|Publication number||US6939394 B2|
|Application number||US 10/767,901|
|Publication date||Sep 6, 2005|
|Filing date||Jan 29, 2004|
|Priority date||Dec 10, 2002|
|Also published as||CN1723072A, CN100349640C, CN101144566A, CN101144566B, EP1569738A1, EP1569738A4, EP1569738B1, EP2614875A2, EP2614875A3, US6743278, US7455719, US20040107838, US20040185254, US20060011064, WO2004052507A1, WO2004053383A2, WO2004053383A3|
|Publication number||10767901, 767901, US 6939394 B2, US 6939394B2, US-B2-6939394, US6939394 B2, US6939394B2|
|Inventors||J. Donald Carruthers|
|Original Assignee||Advanced Technology Materials, Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (61), Non-Patent Citations (9), Referenced by (47), Classifications (36), Legal Events (5)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This is a continuation of U.S. Ser. No. 10/315,635, filed on Dec. 10, 2002, and issued on Jun. 1, 2004 as U.S. Pat. No. 6,743,278.
The present invention relates generally to gas storage and dispensing systems, and particularly to systems of such type utilizing a monolithic carbon sorbent as a gas storage medium.
The physical adsorbent-based gas storage and dispensing system disclosed in Tom et al. U.S. Pat. No. 5,518,528 has revolutionized the transportation, supply and use of hazardous gases in the semiconductor industry. The system includes a vessel holding a physical adsorbent medium such as molecular sieve or activated carbon, having sorptive affinity for the gas that is to be stored in and selectively dispensed from the vessel. The gas is held in the vessel in an adsorbed state on the sorbent medium at reduced pressure relative to a corresponding empty (of sorbent) vessel holding an equivalent amount of gas in the “free” (unadsorbed) state.
By such reduced pressure storage, the safety of the gas storage and dispensing operation is substantially improved, since any leakage will result in a very low rate of egress of gas into the ambient environment, relative to a conventional high pressure gas storage cylinder. Further, the low pressure operation of the adsorbent-based system is associated with a lower likelihood of such gas leakage events, since the reduced pressure reduces the stress and wear on system components such as valves, flow controllers, couplings, joints, etc.
In such adsorbent-based gas storage and dispensing systems, the working capacity of the physical adsorbent medium is an operating constraint. The working capacity is the amount of gas that can be stored (“loaded”) on the sorbent medium and desorptively removed from such sorbent medium for use. The working capacity is a function of the storage pressure of the gas in the sorbent medium-containing gas storage vessel, and the dispensing condition of the desorbed gas (e.g., dispensing pressure of the desorbed gas, when pressure differential is used to effect desorption, and temperature levels of respective storage and dispensing conditions, when thermal desorption of gas is used as the dispensing modality), and the type and character of the sorbent medium itself (e.g., involving such parameters as sorbent media size, shape, porosity, pore size distribution, and tortuosity of interior pore passages).
The art is continually seeking improvement in working capacity of the physical adsorbent-based gas storage and dispensing system.
The present invention relates to physical adsorbent-based gas storage and dispensing systems, and to an improved working capacity system of such type.
In one aspect, the present invention relates to a fluid storage and dispensing apparatus, comprising a fluid storage and dispensing vessel having an interior volume, wherein the interior volume contains a physical adsorbent sorptively retaining a fluid thereon and from which the fluid is desorbable for dispensing from the vessel, and a dispensing assembly coupled to the vessel for dispensing desorbed fluid from the vessel, wherein the physical adsorbent comprises a monolithic carbon physical adsorbent that is characterized by at least one of the following characteristics:
Another aspect of the invention relates to a method of forming a monolithic adsorbent for use in a gas storage and dispensing system, said method comprising: molding a pyrolyzable material into a monolithic shape; and pyrolyzing the pyrolyzable material under pyrolysis conditions producing a monolithic adsorbent that is characterized by at least one of the following characteristics:
A further aspect of the invention relates to a method of storing and dispensing a gas, comprising: fabricating a gas storage and dispensing vessel; disposing a physical adsorbent in the vessel having sorptive affinity for said gas; charging said gas to said vessel for adsorption on the physical adsorbent; sealing the vessel with a valve head containing an actuatable valve, to enclose the physical adsorbent and adsorbed gas, and isolate same from an exterior environment of the vessel; desorbing the adsorbed gas from the physical adsorbent, and actuating the actuatable valve in the valve head, to flow gas from the vessel and through the actuatable valve, for gas dispensing; wherein the physical adsorbent is characterized by at least one of the following characteristics:
Other aspects, features and embodiments of the present invention will be more fully apparent from the ensuing disclosure and appended claims.
The present invention is based on the discovery that a physical adsorbent-based fluid storage and dispensing apparatus may be fabricated utilizing a fluid storage and dispensing vessel having a monolithic carbon adsorbent material therein, with surprising and unexpected advantages as regards the nature and extent of sorption and desorption of gas on the adsorbent, the packing density achievable for the physical sorbent medium in the vessel, and the utility of the fluid storage and dispensing apparatus comprising such vessel for semiconductor manufacturing operations.
The present invention thus achieves a substantial advance in the art over adsorben-based gas storage and dispensing systems of the type described in Tom et al. U.S. Pat. No. 5,518,528 which heretofore have used physical sorbent media in a finely divided form, such as a so-called bead activated carbon. In accordance with the present invention, the gas storage and dispensing system can be significantly improved in working capacity when the activated carbon is provided, not in a bead or particulate form, but rather in a monolithic form of specific character.
The level of improvement achievable by the use of a monolithic form of activated carbon, relative to the finely divided forms used in the prior art, is highly unexpected, and is even more surprisingly improved when the gas storage and dispensing vessel is of a shape conforming to the adsorbent monolith.
For example, when the vessel is of a preferred cube or other rectangular parallelepiped shape, consistent with the disclosure of co-filed U.S. patent application Ser. No. 10/314,777 filed Dec. 9, 2002 in the names of Dennis Brestovarisky, Michael J. Wodjenaki, Jose I. Amo and J. D. Carruthers, for “Rectangular Parallelepiped Fluid Storage and Dispensing System,” the use of a conformably shaped monolith can increase the working capacity of the physical adsorbent-based gas storage and dispensing system by at least 85% relative to a prior art system using a gas storage cylinder of the same “footprint” and vessel interior volume, filled with bead activated carbon.
