the reduced contaminant.
53. A method for separating an intake fluid according to claim 29, wherein the discharge fluid fraction comprises less than about 20 ppb of the contaminant.
54. A method for separating an intake fluid according to claim 29, wherein the discharge fluid fraction comprises less than about 1 ppb of the reduced contaminant.
55. A method for separating an intake fluid according to claim 29, wherein the base comprises sodium hydroxide.
56. A method for separating an intake fluid according to claim 29 further comprising maintaining constant the portion of the fluid reactor output stream combined into the intake fluid and a portion of the fluid reactor output stream fractionated in the catalyst recovery unit.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Some embodiments of the disclosure may be understood by referring, in part, to the present disclosure and the accompanying drawings, wherein:
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
(19)
(20)
(21)
(22)
DETAILED DESCRIPTION
(23) The present disclosure relates, in some embodiments, to apparatus, systems, and methods for reduction and/or removal of one or more heavy metals (e.g., heavy metals, chromium, phosphorous, phosphorous compounds, nitrogen, nitrogen compounds) from a feed composition (e.g., a fluid).
(24) The present disclosure relates, in some embodiments, to efficient defouling mechanisms for removing foulants in a filtration membrane. According to some embodiments, the present disclosure relates to filtration membranes optimized for use with the disclosed defouling mechanisms.
(25)
(26) In a process of using the filtration membrane 10 to decontaminate contaminated media, the performance of the filtration membrane 10 may decline due to organic, inorganic and biological fouling mechanisms in the process. For example, excessive fouling of the substrate 12 and/or the membrane films 16 may decrease flux, increase cross flow and transmembrane pressure, and increase energy consumption.
(27)
(28)
(29) Also shown in
(30)
(31) It is to be appreciated that a dynamic shock is distinct from a back-pulse or a back-wash, and offers performance improvements in at least several aspects. The phases of a dynamic shock may be carried out in less than one second, and substantially little or no permeate is lost back to the concentrate side of the membrane films 16. Consequently, a dynamic shock can be repeated as frequently as desired to prevent matter from fouling the membrane 10. For example, in an embodiment, dynamic shocks may be applied to the membrane 10 about once per minute to prevent the lodging of foulants before they become fixed on the membrane 10 and accumulate. According to some embodiments, dynamic pulses may be applied from about once per seceond to about once per 5 seconds, to about once per 15 seconds, to about once per 30 seconds, to about once per 45 seconds, to about once per 60 seconds, to about once per 75 seconds, to about once per 90 seconds, to about once per 2 minutes, to about once per 5 minutes, or longer. Bursts of multiple pulses (e.g., about 2 to about 5 pulses all applied within about 1-10 seconds) may be applied at the same frequencies as single pulses (e.g., one burst repeated about every minute).
(32) By relying on cavitation instead of physical shearing force to clean the membrane 10, the effect of water channeling becomes irrelevant, and the cleaning of the membrane 10 may be performed consistently throughout the membrane 10. It is to be further appreciated that the ability for more efficient and consistent cleaning throughout the membrane 10 allows for packing more membrane films 12 and channels 14 into one membrane 10.
(33) The dynamic shock of the present disclosure may be generated with any mechanism for a rapid release of energy to the membrane surface, such as the Hammer effect, shot peaning to remove paint, and sonification.
(34) In an embodiment, the valve 74 is opened and closed as quickly as physically possible to complete the first subsecond phase 52 of a dynamic shock. In an embodiment, the valve 74 may be opened and closed in less than 0.50 second; in an optimized embodiment, the valve 74 may be opened and closed in less than 0.25 second. In an embodiment, after less than a second of holding the elevated pressure, the second subsecond phase 54 may be completed. In the third subsecond section, the rapid high pressure in the permeate fluid may be released by opening valve 72 in the permeate line, which creates a rapid de-pressurization in the membrane 10 and causes a second reverse dynamic shock wave. This may be considered a double acting effect. Again, the valve 72 may be opened as quickly as possible. In some embodiments, opening valve 72 may take less than 0.50 second or less than 0.25 second. The above described process of operating the system 70 to provide the dynamic shock may be substantially prevent the fouling of the membrane 10, thereby allowing a continuous filtration process. It is to be appreciated that other suitable methods could be used to provide a dynamic shock. For example, a diaphragm (not shown) or ram (not shown) may transfer the energy required rapidly without moving or displacing the permeate fluid in the membrane 10.
