EP3191214A1 - Procédé et système pour la séparation de mercure élémentaire mis sous forme d'aérosol fin de flux gazeux - Google Patents
Procédé et système pour la séparation de mercure élémentaire mis sous forme d'aérosol fin de flux gazeuxInfo
- Publication number
- EP3191214A1 EP3191214A1 EP15840936.7A EP15840936A EP3191214A1 EP 3191214 A1 EP3191214 A1 EP 3191214A1 EP 15840936 A EP15840936 A EP 15840936A EP 3191214 A1 EP3191214 A1 EP 3191214A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mercury
- wire
- accordance
- strands
- tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000008569 process Effects 0.000 title description 8
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 139
- 239000010970 precious metal Substances 0.000 claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 claims abstract description 73
- 239000002184 metal Substances 0.000 claims abstract description 73
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 46
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 44
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052709 silver Inorganic materials 0.000 claims abstract description 36
- 239000004332 silver Substances 0.000 claims abstract description 36
- 230000009471 action Effects 0.000 claims abstract description 25
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 22
- 239000010948 rhodium Substances 0.000 claims abstract description 22
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 19
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims description 94
- 238000011045 prefiltration Methods 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052762 osmium Inorganic materials 0.000 claims description 15
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 229910052741 iridium Inorganic materials 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 150000002894 organic compounds Chemical class 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 150000001345 alkine derivatives Chemical class 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 125000005456 glyceride group Chemical group 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 2
- 238000010248 power generation Methods 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 6
- 239000011146 organic particle Substances 0.000 claims 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 27
- 229910052737 gold Inorganic materials 0.000 abstract description 24
- 239000010931 gold Substances 0.000 abstract description 24
- 150000002739 metals Chemical class 0.000 abstract description 9
- 239000007789 gas Substances 0.000 description 42
- 229910000679 solder Inorganic materials 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000000356 contaminant Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 241000894007 species Species 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- -1 silver-plated Chemical compound 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000443 aerosol Substances 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000009954 braiding Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- 239000010451 perlite Substances 0.000 description 5
- 235000019362 perlite Nutrition 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000000505 pernicious effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013043 chemical agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 150000002730 mercury Chemical class 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000005067 remediation Methods 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- JJWSNOOGIUMOEE-UHFFFAOYSA-N Monomethylmercury Chemical compound [Hg]C JJWSNOOGIUMOEE-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000012387 aerosolization Methods 0.000 description 2
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000009940 knitting Methods 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005382 thermal cycling Methods 0.000 description 2
- 239000010455 vermiculite Substances 0.000 description 2
- 229910052902 vermiculite Inorganic materials 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000184 acid digestion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical class [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- ATZBPOVXVPIOMR-UHFFFAOYSA-N dimethylmercury Chemical compound C[Hg]C ATZBPOVXVPIOMR-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229940101209 mercuric oxide Drugs 0.000 description 1
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 1
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- ONVGIJBNBDUBCM-UHFFFAOYSA-N silver;silver Chemical compound [Ag].[Ag+] ONVGIJBNBDUBCM-UHFFFAOYSA-N 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
- F23J15/022—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow
- F23J15/025—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow using filters
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2215/00—Preventing emissions
- F23J2215/60—Heavy metals; Compounds thereof
Definitions
- PCT/US2010/002356 is also a continuation-in-part of U.S. Patent Appl. Serial No.
- This invention relates generally to methods and apparatus for removing pernicious contaminants from fluid, particularly gaseous, systems to preclude discharge of the contaminants into the surrounding environment, and more specifically relates to methods and devices for removing elemental mercury from a gaseous stream in which it is dispersed as a fine aerosol.
- gaseous process streams (or more generally "gaseous systems") are produced which are contaminated with pernicious quantities of mercury.
- the mercury contaminants have proved to be particularly difficult to remove or reduce to acceptable levels.
- One of the most harmful forms of mercury pollution is finely aerosolized elemental mercury. This form of mercury is generated by coal-fired power plants and also is present in natural gas. In the U.S. coal-fired power plants are the largest source of man-made mercury emissions to the air, accounting for approximately 40% of all mercury emissions.
- mercury is adsorbed on the aerosolized soot from coal burning. This soot eventually settles and the mercury adsorbed on the carbon is converted to methyl mercury, dimethyl mercury, and other forms, which accumulate in the food chain.
- Elemental mercury also occurs in natural gas in concentrations up to hundreds of micrograms per Nm 3 . This is a significant account considering that a typical plant will process millions of Nm 3 per day.
- mercury can be collected in existing air pollution control devices such as wet SO 2 scrubbers, electrostatic precipitators, and baghouses (fabric filters).
- aqueous or gaseous process streams which are produced in many other commercially important industrial processes, these streams being contaminated with pernicious quantities of mercury in various oxidation and complexation states and including elemental, ionic, and organically-bound mercury.
- Mercury is corrosive to metals and other materials within a facility where the process is practiced, and is harmful to human health and to the surrounding ecosystem.
- Mercury contaminants have proved to be particularly difficult to remove or reduce to acceptable levels. In order to do so, it is important to know the concentration and speciation (organically -bound, ionic, or elemental) of mercury (Hg) in the stream containing same.