By way of background explanation of the unanticipated advantages of the preferred packaging of the monolithic physical adsorbent of the invention in a rectangular parallelepiped conformation vessel in the physical adsorbent-based fluid storage and dispensing apparatus, it would on initial consideration appear to be highly disadvantageous to employ a rectangular parallelepiped conformation for a physical-adsorbent-based fluid storage and dispensing system, since: (i) a rectangular parallelepiped vessel has six faces, and twelve weld-lines required for fabrication if each face of the vessel is a separate piece (by contrast, a cylindrical vessel may be formed without seams from tubular rolled steel stock); (ii) consistent with (i), the fabrication cost of a rectangular conformation vessel would expected to be substantially higher than for a corresponding cylindrical vessel; (iii) a rectangular parallelepiped conformation involves “sharp” corners at the juncture of adjacent perpendicularly oriented walls that offer the potential of forming voids at the line of juncture, wherein the sorbent bed would not “pack” against the corner, relative to a corresponding cylindrical geometry vessel (which is free such corners, and instead is a minimum cross-sectional area shape circumscribing the bed of physical sorbent material in the interior volume of the vessel); and (iv) the intersection of two perpendicular walls with one another produces a joint that is susceptible to rupture by pressure or force directed thereon, relative to a “seamless” cylindrical vessel.
It has been determined, however, that the rectangular parallelepiped conformation results in a vessel which does have less tightly packed sorbent bed regions adjacent the seams at the intersection of adjacent walls, but that rather than being a disadvantage, such lower density sorbent bed regions are in fact advantageous as higher gas flow conductance pathways for interstitial desorbed or unadsorbed gas to flow out of the bulk volume of the sorbent bed.
Further, precisely because the cylindrical vessel is a minimum cross-sectional area conformation, with a minimum circumferential extent of circumscribing wall area, the amount of sorbent that is “presented” to the wall in the cylindrical vessel is maximized. Considering the converse, the peripheral extent of the wall that bounds (is adjacent to) the sorbent bed in cross-section is much greater in the rectangular parallelepiped conformation than in the cylindrical vessel. The rectangular parallelepiped conformation thereby enables higher volume egress of gas from the vessel than from a correspondingly sized cylindrical vessel, because the wall surface bounding the sorbent bed is non-adsorbing in character, and there is proportionally more of it in the rectangular conformation vessel, at the outer margins of the sorbent bed, than there is in the cylindrical vessel. As a result, the desorbed gas at the wall regions is less readsorbed subsequent to its initial desorptive release from the sorbent medium than desorbed gas in the interior portions of the sorbent bed.
For these reasons, the rectangular parallelepiped vessel conformation has particular utility for holding the monolithic form of the physical adsorbent of the present invention.
As used herein, “monolithic” means that the sorbent medium is in a unitary or block-like form, e.g., in the form of blocks, bricks, discs, boules, etc., in contradistinction to conventional finely divided forms such as beads, particles, granules, pellets, and the like, which are generally utilized in the form of a bed comprising a multiplicity of such beads, particles, granules, pellets, etc. Thus, in the bed form of multiple finely divided physical adsorbent elements, the void volume of the active sorbent is in major part interstitial, or inter-particle, in character, varying according to the dimensions, shape and packing density of the sorbent particles. By contrast, in a monolithic form, the void volume of the active sorbent is in form of porosity intrinsic to the sorbent material and voids that may have been formed in the bulk sorbent body during its processing.
The present invention in one aspect relates to a fluid storage and dispensing apparatus, comprising a fluid storage and dispensing vessel having an interior volume, wherein the interior volume contains a physical adsorbent sorptively retaining a fluid thereon and from which the fluid is desorbable for dispensing from the vessel, and a dispensing assembly coupled to the vessel for dispensing desorbed fluid from the vessel, wherein the physical adsorbent comprises a monolithic carbon physical adsorbent that is characterized by at least one of the following characteristics:
The monolithic adsorbent can be in the form of a single monolithic adsorbent article, or a multiplicity of monolithic adsorbent articles. The adsorbent can be suitably shaped to conform to the interior volume of the vessel in which it is disposed, and preferably occupies at least 60% of the interior volume of the vessel, e.g., from 75 to 95% of such interior volume. While the invention is discussed more fully hereinafter in respect of containment of the monolithic adsorbent in the preferred rectangular parallelepiped shaped vessel, it will be appreciated that the invention is not thus limited, and that other vessel shapes and conformations can be utilized, e.g., cylindrical-shaped vessels, barrel-shaped vessels, frustoconical-shaped vessels, etc.
The monolithic adsorbent can be formed as the pyrolysis product of an organic resin, and more generally can be formed from any suitable pyrolyzable material, such as for example polyvinylidene chloride, phenol-formaldehyde resins, polyfurfuryl alcohol, coconut shells, peanut shells, peach pits, olive stones, polyacrylonitrile, and polyacrylamide. The adsorbent can be formed in the fluid storage and dispensing vessel in which the fluid will be stored for subsequent dispensing, i.e., in situ, or the adsorbent can be formed and then introduced into the fluid storage and dispensing vessel. In one embodiment, the adsorbent has at least 20% of its porosity in pores with a diameter of less than 2 nanometers.
The adsorbent can be provided in the fluid storage and dispensing vessel as a multiplicity of monolithic adsorbent articles that aggregatively constitute the adsorbent mass. In such multiple monolithic article arrangement, each of the multiplicity of discrete monolithic adsorbent articles can have a length that is between 0.3 and 1.0 times the height of the interior volume of the vessel, and a cross-sectional area that is between 0.1 and 0.5 times the rectangular cross-sectional area of the vessel. Each of the multiplicity of discrete monolithic articles can have a rectangular parallelepiped shape or alternatively a cylindrical or other suitable shape. In the interior volume of the fluid storage and dispensing vessel, the discrete monolithic articles can be laterally and/or longitudinally abutted in surface contact with adjacent monolithic members. In one embodiment, each of the multiplicity of discrete monolithic articles has a length to cross-sectional dimension ratio, L/D, that is from about 2 to about 20, e.g., in a range of from about 4 to about 15, where L is the length or major axis dimension of the monolithic carbon sorbent article, and D is the transverse or minor axis dimension. In another embodiment, the monolithic adsorbent article can have a disc shape, with a height to diameter ratio, H/D, that is from about 0.10 to about 0.80.