(35)
(36)
(37) The SiC membrane 80 may allow for reduced trans-membrane pressure (TMP) because of the strength of SiC substrate 82 over Alpha Alumina. This allows for the economical use of a smaller pore size. Additionally, the SiC membrane 80 has smaller particles which allows for thinner wall and a thinner membrane. The illustrated dimensions, including the hexagonal cross-sectional shape of the SiC membrane 80, the separations between channels 84, the width of the SiC membrane 80, and the distance of the channels 84 from the edge of the SiC membrane 80, have been substantially optimized for flux, TMP, and cross flow pressure drop. In an embodiment, the separations between the channels 84 (from center to center) may preferably range between 0.2 to 0.25 inches. In an embodiment, width of the SiC membrane 80 may preferably range between 1.25 to 1.75 inches. In an embodiment, the distance between the center of the outside channels 84 to the edge of the SiC membrane 80 may preferably range between 0.14 to 0.18 inches. It is to be appreciated that the above discussed dimensions may be varied according to the needs of particular application.
(38) It is to be appreciated that the filtration membranes and filtration systems of the present disclosure may be integrated with a variety of decontamination technology, such as photocatalytic technology. The integration may be accomplished without break tanks, loss of excessive line pressure, and/or booster pumps.
(39) While various embodiments in accordance with the principles disclosed herein have been described above, it should be understood that they have been presented by way of example only, and not limitation. Thus, the breadth and scope of this disclosure should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with any claims and their equivalents issuing from this disclosure. Furthermore, the above advantages and features are provided in described embodiments, but shall not limit the application of such issued claims to processes and structures accomplishing any or all of the above advantages.
(40) Additionally, the section headings herein are provided for consistency with the suggestions under 37 CFR 1.77 or otherwise to provide organizational cues. These headings shall not limit or characterize the embodiment(s) set out in any claims that may issue from this disclosure. Specifically and by way of example, although the headings refer to a Technical Field, the claims should not be limited by the language chosen under this heading to describe the so-called field. Further, a description of a technology in the Background is not to be construed as an admission that certain technology is prior art to any embodiment(s) in this disclosure. Neither is the Summary to be considered as a characterization of the embodiment(s) set forth in issued claims. Furthermore, any reference in this disclosure to invention in the singular should not be used to argue that there is only a single point of novelty in this disclosure. Multiple embodiments may be set forth according to the limitations of the multiple claims issuing from this disclosure, and such claims accordingly define the embodiment(s), and their equivalents, that are protected thereby. In all instances, the scope of such claims shall be considered on their own merits in light of this disclosure, but should not be constrained by the headings set forth herein.
(41) In some embodiments, a decontamination system for removing contaminants from a fluid comprises a filtration unit and a recovery unit. The filtration unit is operable to receive an adsorbent and the fluid comprising the contaminants. The filtration unit comprises a filter operable to separate the fluid from the adsorbent and contaminants adsorbed onto the adsorbent, the filter comprising a first portion and a second portion separated by a membrane. The filtration unit also comprises a first filter output in cooperation with the first portion and operable to receive the adsorbent and the contaminants adsorbed onto the adsorbent. The filtration unit also comprises a second filter output in cooperation with the second portion and operable to receive the effluent. The recovery unit is operable to receive the adsorbent and the contaminants adsorbed onto the adsorbent from the first filter output of the filtration unit. The recovery unit is also operable to separate the adsorbent and the contaminants adsorbed onto the adsorbent. The recovery unit comprises a stripping unit operable to strip the contaminants from the adsorbents and a separation unit operable to separate the adsorbent to a first recovery output and the contaminants to a second recovery output.
(42) A filtration system for separating contaminants from a fluid in a decontamination system, in some embodiments, is configurable to receive the fluid comprising the contaminants and an adsorbent. The filtration system comprises a filter, a first output, and a second output. The filter is operable to separate the fluid from the adsorbent and the contaminants adsorbed onto the adsorbent. The filter comprises a first portion and a second portion separated by a membrane. The first output is in cooperation with the first portion and operable to receive the adsorbent and the contaminants adsorbed onto the adsorbent. The second output is in cooperation with the second portion and operable to receive the effluent.