- 13/392,357 discloses methods and apparatus for analyzing the concentrations of diverse contaminating mercury species present in a fluid stream, whether aqueous or gaseous, in order that an effective strategy for separating the mercury from the stream may then be formulated.
- Characterization of the particular mercury (Hg) species in a waste stream is important in designing remediation technology, as the three primary forms of mercury (ionic, organically-bound, and elemental) possess very different physical and chemical properties.
- Hg mercury
- the ability to characterize mercuric species has been limited and difficult.
- Mercury is usually present in very low concentrations (usually 1 ppm or less) and there are usually large fluctuations in influent mercury concentration; rendering inaccurate spot sampling.
- the composition of speciation changes when these small amounts of mercury come in contact with the sample vessel. Further, standard tests are destructive and do not differentiate adequately between the three forms.
- the application U.S. Patent Appl. Serial No. 13/392,357 disclosed a multi-stage filtration method and system to address the problems in prior systems.
- the problem associated with capturing finely aerosolized elemental mercury is primarily one of overcoming the surface tension of the aerosolized droplet in order to allow the liquid mercury to wet out on a surface.
- the coalesced mercury must be prevented from re-aerosolizing off the substrate.
- One way to achieve this is by exploiting the contact angle of the droplet with a given interface.
- a metallic capillary surface is contacted with the gaseous stream, causing the aerosolized droplets to deposit on the capillary surface and by capillary action to coalesce with other of such droplets to form increasingly large drops of mercury.
- the surface is oriented to allow the mercury drops to flow by gravitational forces and capillary action to the lowermost portions of the surface or an extension of same where they accumulate, and are then collected at a suitable vessel or the like, e.g. by simply dropping into the vessel.
- the present invention exploits the above phenomena by employing a capillary surface-bearing substrate, preferably comprised of finely braided strands of metal wire (e.g. approximately 40-gauge, 3 mil diameter, 192 wires/strand) which is comprised of a precious metal or a combination of precious metals.
- the precious metal wire can be silver, gold, ruthenium, osmium, rhodium, iridium, palladium, platinum, or combinations of these metals, and the use of the term "precious metal wire" includes combinations thereof, unless otherwise specified.
- Combinations of these metals can include alloys, mixtures, metal solutions, and the like, of two or more of these metals if that combination is suitable for preparing the finely braided wire.
- silver wire works very well to form the finely braided strands, and various combinations of silver with the other precious metals also work well in this regard.
- Gold wire also works very well to form the finely braided strands, as do combinations of gold with the other precious metals.
- Various combinations of the other precious metals that are suitable for preparing finely braided wire can also be used according to this disclosure. These metal wires are found to provide highly stable structures and braids, which resist deterioration from the thermal cycling imposed by typical environments in which the invention is employed.
- the present invention also may exploit the above phenomena by employing a capillary surface-bearing substrate, preferably comprised of finely braided strands of a metal wire, for example, copper wire (e.g. approximately 40-gauge, 3 mil diameter, 192 wires/strand) which has an integral surface deposition of a precious metal.
- a metal wire for example, copper wire (e.g. approximately 40-gauge, 3 mil diameter, 192 wires/strand) which has an integral surface deposition of a precious metal.
- the braided strands of a metal wire can be made of a non-precious metal that is suitable for braiding, has properties that permit its use for fabricating the filtration system disclosed herein, and can be a non-precious metal or a precious metal. Copper wire works very well in this role.
- the precious metal that is coated or deposited on the surface of the braided strands of a metal wire can be any precious metal or a combination of precious metals, where combinations can include alloys, mixtures, metal solutions, and the like, of two or more of these metals if that combination is suitable for coating onto another metal wire that is, or can be made into, a finely braided wire.
- silver-coated copper wire has been found to be particularly useful, and gold-coated copper wire also works well in this regard, as do various combinations of these metals with other precious metals.
- Various combinations of the other precious metals that are suitable for coating onto another metal wire that is, or can be made into, a finely braided wire also can be used according to this disclosure.
- the disclosed method and filtration system can be used as a stand-alone system for removing finely aerosolized mercury, or alternatively, can be used as one of the filtration states of the multi-stage filtration system for mercury characterization and capture, as provide in the U.S. Patent Appl. Serial No. 13/392,357.
- the present method and system can be used as the second stage of the filtration system composed of three distinct filtration stages, with each stage having a specific affinity for each of the three predominant forms of mercury.
- the first stage is composed of filtration devices, which visco-elastically coagulate and incorporate substantially all organically bound forms of Hg.
- the second stage is a filter constructed with precious-metal-plated solder wick as the elemental Hg collection media.
- the finely braided wires in these filters are able to intercept and capture elemental dispersed minute particles of mercury from the fluid stream passed therethrough.
- the third stage is composed of a granular media adapted to collect the ionic mercury.
- ionic mercury refers not only to such ions as may be present in an aqueous stream, but essentially means or is synonymous with inorganic mercury salts. Such salts may be present in the gaseous stream where they are hydrated by water vapor in the gases.
- the collecting media can simply comprise a granular activated carbon.
- the media can comprise one impregnated with one or more chemical agents that are able to precipitate the ionic mercury.
- the granular media can in this latter instance be composed of carbon, clay, paper, perlite, etc., and the precipitating agents can include, but are not limited to, calcium sulfate, sulfides and thiols and the like.