The fluid in the fluid storage and dispensing vessel that is sorptively retained on the adsorbent, and desorbed under suitable desorbing conditions for dispensing of fluid, can be fluid of any suitable type, e.g., fluid having utility in semiconductor manufacturing, such as hydrides, halides and organometallic gaseous reagents, e.g., silane, germane, arsine, phosphine, phosgene, diborane, germane, ammonia, stibine, hydrogen sulfide, hydrogen selenide, hydrogen telluride, nitrous oxide, hydrogen cyanide, ethylene oxide, deuterated hydrides, halide (chlorine, bromine, fluorine, and iodine) compounds, and organometallic compounds.
The fluid in the vessel can be stored at any suitable atmospheric, sub-atmospheric or super-atmospheric pressure, e.g., pressure below 2500 torr, such as in a range of from about 20 torr to about 1200, or pressure in a range of from about 20 torr to about 750 torr for subatmospheric pressure supply of gases for ion implantation or other subatmospheric pressure application.
The vessel holding the adsorbent having fluid adsorbed thereon can be formed of any suitable vessel material(s) of construction, such as metals (e.g., steel, stainless steel, aluminum, copper, brass, bronze, and alloys thereof), glasses, ceramics, vitreous materials, polymers, and composite materials.
The vessel can be of any suitable shape and size, as appropriate to the specific fluid storage and dispensing application. The vessel can, for example, be of a rectangular parallelepiped shape, being of elongate vertically upstanding form, with a square cross-section, or the vessel can be cylindrical with a circular cross-section, or in any other appropriate shape, size and form.
In one embodiment, the invention utilizes a physical adsorbent of monolithic form in a rectangular parallelepiped vessel defining a closed interior volume and having a port to which is coupled a gas dispensing assembly, for selective discharge of gas from the vessel. The sorbent medium in the monolithic form of the present invention provides sufficient capacity for sorptive retention of the sorbate gas in the desired quantity, good desorptive release of gas under desorption conditions, and good working capacity with good heels behavior (i.e., high extent of desorption of initially adsorbed gas), and has an appropriate sorptive affinity for the gas of interest so that low gas pressure is maintained in the interior volume of the vessel during storage of gas therein.
The physical adsorbent in accordance with the present invention can be of any suitable monolithic form, e.g., in the form of blocks, bricks, boules or similar forms of the adsorbent material that are of a size commensurate with the fluid storage and dispensing vessel, so that vessel contains one or a small number, e.g., less than 75, more preferably less than 20, of the discrete monolithic articles. In a further preferred aspect, the vessel contains no more than 8 such discrete monolithic articles, even more preferably no more than four such articles, and most preferably the vessel contains a single monolithic physical adsorbent article.
The monolithic article(s) deployed in the fluid storage and dispensing vessel provide(s) an aggregate sorbent mass that is preferably conformed in size and shape to the interior volume of the fluid storage and dispensing vessel, so that the sorbent mass of the monolithic article(s) occupies at least 60% of the interior volume of the vessel, preferably in a range of from about 75% to about 95% of the interior volume of such vessel.
If provided as a single monolithic sorbent article, the sorbent medium may for such purpose be formed in situ in the vessel, e.g., by pyrolysis of an organic resin that is in liquid or otherwise flowable form, with which the vessel is filled to a desired extent prior to pyrolysis of same in the vessel.
If alternatively provided in the form of multiple monolithic articles, each of such articles can be provided with a length that is between 0.3 and 1.0 times the height of the interior volume of the vessel, and a cross-sectional area that is between 0.1 and 0.5 times the rectangular cross-sectional area of the vessel. Each monolithic member can have a rectangular parallelepiped shape for maximizing the volumetric usage of the interior volume of the vessel when the vessel is of rectangular parallelepiped shape, wherein each of the monolithic members may be laterally and/or longitudinally abutted in surface contact with adjacent monolithic members in the interior volume of the vessel. Alternatively, in some instances, it may be desirable for the sorbent monolithic members to be in the form of solid cylinders, with the respective cylindrical members being loaded into the interior volume so as to tangently abut one another along their facing side surface, and to at least partially abut one another in face-to-face contact at their circular cross-section end surfaces. In fluid storage and dispensing vessels of shapes other than cubic or other rectangular parallelepiped shapes, the monolithic sorbent article(s) may be correspondingly formed to conform to the shape of the interior volume of the vessel. For example, the fluid storage and dispensing vessel can be of cylindrical shape, with monolithic adsorbent articles therein comprising a vertical stack of disc-shaped bodies of adsorbent, each having diameter conforming it at its periphery to the shape of the vessel, in close proximity to the facing inner wall surface of the vessel.
The level of improvement attendant the use of a monolithic form of activated carbon over finely divided particulate forms of the prior art is unexpected because physical adsorbent materials are generally classified in terms of their surface area available for sorptively retaining the working gas (adsorbate), and hence particulate forms with their high surface to volume ratio have been considered inherently superior to bulk forms such as blocks and bricks (i.e., monolithic forms) having a lower apparent surface-to-volume ratio. Thus, one would expect intuitively that monolithic forms of adsorbent would be low efficiency forms, having a reduced sorptive capacity and working capacity.
It has been discovered, however, that a carbon monolith may be formed having a similar micropore volume as corresponding bead carbon, but with a substantially higher density, e.g., a density in a range of from about 25% to about 80% higher than the compacted density of the corresponding bead carbon, and that such high density monolith when used in a physical adsorbent-based gas storage and dispensing system provides a striking improvement in mass of gas adsorbed per unit volume of the sorbent in comparison to a bed of bead carbon.