(43) According to some embodiments, a method of removing a contaminant from a fluid comprises feeding an adsorbent into the contaminated fluid. The method further comprises separating, in a first separation treatment, the adsorbent and contaminant adsorbed onto the adsorbent from the fluid. The method further comprises separating, in a second separation treatment, the contaminant from the contaminant adsorbed onto the adsorbent. The method further comprises recovering the adsorbent and providing the recovered adsorbent for reuse in feeding into contaminated fluid.
(44) Direct treatment costs associated with contaminated fluid treatment processes may include the expenses for the clarifier/filtration costs, pH control, alkalinity control, polymer addition, coagulant addition, sludge thickening, and sludge disposal (land fill). By reducing or eliminating some of these expenses, the cost of waste fluid treatment may be reduced. Periodic or continuous addition of a new supply of coagulants is required in some treatment processes because coagulants may chemically react as they are added to the contaminated fluid and thus become irreversibly consumed. The reacted coagulants and the coagulated contaminants end up in the sludge or solids, which are typically land filled. Using adsorbents that do not react chemically during the treatment process may allow the adsorbents to be separated and recovered from the contaminants. And reusing the recovered adsorbents may reduce or eliminate the need for a new supply of adsorbents, thereby reducing the cost of treatment. As discussed above, in some clarifier operations, a polymeric material may be added to aid in the settling of solids in the clarifier. But the addition of the polymeric material increases costs. By reducing or eliminating the need for the addition of polymeric materials, a cost reduction may be achieved.
(45) One aspect of the present disclosure relates to treating contaminated fluid with suitable adsorbents that are operable to adsorb the contaminants onto the surface of the adsorbents and to be stripped of the contaminants with a desorption process. Using such adsorbents instead of conventional coagulants allows for the recovery of adsorbents for reuse. The recovery and reuse of the adsorbents may reduce the cost of treatment significantly by reducing or eliminating the need for new addition of fresh coagulants and polymeric material into the treatment process. Applying a semi-batch or continuous process by continuously adding adsorbents into the treatment may also improve the efficiency of the overall decontamination process.
(46) As used herein, the term contaminated fluid is a fluid that contains undesirable organics, inorganics, metals, and possibly microbial cells or other microorganisms. Although contaminants are undesirable in the sense that they are usually toxic when ingested or contacted by humans, undesirable should not be understood to be restricted to such toxic substances. As used herein, the term decontaminated effluent means that the undesirable substances in the contaminated fluid have been altered or modified into a desirable or an acceptable substance, again, usually a substance that is non-toxic. Normally such alteration or modification of any organic substance is achieved by decomposing the substance into by-products having a smaller molecular weight than the original contaminated fluid. It should also be noted that the terms fluids and effluents should not be read or interpreted as being limited to liquids. Rather, such terms should be interpreted to include gases, such as air.
(47)
(48)
(49) Filter unit 140 may further include a suitable filter 144 for separating the macromolecules comprising the adsorbents and the adsorbed contaminants. Filter 144 may be a membrane that includes a wall (not shown) separating the interior of filter 144 from its exterior and pores (not shown) defined in the wall of filter 144. As slurry stream 130 passes through the interior of filter 144, the pores of filter 144 allow the movement of decontaminated fluid from the interior to the exterior of filter 144. Filter 144 may have an average pore size that is larger than the anticipated size of the macromolecules formed by the contaminants being adsorbed on the adsorbents. In an embodiment, the pore size of filter 144 is sufficiently large so as to induce micro-filtration of the treated slurry while only permitting negligible amounts of the contaminant-adsorbent macromolecules to permeate through the pores of filter 144. In another embodiment, the pore size of filter 144 may be sized for ultra-filtration.