- the U.S. Patent Appl. Serial No. 13/392,357 is incorporated herein by reference in its entirety and discloses the aspects and features of how the present metallic capillary surface can be used in stage 2 of the disclosed system to cause droplets of mercury to deposit and by capillary action and coalesce, wherein the present metallic capillary surface is comprised of finely braided strands of a precious metal wire or finely braided strands of a precious metal- coated wire according to this disclosure.
- solder wicks are made of metal strands braided to form narrow interstices between the individual strands and to thereby provide a capillary surface at the wick's exterior.
- solder wicks are made of metal strands braided to form narrow interstices between the individual strands and to thereby provide a capillary surface at the wick's exterior.
- the fine metal strands are typically braided together in the form of a tube, which is then flattened to make a braided ribbon.
- the strands In a braided ribbon, the strands all extend in the longitudinal direction along the tube. The individual strands are in rather close engagement, yielding a ribbon with a limited volume between strands within which solder may be drawn.
- solder operation the wick is placed on the solder connection and the connection is heated through the wick with a soldering iron.
- the solder melts and is drawn up onto the wick by capillary forces.
- solder wicks are generally made of copper wire.
- solder wick comprises a braid of strands of 40-gauge copper wire and the strands are in groups of four.
- the wick is braided from a machine having 16 heads so that the wick is 64 strands thick with 23 tucks 27 per inch.
- Other grades of wire and braiding patterns can also be used, e.g., 96 strands of 44 gauge can be braided in 16 groups of six strands, etc.
- Solder wicks have also been proposed for production by other than braiding.
- U.S. Patent No. 4,416,408 mentions the use of an open-mesh structure prepared by "weaving, stranding, braiding, knitting or crochetting", the preferred process therein involving the use of a knitting machine, which results in the
- the wick have a capillary surface capable of wicking the molten solder, and braided wicks have been found most suitable for this function.
- various open mesh structures such as discussed above are useable in the present invention if they possess an adequate capillary surface, the braided wicks are the preferred material for use in the present invention,
- a braided wire that is either formed of silver wire or formed of a silver-coated copper wire.
- the flattened ribbon-shaped wick can be wrapped around a filter or a metal core in the preferred form of a tube, with the wire strands all extending in the longitudinal direction along the tube, and the ribbon being in one or multiple layers so as to achieve the desired degree of filtration efficiency.
- the metal tube has porous walls, e.g.
- differential pressure is only between 1 to 3 psi at a gas flow rate of 600 million ft 3 per day.
- the braided structure of the substrate results in interstitial areas of extreme contact angle (less than 45 degrees), which is able to entrap the aerosol droplets.
- This contact angle (hereinafter defined), along with the affinity of gold for mercury results in the de-aerosolization of the droplets and wetting out on the substrate.
- Silver wire and silver-plated wire also work very well in this way. When sufficient mercury has accumulated, so as to act like a bulk phase material, the surface tension of the liquid mercury will cause it to capillary flow along the axis of winding of the braid. This effect is exploited in combination with gravity to cause the captured liquid mercury to capillary down the filter and along a braided extension to a recovery point.
- a filtration system for separating droplets of finely aerosolized elemental mercury from a gaseous stream in which the droplets are dispersed.
- the apparatus includes a metallic capillary surface and means for contacting metallic capillary surface with the gaseous stream, causing the droplets to deposit on the surface and by capillary action to coalesce with other of the droplets to form increasingly large drops of mercury.
- the said capillary surface is oriented to allow the mercury drops to flow by gravitational forces and capillary action to the lowermost portion of the surface where it accumulates; and means are provided for collecting the accumulating mercury thereby separated from the gas stream.
- the capillary surface is preferably defined at the surface of a wick made of braided copper strands; and the strands are preferably silver, silver-plated, gold, or gold-plated.
- Combinations of the precious metals particularly combinations of silver and/or gold with the other precious metals (ruthenium, osmium, rhodium, iridium, palladium, and platinum, which are the "platinum metals") can also be used to good advantage.
- a filtration system for separating droplets of finely aerosolized elemental mercury from a gaseous stream in which the droplets are dispersed.
- the system includes a generally enclosed tank having an inlet for receiving the gaseous stream and an outlet for discharging the gaseous stream after the mercury has been removed.
- One or more filters are positioned in the tank, which filters include a perforated wall tube wound with a substrate formed from a wick made of metal strands braided to form narrow interstices between the individual strands which thereby provide a capillary surface at the wick's exterior.
- Means are provided for flowing the gas stream entered into the tank through the perforated wall of the tube and the wound substrate to effect contact of the metallic capillary surface of the substrate with the gaseous stream, causing the droplets to deposit on the capillary surface and by capillary action to coalesce with other of said droplets to form increasingly large drops of mercury.
- Means are provided for passing the gas stream having contacted the capillary surface to the gas discharge outlet.
- the tube and capillary surface are oriented to allow the mercury drops to flow by gravitational forces and capillary action to the gravitationally lowermost portion of said surface where the mercury accumulates; and means are provided in the system for receiving and collecting the accumulating mercury thereby separated from the gas stream.
- the gas stream treated by the invention may include undesirable hydrocarbons and oily organic compounds organic compounds dispersed as minute aerosolized particles or mists in the gaseous media
- systems and methods based on the invention may further include means to prefilter the gaseous stream before it is contacted with the capillary surface, to remove the dispersed hydrocarbons and oily organic compounds.