Carbon monoliths useful in the broad practice of the present invention include gross brick, block and ingot forms, as bulk forms, preferably having three-dimensional (x, y, z) character wherein each of such dimensions is greater than 1.5, and preferably greater than 2 centimeters. For example, the carbon monolith may be in the form of a monolith briquette, as made from a polymeric char such as polyvinylidene chloride (PVDC) or other suitable polymer, having a high bulk density (measured with voids), e.g., on the order of from about 0.80 to about 2.0 grams per cubic centimeter, with high working capacity (high microporosity and low heel) and pore tortuosity that is sufficiently low to ensure ready and rapid rate adsorption and desorption.
In one embodiment, the monolithic carbon sorbent of the invention includes a doping agent on the active carbon to minimize decomposition of the sorbate fluid during extended storage. Illustrative of doping agents that can be usefully employed in the broad practice of the invention are boric acid (H3BO3), sodium tetraborate (Na2B4O7), sodium silicate (Na2SiO3) and disodium hydrogen phosphate (Na2HPO4).
The monolithic carbon adsorbent articles in another aspect can have a length to cross-sectional dimension ratio, L/D, that is from about 2 to about 20, and more preferably from about 4 to about 15, where L is the length or major axis dimension of the monolithic carbon sorbent article, and D is the transverse or minor axis dimension. In a specific embodiment, the monolithic carbon adsorbent is provided in the form of 1″×1″ square cross-section PVDC char monolith briquettes, approximately 6″ in height.
A preferred monolithic carbon adsorbent comprises pyrolysis products of Saran A, Saran MC-10S or Saran XPR-1367-D-01452-050 PVDC homopolymers or copolymers, as ultramicroporous carbons having a high proportion of slit-shaped pores of small dimension, e.g., in a range of from about 0.3 to about 0.75 nanometers.
When the monolithic carbon sorbent has pores with a diameter of less than about 2 nanometers, the monolithic carbon sorbent is able to adsorb gases, e.g., boron trifluoride, above their critical temperature to an extent that is proportional to the micropore volume of the sorbent material. Preferred monolithic carbon sorbent materials for such purpose have a high proportion of pores, e.g., at least 50% of porosity, in the small micropore, e.g., ultramicropore, size range. This effect may be seen by reference to
Although micropore volume is an important criterion for selecting carbon for use in the monolithic carbon adsorbent systems of the invention, and micropore volume is desirably maximized, gases stored in a fixed volume vessel are appropriately compared on a volume per liter of adsorbent basis. The adsorbent packing density in such instance becomes extremely important. To this end, the monolithic carbon eliminates void volume in the fluid storage and dispensing vessel in which it is employed.
Void volume in the fluid storage and dispensing vessel in accordance with the present invention, in a preferred embodiment, does not exceed about 40% of the total interior volume of the vessel, and more preferably is as low as possible. The packing density of the monolithic carbon sorbent is desirably as high as possible, with maximum micropore volume on a volume per volume of adsorbent basis, and a high proportion of pore volume being in ultramicropores. The conformation of the micropores is also important, with the pores being desirably slit-shaped to provide high adsorption levels, but not so small so that the slit conformation interferes with ready gas release under desorption conditions, e.g., desorption at pressure levels on the order of 40 torr.
During activation of carbon to form activated carbon, the pores are widened at elevated temperature in the presence of a non-oxidizing gas such as nitrogen, followed by exposure to an oxidizing gas such as oxygen or steam for a short duration, and then cooling in a non-oxidizing atmosphere. In such activation, the level of burn-off of the material is carefully controlled, since a high level of burn-off causes widening of the pores, with an increase in micropore volume and concomitant reduction of particle density.
The monolithic carbon adsorbent of the invention can be suitably formed in any suitable manner. In one embodiment, the monolithic carbon is formed from a polymeric material such as the polyvinylidene chloride polymer commercially available from The Dow Chemical Company (Midland, Mich.) as Saran A or Saran MC-10S polymer, as pressure molded at suitable pressure, e.g., a pressure in a range of from about 10 kilopounds per square inch to about 20 kilopounds per square inch, and then pyrolyzed in a nitrogen gas stream at a temperature of from about 600° C. to about 900° C., e.g., on the order of about 700° C. This process produces a carbon sorbent material having a greatly increased fill density (viz., the weight of gas adsorbed, e.g., in grams, per liter of carbon), as shown in the graphs of
The monolithic carbon adsorbent of the invention represents a significant departure from the practice of the prior art, which has utilized finely divided particles, such as bead activated carbon having a particle diameter of 0.1-1.0 centimeter and more typically a particle diameter of 0.25-2.0 millimeters, or which, in the case of bulk microporous carbon materials (see Wojtowicz et al. U.S. patent application Publication US2002/0020292 A1 published Feb. 21, 2002), has utilized high temperature, e.g., >1000° C. and preferably >1100° C., to induce high graphitization levels, in combination with activation involving repetitive chemisorption/desorption steps performed as many as 76 times (see Quinn, et al. U.S. Pat. No. 5,071,820) to achieve suitable micropore volume, surface area and micropore volume per unit volume of carbon adsorbent, a time-consuming and costly approach to obtaining a suitable sorbent material for high-pressure gas storage applications (Wojtowicz et al. U.S. patent application Publication US2002/0020292 A1 discloses that optimal storage capacity for the sorbate gas requires that the gas “be introduced into the storage vessel at a pressure in the range of from about 500 psi to about 3500 psi,” page 2, paragraph , last sentence).
In contrast to these prior art approaches, the monolithic carbon sorbent of the present invention is formed from a suitable polymeric material, e.g., a polymer selected from among polyvinylidene chloride, phenol-formaldehyde resins, polyfurfuryl alcohol, coconut shells, peanut shells, peach pits, olive stones, polyacrylonitrile, polyacrylamide, etc., that is pressure-moldable, e.g., at a molding pressure up to about 20,000 psi or higher, to yield a pressure-molded “green resin” body that is pyrolyzable at temperature below 1000° C., preferably not exceeding about 900° C., e.g., in a range of from about 500° C. to about 900° C., and more preferably in a range of from about 600° C. to about 900° C., to yield a monolithic carbon material having a fill density of suitably high value for the intended gas storage and dispensing application. Monolithic carbon sorbents useful in the practice of the present invention include those having a fill density measured for arsine gas at 25° C. and a pressure of 650 torr that is in excess of 400 grams arsine per liter of carbon adsorbent, and preferably greater than 450 grams arsine per liter of carbon adsorbent.