(50) It is to be appreciated that during the operation of system 100, the flow rate of the slurry 130 and the pressure across the membrane of filter 144 may be maintained to allow for either dead-end filtration or cross-flow filtration. In dead-end filtration, the contaminant-adsorbent macromolecules are directed towards and collect on the wall of filter 144. In cross-flow filtration, two directional components are employed. First, a substantial linear velocity is maintained through the filter, i.e., parallel to the wall of filter 144. Second, a substantial pressure differential, also referred to as a transmembrane pressure, is applied across filter 144. The transmembrane pressure drives the decontaminated fluid through the wall of filter 144 while the high linear velocity continually removes most of the contaminant-adsorbent macromolecules away from the wall of the filter 140. This prevents the buildup of the contaminant-adsorbent macromolecules on the wall of the filter 140.
(51) As shown in
(52) The contaminant-adsorbent macromolecules may be provided to desorption unit 160 to strip the contaminants from the adsorbents. Desorption unit 160 may be configured according to a variety of desorption processes known in the art. In an embodiment, the desorption unit may include a heating unit to raise the temperature and thereby promote the natural desorption of the contaminants from the adsorbents. In the example embodiment shown in
(53) UV irradiation may be implemented in the decontamination system 100 in a variety of configurations. In an embodiment, filter unit 140 may include a light source (not shown) configured to irradiate feed stream 110, slurry stream 130, and/or the contents of filter unit 140, such as the contents of mixer 142, with UV light to allow for a photocatalytic oxidation or reduction reaction. While filter unit 140 may include the UV light source in some embodiments, the decontamination system 100 may include one or more separate UV reactors 102 upstream of filter unit 140 as shown in
(54) In another embodiment, a non-photocatalytic oxidation or reduction of the contaminants in the contaminant fluid 110 may be affected in addition to or in replacement of the above-described UV irradiation by adding a suitable oxidizing chemical, such as chlorine, or a reducing agent, such as sodium metabisulphite, into the contaminated fluid 110 and/or into slurry stream 130. Referring to
(55) Another aspect of the present disclosure relates to a filtration unit that is synergistically employed with insoluble particles. An example embodiment of such a filtration unit 200 is shown in
(56) The synergistic effects of employing insoluble particles 208 about membrane 202 may be achieved by maintaining the flow rate of the contaminated fluid and the transmembrane pressure such that filtration unit 200 is operating in cross-flow conditions. One resultant synergistic effect when the cross-flow condition is maintained is that insoluble particles 208 form a temporary membrane along the sidewall 204 of the membrane. The temporary membrane formed by insoluble particles 208, in turn, allows for increased flux across the membrane. For example, in an embodiment having a microfiltration membrane 202, the addition of a temporary membrane allows for ultra-filtration performance while maintaining the flux of a micro-filtration system. For example, in an embodiment the temporary membrane allows filtering of particles of about 1 micrometer to 1 nanometer in diameter. Typical ultra-filtration flux achieved in the industry are in the 50-100 GFD range, but a temporary membrane created by insoluble particles in a micro-filtration system can achieve flux in the 2000 GFD range.
(57) While insoluble particles 208 may include any adsorbents disclosed in the present disclosure, insoluble particles 208 may also include substantially non-adsorptive particles. In a synergistic embodiment, insoluble particles 208 may be adsorptive and non-photocatalytic. Using adsorptive, insoluble particles 208, additional benefits may be realized in addition to the increase in flux. In an example embodiment in which insoluble, adsorptive particles are used in decontamination system 100 and a cross flow is maintained in filter 144, the resultant temporary membrane would allow for a synergistic combination of benefits, including high flux, elimination or reduction in the need for polymer addition, and recovery and reuse of adsorbent. Further advantages may be realized by using non-photocatalytic particles 208. Some of the biggest costs in a photocatalytic process include the energy cost for providing the UV light and the maintenance cost of the UV source. By running the treatment process in a non-photocatalytic system eliminates these costs and allows for significant cost savings.