- FIG. 1 is a schematic longitudinal cross-section showing a filtering system utilizing a metal capillary (“MC”) filter in accordance with the invention to remove and collect finely aerosolized mercury, the depiction showing the MC filter in an outside-in gas stream flow arrangement;
- MC metal capillary
- FIG. 2 is a schematic longitudinal cross-section similar to FIG. 1, except that the depiction shows the MC filter in an inside-out flow arrangement;
- FIG. 3 is an enlarged schematic cross-section of the mercury removal reservoir of FIGS. 1 and 2, showing the lower portions of the capillary braid delivering the collected mercury to the reservoir;
- FIG. 4 is a schematic elevational view of a portion of the MC filter showing the core of the filter and portions of the braid which is wound on the core, the braided strands comprising a precious metal wire or a precious metal-coated wire which forms the metallic capillary surface;
- FIG. 4A is an enlarged view of a portion of the braid in FIG. 4;
- FIG. 5 is a schematic showing of the capillary surface of the braid in the MC filters of the prior Figures and together with adjacent FIG. 5A shows the progressive change in the contact angles at the mercury-capillary surface interface as the coalescing drops proceed downwardly on the braid;
- FIG. 6 is a schematic longitudinal cross-section showing an oleophilic prefilter which may be used in a gas filtering system upstream of the metal capillary (“MC") filter in order to remove organic and other contaminants that may be present in the gas flow, prior to the flow being acted upon by the MC filter or filters, the depiction showing the oleophilic prefilter in an outside-in flow arrangement;
- MC metal capillary
- FIG. 7 is a schematic longitudinal cross-section showing a two stage mercury removal filtering system in which the first stage is an oleophilic prefilter as in FIG. 6, and the second stage is a metal capillary (“MC") filter for removing and collecting finely aerosolized mercury, the depiction showing the MC filter in an inside-out flow
- FIG. 8 is a schematic elevational view, partly sectioned, which shows a composite filter incorporating the two stages used in the FIG. 7 embodiment, the oleophilic prefilter being coaxial with but outside of the MC filter, and with the gas stream flow proceeding radially inward toward the composite filter axis;
- FIG. 9 is a schematic elevational view, partly sectioned, which shows a composite filter incorporating the two stages used in the FIG. 7 embodiment, but differing from the FIG. 8 embodiment in that the oleophilic prefilter is coaxial with but inside of the MC filter, and with the gas flow proceeding outwardly from the axis of the composite filter.
- FIG. 10 is a schematic partially cross-sectioned diagram, illustrating the three- stage filtration system operating in accordance with this disclosure, in which stage two includes the metallic capillary surface is comprised of finely braided strands of a precious metal wire or finely braided strands of a precious metal-coated wire.
- precious metal is defined according to the art- recognized technical definition provided in the Academic Press Dictionary of Science and Technology (ed. C. Morris, p. 171 1, Academic Press, Inc.; San Diego, c. 1992), namely, precious metal means silver, gold, or any of the platinum group metals.
- a platinum group metal is defined according to the Academic Press Dictionary of Science and Technology (ed. C. Morris, p. 1670 Academic Press, Inc.; San Diego, c. 1992) as any of the six metals belonging to group VIII B of the Periodic Table, that is, ruthenium, osmium, rhodium, iridium, palladium, and platinum, which is understood by the skilled person.
- This disclosure provides generally a method and a filtration system that can separate droplets of finely aerosolized elemental mercury from a gaseous stream in which the droplets are dispersed.
- the method and system address the limitations of the prior art by, among other things, overcoming the surface tension of the aerosolized droplet in order to allow the liquid mercury to wet out on a surface, in combination with using the contact angle of the droplet with a given interface to prevent the coalesced mercury from re- aerosolizing and re-entering the gaseous stream.
- the present invention exploits the above phenomena by employing a capillary surface-bearing substrate, preferably comprised of finely braided strands of a precious metal wire or a precious metal-coated wire.
- a method for separating droplets of finely aerosolized elemental mercury from a gaseous stream in which the droplets are dispersed comprising:
- the metallic capillary surface is comprised of braided strands of metal wire, the metal wire being made of a precious metal or a combination of precious metals, or the metal wire being made of a non-precious metal which is coated with a precious metal or a combination of precious metals;
- said surface is oriented to allow the mercury drops to flow by gravitational forces and capillary action to the lowermost portion of said surface where it accumulates.
- the disclosed method can be carried out using a metal wire that comprises braided strands of silver wire, gold wire, palladium wire, platinum wire, rhodium wire, iridium wire, ruthenium wire, or osmium wire, or any combination thereof.
- the disclosed method can be carried out using a metal wire that comprises braided strands of a non-precious metal which is coated with silver, gold, palladium, platinum, rhodium, iridium, ruthenium, osmium, or any combination thereof.
- a filtration system for separating droplets of finely aerosolized elemental mercury from a gaseous stream in which the droplets are dispersed comprising:
- a metallic capillary surface comprised of finely braided strands of metal wire, the metal wire being made of a precious metal or a combination of precious metals, or the metal wire being made of a non-precious metal which is coated with a precious metal or a combination of precious metals;
- capillary surface is oriented to allow the mercury drops to flow by gravitational forces and capillary action to the lowermost portion of said surface where it accumulates;
- the filtration system can include a metal wire that comprises braided strands of silver wire, gold wire, palladium wire, platinum wire, rhodium wire, iridium wire, ruthenium wire, or osmium wire, or any combination thereof.