The pyrolysis product may be employed as a monolithic sorbent body in accordance with the present invention, as is, but such pyrolysis product preferably is activated in a manner producing a monolithic carbon sorbent product with ultramicroporosity having a high proportion, e.g., at least 30% of porosity, and preferably at least 60% of porosity, of slit-shaped pores having a size in a range of from about 0.3 to about 0.72 nanometer and a significant porosity, e.g., at least 20%, and preferably at least 30%, of the overall porosity comprising micropores, with diameter <2 nanometers. The activation process can include any suitable processing steps for enhancing the sorptive affinity of the material for the sorbate gas of interest or otherwise improving the characteristics of the sorbent medium for adsorption/desorption duty. For example, the activation process can include heating in a non-oxidizing atmosphere, e.g., of nitrogen, argon, helium or other non-oxidizing gas, followed by switching of the atmosphere to an oxidizing atmosphere, such as carbon dioxide or steam for a brief duration, before switching to a non-oxidizing atmosphere and cooling to ambient temperature (e.g., room temperature). The specifics of the activation process, e.g., the temperature levels and duration of the successive steps can be readily determined within the skill of the art without undue experimentation, by simple variation of respective process conditions and analytic determination of the resulting sorbent performance, such as fill density, porosimetry characterization, etc.
The data in
Set out below in Table 1 are fill density values of arsine on the three types of adsorbent materials discussed above in connection with
Arsine Capacity on Non-Monolithic Activated
Carbon and Monolithic Carbon
Fill Density at 650
Fill Density at 650
gram of adsorbent)
liter of adsorbent)
Kureha 578-66-6 (sample 1)
Kureha 578-66-6 (sample 2)
14-03 (sample 1)
14-03 (sample 2)
PVDC char (sample 1)
PVDC char (sample 2)
The results in Table 1 show that while the fill density on a weight basis for the monolithic carbon adsorbent was approximately 15-20% lower than for the non-monolithic activated carbon adsorbents, the fill density of the monolithic carbon adsorbent on a volumetric basis was well over 50% higher than the corresponding fill densities of the non-monolithic activated carbon adsorbents.
Table 2 below is a corresponding fill density tabulation for fill density values of phosphine on the three types of adsorbent materials discussed above in connection with
Phosphine Capacity on Non-Monolithic Activated
Carbon and Monolithic Carbon
Fill Density at
Fill Density at
650 Torr Pressure
650 Torr Pressure
Takachiho ABF 14-03
The results in Table 1 show that the monolithic carbon adsorbent (PVDC char) had a fill density on both weight and volumetric basis that were above those of the non-monolithic forms of activated carbon adsorbent, with the fill density on a volumetric basis being on the order of 100% higher than the volumetric fill density of phosphine on the non-monolithic forms of activated carbon.
The sorbate fluid retained on the monolithic carbon adsorbent in the broad practice of the present invention can be of any suitable type, including for example, hydride gases (such as arsine, phosphine, germane, silane, mono-, di-, and tri-substituted silanes, e.g., alkyl silanes of such types), halide gases (such as boron trifluoride, boron trichloride, halogen-substituted silanes, etc.) and gaseous organometallic compositions.
Illustrative sorbate gas species that are usefully storable and dispensable in the practice of the invention include silane, germane, arsine, phosphine, phosgene, diborane, germane, ammonia, stibine, hydrogen sulfide, hydrogen selenide, hydrogen telluride, nitrous oxide, hydrogen cyanide, ethylene oxide, the deuterated hydrides, halide (chlorine, bromine, fluorine, and iodine) compounds, including such compounds as F2, SiF4, Cl2, ClF3, GeF4, SiF4, boron halides, etc., and organometallic compounds of metals such as aluminum, barium, strontium, gallium, indium, tungsten, antimony, silver, gold, palladium, gadolinium, etc.
The pressure at which the sorbate gas is stored in the vessel may be any suitable pressure appropriate to the application for which the gas storage and dispensing system of the invention is employed. Illustrative pressure levels generally useful in the practice of the invention include pressures not exceeding about 2500 torr, more preferably not exceeding 2000 torr, e.g., a pressure in a range of from about 20 torr to about 1800 torr, or more restrictively from about 20 torr to about 1200 torr. For applications such as ion implantation, the pressure of the gas in the gas storage and dispensing vessel typically does not exceed about 800 torr, and the stored gas may be at subatmospheric pressure, e.g., a pressure in a range of from about 20 torr to about 750 torr.
As shown, the storage and dispensing system 200 comprises a storage and dispensing vessel 204 that is joined at its upper portion to a valve head 206 comprising part of a dispensing assembly including manual actuator 208 for the valve head on the cylinder. The vessel may be formed of any suitable material of construction, e.g., comprising material such as metals, glasses, ceramics, vitreous materials, polymers, and composite materials. Illustrative metals for such purpose include steel, stainless steel, aluminum, copper, brass, bronze, and alloys thereof. The valve head is joined by means of coupling 210 to a dispensing conduit 212 having disposed therein a pressure transducer 214, an inert purge unit 216 for purging the dispensing assembly with inert gas, a mass flow controller 220 for maintaining constant flow rate through the dispensing conduit 212 during the dispensing operation, and a filter 222 for removing particulates from the dispensed gas prior to its discharge from the dispensing assembly.
The dispensing assembly further comprises a coupling 224, for matably engaging the dispensing assembly with downstream piping, valving, or other structure associated with the locus of use of the desorbed fluid, e.g., involving a semiconductor manufacturing facility such as an ion implantation tool using the dispensed gas as an implant species.
The fluid storage and dispensing vessel 204 is shown as having a wall 226 that is partially broken away to show the interior monolithic sorbent body 205.
The dispensing valve of the pipe valve connection valve head 312 is threadably engaged with the vessel 310, by a 1½″ pipe thread connection. The valve head may have any suitable number of ports, e.g., single port valve heads, dual port valve heads, 3-port valve heads, etc.