(58) Referring back to
(59) In another example application, the above process was slightly modified so as to provide for a semi-batch or continuous process. In this regard, as the contaminant stream 110 is continuously added in the first step, appropriate amounts of citric acid is also continuously added to the contaminant stream prior to subjecting contaminant stream 130 to a photocatalytic process 102. In the second step, the TiO.sub.2 adsorbents are also continuously added to the contaminant stream in the form of a slip stream of TiO.sub.2 prior to and after entering the filtration unit 140 so as to ensure the continuous feeding of contaminant stream 130 into the filtration unit 140 will meet with sufficient quantities of the TiO.sub.2 adsorbent. In the third step, a dewatering step using a ceramic membrane is performed both prior to and after entering the acid bath. In this step, the recovered TiO.sub.2 adsorbent is also continuously removed from desorption unit 160 and continuously recycled back for reuse. In performing a semi-batch or continuous process, the overall decontamination process will achieve consistently excellent efficiency throughout and not suffer from drops in efficiency during each batch, as encountered in a batch process.
(60)
(61) In some embodiments, acid stream 802 (e.g., citric acid) may be dosed into stream 820 from tank 822. Citric acid plugs the photogenerated hole of the activated TiO2, providing conduction band electrons for enhanced photocatalytic reduction rates as described, for example, in U.S. Pat. No. 5,554,300. Testing has demonstrated substantial power reductions with the use of citric acid. For example, order of magnitude increases in hexavalent chromium first order reduction rates have been observed.
(62) Also shown in
(63) In some embodiments, photocatalytic reactor 825 and catalyst recovery unit 835 may operate like a photocatalytic system used for organic destruction. After the photocatalytic reaction, the Cr.sup.3TiO.sub.2 slurry discharges from the photocatalytic racks and enters an atmospheric accumulator tank 830. A ceramic membrane (catalyst recovery unit or CRU) may operate in a standard cross flow manner to remove the Cr.sup.3TiO.sub.2 slurry (804), and the treated water 860 (e.g., <1 ppb Cr.sup.6) may be discharged. The CRU may concentrate the TiO.sub.2 10-20 times in the CRU loop.
(64) A slip stream of the contaminant/adsorbent concentrate in CRU loop may be discharged (e.g., continuously discharged) to a contaminant removal and recovery process. For example, a slip stream of TiO.sub.2 concentrate in loop 805 may be discharged to a Cr.sup.3 removal and recovery process. This step may not be included in a photocatalytic process for organic destruction.
(65) According to some embodiments, the flow rate of slurry 805 to the Cr.sup.3 removal process may be minimized, for system optimization. Similarly, some of the TiO.sub.2 slurry from the CRU loop 803 may be recycled back to the inlet of photocatalytic reactor 825. This may reduce the mass of clean adsorbent (e.g., TiO.sub.2) required from reservoir 821. The amount of the TiO.sub.2 slurry to be recycled back to reactor 825 and the amount of slurry 805 may be configured (e.g., optimized), according to some embodiments, to reduce the mass (e.g., kg/hr) of TiO.sub.2 sent to the Cr.sup.3 removal process while still maintaining discharge water 860 at or below a specified threshold (e.g., <1 ppb Cr.sup.6).
(66) Under some circumstances, the efficiency of the photocatalytic reduction of the Cr.sup.6 to Cr.sup.3 may decrease as the amount of Cr.sup.3 adsorbing onto the TiO.sub.2 increases due to reduction of available TiO.sub.2 surface area. For example, batching a fixed mass of TiO.sub.2 in a standard photocatalytic system may result in a continual loss of efficiency (e.g., where efficiency decreases as the surface of TiO.sub.2 decreases), until the rate of chromium reduction in the photocatalytic reactor decreases to a point at which the Cr.sup.6 in the effluent water would increase over the desired threshold (e.g., 1 ppb Cr.sup.6). At this point, all of the TiO.sub.2 in the system would need to be removed and replaced with cleaned TiO.sub.2. This type of batch processing is difficult to operate and ensure that the Cr.sup.6 discharge is maintaining its desired discharge specification at all times.
(67) As shown in
(68) As the TiO.sub.2Cr.sup.3 slurry gets pumped into the dead end membrane, the TiO.sub.2Cr.sup.3 is filtered, and the filtered water is sent to discharge 806. Inside the membrane housing, the combination of gravity and air shock waves make the TiO.sub.2Cr.sup.3 solids drop down into a collection weir located immediately below the membrane. This process concentrates the TiO.sub.2Cr.sup.3, and it also keeps the TiO.sub.2Cr.sup.3 from filling or plugging inside the ceramic membrane channels, keeping them free. The free channels may provide consistent flux in the membrane(s), unlike most dead-end filters which accumulate the solids inside the filter itself (and thus flux continuously reduces).