- the filtration system can include a metal wire that comprises braided strands of a non-precious metal which is coated with silver, gold, palladium, platinum, rhodium, iridium, ruthenium, osmium, or any combination thereof.
- the metallic capillary surface can be comprised of finely braided strands of silver, gold, palladium, platinum, rhodium, or a combination thereof.
- the metallic capillary surface can be comprised of finely braided strands of a wire made of a non-precious metal such as copper, that is coated with silver, gold, palladium, platinum, rhodium, or a combination thereof.
- the underlying wire can also be a different precious metal than the precious metal used in the coating.
- the metallic capillary surface can be comprised of finely braided strands of silver, gold, palladium, or platinum or a combination thereof, or copper wire coated with silver, gold, palladium, or platinum, or a combination thereof.
- Combinations of more than one of these metals can include alloys, mixtures, metal solutions, and the like, if that combination is suitable for preparing the finely braided wire or for coating onto a finely braided wire.
- Particularly useful are metallic capillary surfaces comprised of finely braided strands of silver or silver-coated wire, or gold or gold-coated wire.
- the coated wire can be a precious or non-precious metal.
- copper wire works very well to form the finely braided strands used in fabricating the filtration system as disclosed herein.
- This disclosure describes in detail the filtration system and method used as a stand- alone system for removing finely aerosolized mercury, but also discloses the use of this filtration system as one of the filtration states of the multi-stage filtration system for mercury characterization and capture, as provide in the U.S. Patent Appl. Serial No.
- the present precious metal braided wire and precious metal- coated braided wire can be used to fabricate the second stage of the filtration system composed of three distinct filtration stages, in which the second stage is constructed with precious metal wire or precious metal-plated wire that forms a solder wick as the elemental Hg collection media.
- a filtering system 10 which utilizes metal capillary (“MC”) filters 12 in accordance with the invention to remove and collect finely aerosolized mercury.
- MC filters 12 are mounted in a tank 14 to function in parallel in treating a gas flow stream 16 provided to tank 14 via inlet 18.
- the actual number of MC filters 12 can be greater or smaller than the exemplary four shown.
- the gas flow in tank 14 enters into each of the MC filters by passing through the capillary surface presented by the metallic braid 20 which in the MC filter is wound upon a stainless steel core or tube 21, the walls of which, as seen in FIG. 4, are perforated by openings 23.
- solder wicks are made of metal strands braided to form narrow interstices between the individual strands and to thereby provide a capillary surface at the wick's exterior.
- metal strands are typically braided together in the form of a tube, which is then flattened to make a braided ribbon 25 as seen in FIG. 4A.
- the wick discussed In U.S. Patent No. 3,627,191 comprises a braid of strands of copper wire, which unlike the present braid is overcoated with flux.
- the wire is 40-gauge and the strands are in groups of four.
- the wick is braided from a machine having 16 heads so that the wick is 64 strands thick with 23 tucks 27 per inch.
- Such a wick (minus the flux) is suitable for use in the present invention, preferably when modified by a silver or gold plating, but other grades of wire, and braiding patterns can also be used, e.g., 96 strands of 44 gauge can be braided in 16 groups of six strands, and so forth.
- the fundamental requirement is that the wick have a capillary surface capable of wicking the mercury that pursuant to the present invention is deposited on the capillary surface.
- the preferred braided wire 20 is of copper and silver- or gold-plated and the flattened ribbon-shaped wick is wrapped around a filter or the porous wall metal tube 21 in one or multiple layers so as to achieve the desired degree of filtration efficiency.
- high removal efficiency of aerosol mercury is achieved at very low differential pressures.
- differential pressure is only between 1 to 3 PSI at a gas stream flow rate of 600 million ft 3 per day.
- FIG. 5 shows how the aerosolized mercury droplets 33 in the gas stream deposit on the capillary surface of braid 20 and then gradually coalesce and increasingly wet the said surface as they advance downwardly in the sense of the Figure, driven by capillary action and aided by gravity.
- FIG. 5A to the right of FIG. 5 graphically depicts the approximate change in contact angle as the collected mercury droplets coalesce and advance downwardly in FIG. 5, where the well-known parameter "contact angle" is defined here as the angle formed by the solid/liquid interface measured from the side of the liquid.
- Four approximate regions (a), (b), (c), and (d) are shown in FIG. 5 in the descending direction on braid 20.
- FIG. 3 shows the several braid extensions 24 which at this point can be intertwined together, exit the tank through port 37 (FIG. 1), pass through duct 26 and enter the mercury removal reservoir 28, where the mercury is collected as it wicks down the braids and drops from the bottom ends thereof.
- the gas stream 17 from which the aerosolized mercury has been removed exits the core interiors 21 of MC filters at outlets 29 into plenum 27, which is separated from the rest of tank 14 by a plate 31, which extends across the tank, and then exits tank 14 via outlet 32. Since some condensation will tend to occur in the plenum 27, the bottom of the plenum defines a sump 30 for which a drain outlet 34 and valve 36 are provided.
- connection ports to the tank 14, such as at 38 enable gauges or other instrumentation to be connected as desired to the tank 14 or to one or more of the MC filters 12 or portions thereof.