The rectangular parallelepiped fluid storage and dispensing vessel 310 contains a monolithic carbon adsorbent in its interior volume, wherein the monolithic mass may include one or alternatively multiple monolithic carbon bodies, each preferably of a rectangular parallelepiped shape to conform to the shape of the interior volume of the vessel, as previously described.
It will be appreciated that the compositions and methods of the invention may be practiced in a widely variant manner, consistent with the broad disclosure herein. Accordingly, while the invention has been described herein with reference to specific features, aspects, and embodiments, it will be recognized that the invention is not thus limited, but is susceptible of implementation in other variations, modifications and embodiments. Accordingly, the invention is intended to be broadly construed to encompass all such other variations, modifications and embodiments, as being within the scope of the invention hereinafter claimed.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3539467||Nov 30, 1967||Nov 10, 1970||Kewanee Oil Co||Hot briquetting and oxidation of coal-pitch mixtures in preparing activated carbon|
|US3884830||Oct 2, 1973||May 20, 1975||Calgon Corp||Controlled selectivity activated carbon|
|US4000236||Aug 11, 1970||Dec 28, 1976||Patent Protection Limited||Making a conglomerated bonded mass consisting of particles of activated carbon|
|US4082694||Jun 16, 1976||Apr 4, 1978||Standard Oil Company (Indiana)||Active carbon process and composition|
|US4139416||Aug 1, 1977||Feb 13, 1979||Centro Sperimentale Metallurgico S.P.A.||Carbonaceous material with high characteristics of surface area and activity and process for producing the same|
|US4526887||Dec 13, 1983||Jul 2, 1985||Calgon Carbon Corporation||Carbon molecular sieves and a process for their preparation and use|
|US4528281||Mar 16, 1983||Jul 9, 1985||Calgon Carbon Corporation||Carbon molecular sieves and a process for their preparation and use|
|US4540678||Dec 13, 1983||Sep 10, 1985||Calgon Carbon Corporation||Carbon molecular sieves and a process for their preparation and use|
|US4738753||Sep 23, 1985||Apr 19, 1988||Alusuisse Italia S.P.A||Method of producing carbonaceous bodies|
|US4880765||May 22, 1987||Nov 14, 1989||Bergwerksverband Gmbh||Process for producing carbon molecular sieves|
|US4957897 *||Feb 7, 1989||Sep 18, 1990||Rohm And Haas Company||Carbonaceous adsorbents from pyrolyzed polysulfonated polymers|
|US5071820||May 25, 1990||Dec 10, 1991||Atlanta Gas Light Company||Carbonaceous material with high micropore and low macropore volume and process for producing same|
|US5110328||Jun 5, 1990||May 5, 1992||Kabushiki Kaisha Kobe Seiko Sho||Solvent adsorber and solvent recovery system|
|US5356852 *||Jan 13, 1993||Oct 18, 1994||Corning Incorporated||Activated carbon structures|
|US5372610||Sep 3, 1992||Dec 13, 1994||Bayer Aktiengesellschaft||Process for the after-bleaching of dyed raw cellulose using cationic compounds|
|US5376609 *||Aug 23, 1993||Dec 27, 1994||Corning Incorporated||Activated carbon bodies having bentonite and cellulose fibers|
|US5416056||Oct 25, 1993||May 16, 1995||Westvaco Corporation||Production of highly microporous activated carbon products|
|US5518528||Oct 13, 1994||May 21, 1996||Advanced Technology Materials, Inc.||Storage and delivery system for gaseous hydride, halide, and organometallic group V compounds|
|US5658372||Jul 10, 1995||Aug 19, 1997||Corning Incorporated||System and method for adsorbing contaminants and regenerating the adsorber|
|US5674462||Jul 25, 1994||Oct 7, 1997||Calgon Carbon Corporation||Method for the removal of non-metal and metalloid hydrides|
|US5710092||Mar 14, 1995||Jan 20, 1998||Westvaco Corporation||Highly microporous carbon|
|US5744421||Feb 13, 1996||Apr 28, 1998||Mega-Carbon Company||Monolithic carbonaceous article|
|US5837741 *||Aug 19, 1996||Nov 17, 1998||Syracuse University||Composite microporous carbons for fuel gas storage|
|US5846639||Feb 13, 1996||Dec 8, 1998||Mega-Carbon Company||Monolithic activated carbon|
|US5851403||Jun 4, 1997||Dec 22, 1998||Northrop Grumman Corporation||Ceramic honeycomb and method|
|US5902562||Oct 27, 1997||May 11, 1999||Sandia Corporation||Method for the preparation of high surface area high permeability carbons|
|US5912424||Mar 31, 1997||Jun 15, 1999||Lockheed Martin Energy Research Corporation||Electrical swing adsorption gas storage and delivery system|
|US5914294||Apr 23, 1996||Jun 22, 1999||Applied Ceramics, Inc.||Adsorptive monolith including activated carbon and method for making said monlith|
|US5965483||Oct 20, 1994||Oct 12, 1999||Westvaco Corporation||Highly microporous carbons and process of manufacture|
|US5972253||Sep 23, 1997||Oct 26, 1999||University Of Kentucky Research Foundation||Preparation of monolithic carbon fiber composite material|
|US6006797||Oct 31, 1996||Dec 28, 1999||The Boc Group Plc||Method and vessel for the storage of gas|
|US6019823||May 18, 1998||Feb 1, 2000||Advanced Technology Materials, Inc.||Sorbent-based fluid storage and dispensing vessel with replaceable sorbent cartridge members|
|US6030698||Nov 8, 1996||Feb 29, 2000||Lockheed Martin Energy Research Corporation||Activated carbon fiber composite material and method of making|
|US6156697||Oct 13, 1998||Dec 5, 2000||Corning Incorporated||Method of producing high surface area carbon structures|