(69) Once the weir is nearly full of TiO.sub.2Cr.sup.3, a valve may be opened and the mixture 807 may pass into dewater/mixer tank 845, which may be configured to perform one or more functions. For example, dewater/mixer tank 845 may be configured to further dewater mixture 807. It may include dewatering membranes in some embodiments. Compressed air 817 from tank 836 may be used to push the TiO.sub.2Cr.sup.3 slurry into the dewatering membranes. The pressure pushes the water through the membranes and the treated water is sent to the discharge 810, while the dewatered TiO.sub.2Cr.sup.3 slurry is retained for further processing.
(70) Dewater/mixer tank 845 may be configured, according to some embodiments, to add acid 808 from acid storage tank 850 to desorb contaminant (e.g., Cr.sup.3) from adsorbent (e.g., TiO.sub.2), according to some embodiments. For example, a volume of heated (e.g., ?40 to ?60? C.) sulfuric acid (e.g., ?1 wt. %-?5 wt. %), may be added to dewater/mixer tank 845 where it may mix with dewatered Cr.sup.3TiO.sub.2. In some embodiments, it may be desirable to avoid using a pump to move heated acid into dewater/mixer tank 845. Instead, it may be desirable to use compressed air 817 to push acid 808 into dewater/mixer tank 845. Once the acid is added, compressed air 817 is sent up through the bottom of dewater/mixer tank 845. The internal design of dewater/mixer tank 845 may be arranged to create small bubbles of air which flow up through the acid TiO.sub.2Cr.sup.3 mixture, providing significant mixing required to strip off the Cr.sup.3 from the TiO.sub.2. The heated acid and agitation transfers the Cr.sup.3 from the TiO.sub.2 into the acid mixture. Tests show that this process may take about 20 to about 30 minutes. In some embodiments, it may be desirable to maintain the contents of acid storage tank 850 at constant free acid concentration (i.e., pH). In such cases, make-up acid 814 from make-up tank 849 may be added to tank 850.
(71) Fluid mixture 809 may pass from dewater/mixer tank 845 into acid storage tank 850. Fluid mixture 809 may comprise or consist of acid (e.g., sulfuric acid) and contaminant (e.g., dissolved trivalent chromium). Compressed air 817 from tank 836 may be used to push fluid mixture 809 into acid storage tank 850.
(72) The remaining TiO.sub.2 in dewater/mixer tank 845 may be expected to have some acid with dissolved Cr.sup.3 in it. In some embodiments, the acid and dissolved Cr.sup.3 must be flushed out of the TiO.sub.2 before the TiO.sub.2 can be sent to reservoir 821. In these embodiments, the concentration of Cr.sup.3 entrained in the TiO.sub.2 mixture will be too high if this flush is not performed. Eventually the mass of contaminant (e.g., Cr.sup.3) going back to reservoir 821 (and eventually back to photocatalytic reactor 825) will cause the total contaminant (e.g., chromium) concentration to exceed the desired threshold concentration (e.g., <20 ppb chromium). (During pilot experiments, dissolved Cr.sup.3 in the feed water was not observed to adsorb onto the TiO.sub.2. Instead, it only seemed to adsorb after Cr.sup.6 reduction). A volume of treated water 810 is sent into dewater/mixer tank 845 and it is then pushed through the membrane (e.g., like stream 807 above) and placed in rinse water tank 855 via stream 812. Stream 812 may have a low pH (e.g., ?0.5 to ?3.0) and comprise dissolved Cr.sup.3.
(73) Base 815 (e.g., NaOH) is then added to the rinse water tank 855 (from tank 854) to neutralize the water and precipitate the Cr.sup.3 into Cr(OH).sub.3.
(74) Precipitate 865 may be recovered by, for example, (a) gravity thickening and/or using ceramic membrane filtration and/or (b) using the dewatering approach used above. Chromium solid 816 is the recovered chromium, which can either be hauled away, or re-used in some other manufacturing process. If it is re-used, this remediation process could also be called a mining process. In some embodiments, a decontamination process may have zero contaminated liquid discharge.