- FIG. 1 the depiction shows the MC filter in an outside-in flow arrangement.
- FIG. 2 shows the MC filters being used in inside-out flow arrangements.
- the stream 40 enters the plenum 27 via inlet 41 at the bottom of tank 42, and passes into MC filters 44 via the hollow axial interiors 46 of cores 21. Then after passing through the openings of the perforated walls of cores 21 the stream 40 passes to the metallic braid 20 wound upon the core 46 of each MC filter 44, where the same action occurs as discussed in connection with FIG. 1, with the depositing mercury droplets again coalescing and advancing by capillary action aided by gravity, to reach the mercury removal reservoir 28.
- the gas stream 47 with the mercury removed exits tank 42 via outlet 48.
- the gaseous streams treated by the invention in many instances may additionally include undesirable organic compounds such as hydrocarbons and various oily compounds dispersed as minute aerosolized particles or mists in the gaseous media.
- undesirable organic compounds such as hydrocarbons and various oily compounds dispersed as minute aerosolized particles or mists in the gaseous media.
- the fluid-pervious filtration media in my U.S. Patent No. 6,805,727 is treated with an absorption composition cured in situ at the media, the composition comprising a homogeneous thermal reaction product of an oil component selected from the group consisting of glycerides, fatty acids, alkenes, and alkynes, and a methacrylate or acrylate polymer component.
- Filter configurations incorporating the said may be based on various air or gas stream permeable substrates, such as shredded, spun or otherwise configured polypropylene, polyethylene or shredded or spun cellulose, or polyester cellulose which substrates are infused or otherwise treated with the absorbent compositions, which are then cured to produce the surface modified filter.
- the said absorbent compositions can be incorporated into or upon other filtering substrates and media, such as paper, including compressed pulp materials, particulate porous foamed plastics, fiberglass, mineral particulates such as perlite and vermiculite, and particulate, fibrous or porous ceramic media.
- the resulting substrate filter may be used independently to treat an air or other gas stream from which contaminating mists or other dispersed or suspended particles are to be removed, or can be used (especially for removal of mists) in conjunction with a conventional filter, as for example by being placed in front of (i.e., in series with) the conventional filter through which the air or gas stream passes.
- FIG. 6 is a schematic longitudinal cross-section showing a prefiltration stage, which shall herein be referred to as an "oleophilic prefilter", which makes use of the foregoing filtration media.
- the oleophilic prefilter system 50 which thus may be used in a gas filtering system upstream of the metal capillary (“MC") filter in order to remove aerosolized and particulate organic and other contaminants that may be present in the gas flow prior to the flow being acted upon by the MC filter or filters, is shown in an outside- in flow arrangement.
- the oleophilic prefilter system 50 has an overall similarity in arrangement of its components to the devices of FIGS. 1 through 5.
- a prefiltration tank 52 in which are mounted in parallel feed fashion four oleophilic filters 54 which are arranged for outside-inside stream flow.
- Stream 56 enters the tank 52 through inlet 58, and then passes into each hollow core filter 54 via the oleophilic filtration media 60, which is positioned about the cores 62.
- This media 60 is in accord with that described in my aforementioned U.S. Patent No. 6,805,727, and thus serves to remove the said aerosolized organics from the gas stream.
- the gas stream from the several in-parallel filters then exits the axial passages of cores 62 via the bottom core outlets 63 and enters the plenum 27 from which the stream 66 is discharged at outlet 64.
- drain 34 and valve 36 identify additional elements in the Figure, which are functionally the same as in prior Figures.
- Two extra ports 68 and 69 are shown, the first connecting to the tank 52 interior above plate 31, and the second to plenum 27 below plate 31. These ports can be used with instrumentation or the like for measuring desired parameters in the spaces with which the ports communicate.
- FIG. 7 is a schematic longitudinal cross-section showing a two stage mercury removal filtering system 55 in which the first stage is an oleophilic prefilter system 50 as in FIG. 6, and the second stage is an MC filter system 45 as in FIG. 2 for removing and collecting finely aerosolized mercury.
- Corresponding elements of the filter systems 50 and 45 are identified here by corresponding reference numerals of FIGS. 6 and 2.
- the output flow 66 from outlet 64 of prefilter system 50 is schematically shown entering MC filter system 45 as stream 40.
- the physical duct between outlet 64 and inlet 41 is not shown, but can take any convenient form such as a pipe or the like.
- the oleophilic filter is thus disposed upstream of the MC filter so that the former acts as a prefilter for the latter.
- the present invention is inter alia applicable to remediation of various flue and exhaust gases, such as those produced in coal-fired power generation.
- mercury droplets may not be the only pernicious aerosolized droplets.
- finely aerosolized organic compounds such as hydrocarbons in the C6 to C13 range, which encompass various diesel and gasoline components.
- these aerosolized organic droplets can be coalesced with great efficacy by the use of the invention.
- coalescing organics can thus be collected primarily in prefilter system 50 at the sump 30 of prefiltration tank 52, while the mercury is coalesced primarily in the mercury filtration tank 42 of the MC filter system 45, where it is then collected at an external mercury collection vessel 28.