|US6171373||Mar 10, 1999||Jan 9, 2001||Applied Ceramics, Inc.||Adsorptive monolith including activated carbon, method for making said monolith, and method for adsorbing chemical agents from fluid streams|
|US6187713||Jan 14, 1999||Feb 13, 2001||Corning Incorporated||Method of making activated carbon bodies having improved adsorption properties|
|US6207264||Dec 7, 1998||Mar 27, 2001||Mega-Carbon Company||Monolithic activated carbon|
|US6225257||Sep 14, 1999||May 1, 2001||Niagara Mohawk Power Corporation||Post-carbonization treatment of microporous carbons for enhancement of methane and natural gas storage properties|
|US6258300||Aug 27, 1999||Jul 10, 2001||Ut-Battelle, Llc||Activated carbon fiber composite material and method of making|
|US6284705||Mar 27, 2000||Sep 4, 2001||Westvaco Corporation||Adsorptive monolith including activated carbon, method for making said monolith, and method for adsorbing chemical agents from fluid streams|
|US6309446||Aug 16, 1999||Oct 30, 2001||Kanebo, Ltd.||Activated carbon for adsorptive storage of gaseous compound|
|US6309449 *||Oct 6, 1998||Oct 30, 2001||Mannesmann Ag||Gas accumulator|
|US6406519 *||May 3, 2000||Jun 18, 2002||Advanced Technology Materials, Inc.||Gas cabinet assembly comprising sorbent-based gas storage and delivery system|
|US6475411 *||Jul 26, 2000||Nov 5, 2002||Ut-Battelle, Llc||Method of making improved gas storage carbon with enhanced thermal conductivity|
|US6500238 *||Aug 10, 2000||Dec 31, 2002||Advanced Technology Materials, Inc.||Fluid storage and dispensing system|
|US6592653 *||Nov 12, 2001||Jul 15, 2003||Advanced Technology Materials, Inc.||Fluid storage and delivery system utilizing low heels carbon sorbent medium|
|US6699561 *||Jan 31, 2002||Mar 2, 2004||Helsa-Werke Helmut Sandler Gmbh & Co. Kg||Activated carbon molded body and use thereof|
|US6743278 *||Dec 10, 2002||Jun 1, 2004||Advanced Technology Materials, Inc.||Gas storage and dispensing system with monolithic carbon adsorbent|
|US6764755 *||Dec 17, 2001||Jul 20, 2004||Advanced Technology Materials, Inc.||Channelized sorbent media, and methods of making same|
|US20010027723||Jan 18, 2001||Oct 11, 2001||Ravi Jain||Air separation using monolith adsorbent bed|
|US20020020292||Jul 6, 2001||Feb 21, 2002||Wojtowicz Marek A.||Microporous carbons for gas storage|
|US20020073847||Dec 15, 2000||Jun 20, 2002||Sheline Matthew R.||Cell within a cell monolith structure for an evaporative emissions hydrocarbon scrubber|
|US20020103081 *||Jan 31, 2002||Aug 1, 2002||Helsa-Werke Helmut Sandler Gmbh & Co. Kg.||Activated carbon molded body and use thereof|
|US20030145731||Jan 21, 2003||Aug 7, 2003||Biasio Ennio De||Storage apparatus|
|US20030196553 *||Apr 4, 2003||Oct 23, 2003||Cataler Corporation||Adsorbent for adsorbing fuel vapors|
|US20040118286 *||Dec 9, 2002||Jun 24, 2004||Dennis Brestovansky||Rectangular parallelepiped fluid storage and dispensing vessel|
|JPH01131015A||Title not available|
|JPH07124468A||Title not available|
|JPS5573315A||Title not available|
|WO2000015330A1||Sep 10, 1999||Mar 23, 2000||Lockheed Martin Energy Research Corporation||Gas storage carbon with enhanced thermal conductivity|
|WO2001093985A1||Jun 7, 2000||Dec 13, 2001||Gas Authority Of India Limited||Process for storage, transmission & distribution of gaseous fuel|
|1||Carrott, P.J.M., Roberts, R.A., Sing, K.S.W., Characterization of Porous Solids, K.K. Unger et al. Editors, Elsevier Science, Amsterdam, 1988, p. 89.|
|2||D.F. Quinn and J.A. MacDonald, "Natural Gas Storage", Carbon, vol. 30, No. 7, pp. 1097-1103, 1992.|
|3||Dacey, J.R., Thomas, D.G., Trans. Farad. Soc, 50 (1954), 740.|
|4||J.A.F. MacDonald and D.F. Quinn, "Carbon Adsorbents for Natural Gas Storage", Fuel, 1998, vol. 77, No. 1/2, pp. 61-64.|
|5||J.R. Dacey and D.A. Cadenhead, The Roayl Military College of Canada, Kingston, Ontario "The Formation of Carbon From Polyvinylidene Choride", Reprint from "Proceedings of the Fourth Conference on Carbon", Pergamon Press, 1960, pp. 315-319.|
|6||Parkyns, N.D.,, Quinn, D.F., Porosity in Carbons: Characterization and Applications, Editor: Patrick, J.P. Halsted Press, (John Wiley) N.Y., 1995, p. 292.|
|7||Rouquerol, F., Rouquerol, J., Sing, K.S.W., Adsorption by Powders & Porous Solids, Academic Press, 1999, p. 276.|
|8||Sing, K.S.W., Everett, D.H., haul, R.A.W., Mousou, L., Pierotti, R.A., Rouquerol, J., Siemieniewska, T., Pure & Appl. Chem., 57 (1985) 603.|
|9||Wojtowicz, M.A., Markowitz, B.L., Smith, W.W., Serio, M.A., Int. J. of the Soc. Of Mat. Eng. for Resources, 7, 2 , (1999) 253.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
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|US7779608||May 26, 2007||Aug 24, 2010||Lim Walter K||Pressurized containers and methods for filling them|
|US7862646||Jul 30, 2008||Jan 4, 2011||Advanced Technology Materials, Inc.||Nanoporous articles and methods of making same|
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|US8002880||Feb 24, 2009||Aug 23, 2011||Advanced Technology Materials, Inc.||Gas storage and dispensing system with monolithic carbon adsorbent|
|US8119853||Jan 12, 2009||Feb 21, 2012||L'Air Liquide SociétéAnonyme pour l'Etude et l'Exploitation des Procédés Georges Claude||Low pressure acetylene storage|
|US8147599||Aug 16, 2010||Apr 3, 2012||Mcalister Technologies, Llc||Apparatuses and methods for storing and/or filtering a substance|