(75) Once the TiO.sub.2 has been flushed and dewatered, it is deemed clean, and treated water 810 is sent back to dewater/mixer tank 845 where the TiO.sub.2 is slurried (required to transport it) and then sent back to the Clean TiO.sub.2 Storage Tank for reuse via stream 811 using compressed air 817.
(76) As will be understood by those skilled in the art who have the benefit of the instant disclosure, other equivalent or alternative compositions, devices, methods, and systems for reduction and/or removal of one or more heavy metals (e.g., heavy metals, chromium, phosphorous, phosphorous compounds, nitrogen, nitrogen compounds) from a feed composition (e.g., a fluid) can be envisioned without departing from the description contained herein. Accordingly, the manner of carrying out the disclosure as shown and described is to be construed as illustrative only.
(77) Persons skilled in the art may make various changes in the shape, size, number, and/or arrangement of parts without departing from the scope of the instant disclosure. For example, the position and number of inlets, valves, fluid connections, tanks, reactors, and discharges may be varied. In some embodiments, inlets, valves, fluid connections, tanks, reactors, and discharges may be interchangeable with like or different structures. Interchangeability may allow volume, flow rate, processing time, and yield to be custom adjusted. In addition, the size of a device and/or system may be scaled up (e.g., to be used for industrial embodiments) or down (e.g., to be used for portable embodiments) to suit the needs and/or desires of a practitioner. Each disclosed method and method step may be performed in association with any other disclosed method or method step and in any order according to some embodiments. Where the verb may appears, it is intended to convey an optional and/or permissive condition, but its use is not intended to suggest any lack of operability unless otherwise indicated. Persons skilled in the art may make various changes in methods of preparing and using a composition, device, and/or system of the disclosure.
(78) Also, where ranges have been provided, the disclosed endpoints may be treated as exact and/or approximations as desired or demanded by the particular embodiment. Where the endpoints are approximate, the degree of flexibility may vary in proportion to the order of magnitude of the range. For example, on one hand, a range endpoint of about 50 in the context of a range of about 5 to about 50 may include 50.5, but not 52.5 or 55 and, on the other hand, a range endpoint of about 50 in the context of a range of about 0.5 to about 50 may include 55, but not 60 or 75. In addition, it may be desirable, in some embodiments, to mix and match range endpoints. Also, in some embodiments, each figure disclosed (e.g., in one or more of the examples, tables, and/or drawings) may form the basis of a range (e.g., depicted value +/?about 10%, depicted value +/?about 50%, depicted value +/?about 100%) and/or a range endpoint. With respect to the former, a value of 50 depicted in an example, table, and/or drawing may form the basis of a range of, for example, about 45 to about 55, about 25 to about 100, and/or about 0 to about 100.
(79) All or a portion of a device and/or system for reduction and/or removal of one or more heavy metals (e.g., heavy metals, chromium, phosphorous, phosphorous compounds, nitrogen, nitrogen compounds) from a feed composition (e.g., a fluid) may be configured and arranged to be disposable, serviceable, interchangeable, and/or replaceable. These equivalents and alternatives along with obvious changes and modifications are intended to be included within the scope of the present disclosure. Accordingly, the foregoing embodiments are intended to be illustrative, but not limiting, of the scope of the disclosure as illustrated by the appended claims.
(80) Additionally, the section headings herein are provided for consistency with the suggestions under 37 C.F.R. ? 1.77 or otherwise to provide organizational cues. These headings shall not limit or characterize the invention(s) set out in any claims that may issue from this disclosure. Specifically, a description of a technology in the Background is not to be construed as an admission that technology is prior art to any invention(s) in this disclosure. Furthermore, any reference in this disclosure to invention in the singular should not be used to argue that there is only a single point of novelty in this disclosure. Multiple inventions may be set forth according to the limitations of the multiple claims issuing from this disclosure, and such claims accordingly define the invention(s), and their equivalents, that are protected thereby. In all instances, the scope of such claims shall be considered on their own merits in light of this disclosure, but should not be constrained by the headings herein.