- the prefilter system 50 may also act to remove small portions of the dispersed mercury along with the various condensates that collect at sump 30. These mercury components can, if sufficient in quantities to warrant such action, be separated from the discharge at drain 34 of tank 52 by conventional chemical or physical methods. Alternatively, portions of the condensate can be converted to a vaporous form and recycled through MC filter 45 to recover such additional mercury.
- FIG. 8 is a schematic elevational view, partly sectioned which shows a composite filter 70 incorporating the two stages used in the FIG. 7 embodiment, the oleophilic prefilter 72 being coaxial with but outside of the MC filter 76, and with the gas stream flow 82 proceeding radially inward toward the composite filter 70 axis.
- the oleophilic filtration media 74 may be wound or packed about MC filter 76 and held in place by retaining means such as string, and comprises the same materials as discussed for media 60 in FIG. 6.
- the MC filter 76 is formed of a perforate walled hollow core 79 of stainless steel or the like, about which the metallic braid 80 is wound.
- FIG. 9 a schematic elevational view, partly sectioned, shows a composite filter system 85 incorporating the two stages used in the FIG. 8 embodiment, but differing from the FIG. 8 embodiment in that the oleophilic prefilter 84 is coaxial with but inside of the MC filter 76, and with the gas flow 87 being introduced to and then proceeding outwardly 89 from the hollow axial portion of the perforated wall core 78.
- Braid 80 is therefore wound at the outside of the composite filter so that the gas stream being treated passes radially through the oleophilic prefilter 84 prior to reaching the MC filter 76, at which the mercury droplets are collected as previously described.
- the mercury accumulating at the bottom portions of the wound braid 80 can then be collected, e.g. by the braid extending to a suitable collection point or vessel.
- this disclosure also encompasses a method and means of in-situ sampling and characterization, which overcomes the above limitations.
- the method of the invention is practiced in a filtration system composed of three distinct filtration stages, with each stage having a specific affinity for each of the three predominant forms of mercury.
- the first stage is composed of filtration devices, which visco-elastically coagulate and incorporate substantially all organically bound forms of Hg.
- the second stage is a filter that can be constructed with a silver or silver-plated solder wick, or any precious metal or precious metal-plated solder wick, as the elemental Hg collection media.
- the finely braided wires in these filters are able to intercept and capture elemental dispersed minute particles of mercury from the fluid stream passed there through.
- the third stage is composed of a granular media adapted to collect the ionic mercury.
- ionic mercury refers not only to such ions as may be present in an aqueous stream, but essentially means or is synonymous with inorganic mercury salts. Such salts may be present in the gaseous stream where they are hydrated by water vapor in the gases.
- the collecting media can simply comprise a granular activated carbon.
- the media can comprise one impregnated with one or more chemical agents that are able to precipitate the ionic mercury.
- FIG. 10 is a schematic partially cross-sectioned diagram illustrating a system 90 operating in accordance with the present invention.
- system 90 will be first described on the assumption that it is operating upon an aqueous stream, such as a produced water stream as discussed above.
- System 90 is thus supplied by a side stream 92 (e.g. 1 to 5 gal/min) diverted from the primary stream 94 (e.g.
- the first filtration stage 96 preferably comprises a container within which is a fluid pervious filtration media which has been infused with an oleophilic absorption composition, whereby the removed organically bound Hg contaminants are immobilized at the media.
- the influent side stream 92 at stage 96 is thus passed through absorption composition-infused filtration media (referred to for convenience herein as an "ACI filtration media").
- ACI filtration media preferably comprises a fluid pervious filtration media which has been infused with an absorption composition comprising a homogeneous thermal reaction product of an oil component selected from the group consisting of glycerides, fatty acids, alkenes and alkynes, and a methacrylate or acrylate polymer component, whereby the organically-bound Hg contaminants are immobilized at the media.
- Filtration media of this type are disclosed in detail in the present applicant's U.S. Patent No.
- the filters of the U.S. Patent No. 6, 180,010 are thus oleophilic in nature and suitable as the first filtration stage of the present invention. In that capacity they cooperate with the remaining downstream second and third mercury removal filtration stages.
- the filtration media (which is infused) can comprise a non-woven polypropylene, paper, a porous ceramic, a porous metal, a mineral particulate such as vermiculite or perlite, or so forth.
- a capillary surface-bearing substrate preferably comprised of finely braided strands of copper wire (e.g. approximately 40-gauge, 3 mil diameter, 192 wires/strand) which has an integral surface deposition of a precious metal such as silver, gold, ruthenium, osmium, rhodium, iridium, palladium, platinum, or combinations thereof.
- a precious metal such as silver, gold, ruthenium, osmium, rhodium, iridium, palladium, platinum, or combinations thereof.
- Gold has an affinity for mercury, and silver is also particularly useful for this second filtration stage.
- an intermediate metal such as nickel is first plated on the copper to act as a barrier to prevent inter- metallic formation of the copper and gold.
- this intermetallic formation is desirable as it results in a highly stable substantially unitary structure in the strands of the braid, which resist deterioration from the thermal cycling imposed by typical environments in which the invention is employed.
- a barrier layer of nickel present between the copper and gold peeling or undercutting of the gold surface would over time become a serious problem.
- precious metal wire such as silver wire, rather than using a plated wire, to form the braided capillary surface.
- a preferred braided wire 100 for the filter or filters is formed of copper and is preferably silver or silver-plated.