|US8221532 *||Jul 17, 2012||Carruthers J Donald||Nanoporous articles and methods of making same|
|US8282023||Oct 9, 2012||Advanced Technology Materials, Inc.||Fluid storage and dispensing systems, and fluid supply processes comprising same|
|US8282714||Aug 23, 2011||Oct 9, 2012||Advanced Technology Materials, Inc.||Gas storage and dispensing system with monolithic carbon adsorbent|
|US8506689||Jun 26, 2011||Aug 13, 2013||Advanced Technology Mateials, Inc.||Rectangular parallelepiped fluid storage and dispensing vessel|
|US8539781||Jun 22, 2008||Sep 24, 2013||Advanced Technology Materials, Inc.||Component for solar adsorption refrigeration system and method of making such component|
|US8555705||Jun 28, 2011||Oct 15, 2013||Advanced Technology Materials, Inc.||Fluid storage and dispensing system including dynamic fluid monitoring of fluid storage and dispensing vessel|
|US8617399||Aug 13, 2012||Dec 31, 2013||Mcalister Technologies, Llc||Dynamic filtration system and associated methods|
|US8641810||Apr 2, 2012||Feb 4, 2014||Mcalister Technologies, Llc||Apparatuses and methods for storing and/or filtering a substance|
|US8679231||Dec 17, 2011||Mar 25, 2014||Advanced Technology Materials, Inc.||PVDF pyrolyzate adsorbent and gas storage and dispensing system utilizing same|
|US8858685||Aug 31, 2012||Oct 14, 2014||Advanced Technology Materials, Inc.||Gas storage and dispensing system with monolithic carbon adsorbent|
|US8882889 *||Jun 22, 2011||Nov 11, 2014||Advanced Technology Materials, Inc.||Recovery of Xe and other high value compounds|
|US9062829||Aug 13, 2013||Jun 23, 2015||Entegris, Inc.||Rectangular parallelepiped fluid storage and dispensing vessel|
|US9097611||Jun 7, 2011||Aug 4, 2015||Entegris, Inc.||Fluid storage and dispensing system including dynamic fluid monitoring of fluid storage and dispensing vessel|
|US9126139||May 29, 2013||Sep 8, 2015||Entegris, Inc.||Carbon adsorbent for hydrogen sulfide removal from gases containing same, and regeneration of adsorbent|
|US9132412||Sep 24, 2013||Sep 15, 2015||Entegris, Inc.||Component for solar adsorption refrigeration system and method of making such component|
|US9170246||Oct 15, 2013||Oct 27, 2015||Entegris, Inc.|
|US9186650||Apr 5, 2013||Nov 17, 2015||Entegris, Inc.||Adsorbent having utility for CO2 capture from gas mixtures|
|US9234628||Mar 25, 2014||Jan 12, 2016||Entegris, Inc.||PVDF pyrolyzate adsorbent and gas storage and dispensing system utilizing same|
|US9283512||Aug 24, 2015||Mar 15, 2016||Entegris, Inc.||Adsorbent having utility for CO2 capture from gas mixtures|
|US9314719||Aug 13, 2012||Apr 19, 2016||Mcalister Technologies, Llc||Filter having spiral-shaped distributor channels|
|US9327226||Dec 31, 2013||May 3, 2016||Mcalister Technologies, Llc||Dynamic filtration system and associated methods|
|US20050188846 *||Apr 11, 2005||Sep 1, 2005||Carruthers J. D.||Gas storage and dispensing system with monolithic carbon adsorbent|
|US20060011064 *||Sep 6, 2005||Jan 19, 2006||Carruthers J D||Gas storage and dispensing system with monolithic carbon adsorbent|
|US20060054018 *||Sep 15, 2005||Mar 16, 2006||Dennis Brestovansky||Rectangular parallelepiped fluid storage and dispensing vessel|
|US20080185067 *||May 26, 2007||Aug 7, 2008||Lim Walter K||Pressurized containers and methods for filling them|
|US20080245676 *||Aug 22, 2006||Oct 9, 2008||Mcmanus James V||Material Containment System|
|US20080280380 *||Oct 24, 2005||Nov 13, 2008||Advanced Technology Materials, Inc.||Fluid Storage and Dispensing System Including Dynamic Fluid Monitoring of Fluid Storage and Dispensing Vessel|
|US20080302246 *||Jul 30, 2008||Dec 11, 2008||Advanced Technology Materials, Inc.||Nanoporous articles and methods of making same|
|US20090173225 *||Mar 10, 2009||Jul 9, 2009||Advanced Technology Materials, Inc.||Rectangular parallelepiped fluid storage and dispensing vessel|
|US20090182180 *||Jan 12, 2009||Jul 16, 2009||Shih-Wen Huang||Low pressure acetylene storage|
|US20100000064 *||Jan 7, 2010||Michael Ernest Garrett||Method for manufacturing a product dispensing canister|
|US20100213083 *||May 3, 2006||Aug 26, 2010||Advanced Technology Materials, Inc.||Fluid Storage and Dispensing Systems, and Fluid Supply Processes Comprising Same|
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|US20110048063 *||Jun 22, 2008||Mar 3, 2011||Advanced Technology Materials, Inc.||Component for solar adsorption refrigeration system and method of making such component|
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|US20110232367 *||Sep 29, 2011||Advanced Technology Materials, Inc.|
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|U.S. Classification||96/108, 55/DIG.5, 502/417, 502/426, 96/154, 96/134|
|International Classification||F17C11/00, B01D53/04, B01J20/20|
|Cooperative Classification||Y10T428/30, Y10S95/901, Y10S55/05, B01D2257/553, B01J20/20, B01D2259/4525, F17C2270/0518, B01D53/02, B01D53/0407, F17C11/00, B01J20/28042, B01D2253/342, B01D2253/308, B01D2253/102, B01D53/0415, B01D2253/304, B01D2259/40003, B01D2259/455, B01D2256/26, Y02C20/10, Y02C10/08, Y02E60/321|
|European Classification||B01J20/28D28, B01D53/04C2, B01J20/20, F17C11/00, B01D53/04C|
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Year of fee payment: 4
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