- the flattened ribbon-shaped wick or ribbon (e.g. FIGS. 4 and 4A) can be wrapped around a filter or a metal core in the preferred form of a tube 102, with the wire strands all extending in the longitudinal direction along the tube, and the ribbon being in one or multiple layers so as to achieve the desired degree of filtration efficiency.
- the metal tube 102 has porous walls, e.g.
- Such contact causes the droplets to deposit on the capillary surface and by capillary action to coalesce with other of said droplets to form increasingly large drops of mercury.
- high removal efficiency of the elemental mercury is achieved at very low differential pressures as the aqueous stream passes through the wound core.
- the braided structure of the substrate results in interstitial areas of extreme contact angle (less than 45 degrees), which is able to entrap the droplets.
- the combination of this contact angle, along with the affinity mercury for the precious metal capillary surface results in the de-dispersion of the droplets and wetting out on the substrate.
- the effluent stream 106 from which the elemental mercury has been removed exits the second filtration stage and proceeds to the third filtration stage 108.
- the effluent stream 106 from the second stage 98 is passed through a filter or filters, where it is subjected to conditions, which remove the ionic mercury. In the case of an aqueous stream, this can be readily accomplished by passing the stream though a granular media impregnated with one or more chemical agents that are able to effect the desired precipitation.
- the granular media can be composed of carbon, clay, paper, mineral particulates such as perlite, etc., and the precipitating agents can include, but are not limited to, calcium sulfate, sulfides and thiols.
- These substrates may be packed or otherwise disposed in a cartridge or canister filter; or can be formed into bag filters which can be emplaced in canisters through which the contaminated water is flowed.
- the effluent stream 1 10 from third filtration stage 108 is then returned to the main or primary aqueous stream 94.
- the third stage is removed after the period of operation, and the collecting media (typically activated carbon) is subjected to
- Inorganic salts of Hg with CI, S or oxygen will behave as acids upon exposure to alkaline media such as the modified carbon resulting in formation of elemental Hg which will then be adsorbed onto the carbon substrate.
- alkaline media such as the modified carbon resulting in formation of elemental Hg which will then be adsorbed onto the carbon substrate.
- ionic mercury essentially means or is synonymous with inorganic mercury salts.
- Such salts may be present in the gaseous steam where they are hydrated by water vapor in the gases.
- Reaction products at the third filter stage 108 media will predominately be calcium chloride, sulfide, oxide or hydroxide and elemental Hg which will be adsorbed on the carbon media.
- the first filtration stage is optionally removed from the filter housing after a specified time period, for total organic analysis. This is carried out by filter sectioning, hexane extraction, and running gas chromatography mass spectrometry. This is for elucidation of organic specie types and concentrations. Total Organic Concentration in the inlet stream is determined by knowing the complete mass of the filter, the mass of the section subjected to extraction, and the flow rate and time the filter was subjected to, hereby allowing the analyst to determine concentration in the stream per volume.
- each of the stages is removed and analyzed for Hg.
- testing can be destructive because characterization of the species was done during sampling.
- Each one of the stages can be analyzed by acid digestion followed by atomic absorption spectrophotometry (AA) or induction-coupled plasma (ICP) or a number of other well-known spectrographic techniques.
- AA atomic absorption spectrophotometry
- ICP induction-coupled plasma
- the system 90 may be connected through a regulator at 1 to 80 pounds per square inch (psi). The system is typically engaged from 1 to 8 hours. At the end of the sampling period the system is disengaged and the three filtration stages are analyzed for content of the particular mercury species collected at the stage.
- the data presents an accurate picture of the relative proportions of the three species of mercury present in the primary stream of interest, as well as the concentrations of the species.
- This analysis may then be dependably used to design a system for removing the mercury contamination from the primary stream.
- the analysis can be used to establish that a specific number of filtration units corresponding to stage one of the present invention are required, a specified number of filtration units as in stage two, and a specific number of filtration units as in stage three.
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Abstract
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US14/480,314 US9504946B2 (en) | 2006-12-14 | 2014-09-08 | Process and system for separating finely aerosolized elemental mercury from gaseous streams |
PCT/US2015/047693 WO2016040027A1 (fr) | 2014-09-08 | 2015-08-31 | Procédé et système pour la séparation de mercure élémentaire mis sous forme d'aérosol fin de flux gazeux |
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US5322628A (en) * | 1992-09-08 | 1994-06-21 | Mobil Oil Corporation | Method for simultaneously drying and removing metallic and organic mercury from fluids |
US7033419B1 (en) * | 2003-09-16 | 2006-04-25 | The United States Of America As Represented By The United States Department Of Energy | Method for high temperature mercury capture from gas streams |
US7314507B1 (en) * | 2003-11-19 | 2008-01-01 | Montana Tech Of The University Of Montana | Apparatus and method for removing mercury vapor from a gas stream |
US8105423B2 (en) * | 2006-12-14 | 2012-01-31 | Hal Alper | Process and system for separating finely aerosolized elemental mercury from gaseous streams |
US7981298B2 (en) * | 2006-12-14 | 2011-07-19 | Hal Alper | Process for removal of contaminants from industrial streams |
EP2470288B1 (fr) * | 2009-08-28 | 2020-01-01 | Hal Alper | Procédé et système d'analyse de concentrations de diverses espèces de mercure dans un support fluidique |
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